JPH11170468A - Moisture permeable waterproof laminated woven fabric and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a fiber permeable waterproof laminated woven fabric of superior wearing comfortability provided with high waterproof performance and fiber permeable performance combinedly. SOLUTION: A porous resin layer formed of a synthetic polymer composed mainly of polyurethane resin is disposed on a fiber cloth, and the resin layer is provided with hollow sections of honeycomb skin core structure and very fine hollow sections in its sectional direction, and the long diameter of the hollow section of honeycomb skin core structure is 1-40 μm and its area ratio is 50-70% and the number of hollows is (2-10)×10<3> pcs/mm<2> , while the long diameter of fine hollow section is 1 or less and its area ratio is 1-20%, and the number of hollowsis (1-30)×10<5> pcs./mm<2> . If necessary, substantially solid synthetic polymer layer composed mainly of polyurethane resin is disposed on the resin layer, and a polyamide fiber towel is disposed on the resin layer or the synthetic polymer layer through bonding agent layers of polyurethane resin and polyamide resin formed partially on the whole surface of the layer. Waterproofness is provided even in the rain or under the water, and also wearing comfortability of little stuffy feeling at the time of taking physical exercise is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art A moisture-permeable waterproof fabric having both moisture permeability and waterproofness has a function of releasing water vapor due to sweat from the body to clothes and a function of preventing rain from entering the clothes. In order to provide these functions, high-density woven fabric with high-density yarns, polyurethane resin, polyamino acid resin, polyester resin, polyamide resin,
A material in which a polytetrafluoroethylene resin or the like is coated on a fabric or laminated in the form of a film is well known. These are used for sports clothing and winter clothing, among which sports clothing and outdoor clothing, which have a relatively large amount of sweat due to exercise, are indispensable in fields such as skiing, athletic, and mountain climbing. Material.

[0003] Among such conventional moisture-permeable and waterproof fabrics,
The high-density woven fabric type has sufficient moisture permeability,
The waterproof performance is at most about 0.1 kgf / cm ² , while among the types with a resin layer, those with a perforated resin layer are generally easy to obtain excellent moisture permeability, but the waterproof performance is 0.2. ~ 0.3
kgf / cm ² approximately only be obtained, while those resin layer is nonporous has excellent easily obtained waterproof performance, or moisture permeability is little, at most 4000g / m ² · 24hrs
Only a degree is obtained.

In order to compensate for such a drawback, a perforated highly moisture-permeable resin layer is first formed on a fiber cloth, and a non-porous resin layer is formed on the perforated resin layer to provide excellent moisture permeability and waterproofness. Attempts have been made to obtain a high performance. In this method, although excellent waterproof performance can be obtained, moisture permeability is at most 3000 to 5000.
g / m ² · 24 hrs.

Accordingly, the present inventors have disclosed in Japanese Patent Laid-Open No. 6-280.
No. 163, the average particle size is 1 μm or less, and the amount of adsorbed N, N-dimethylformamide is 200 ml / 1
A method of processing a coated fabric for forming a polyurethane resin film containing at least 1% by weight of inorganic fine powder of not less than 00g is proposed, which has a moisture permeability of 7000g / m ² · 24hrs or more and a water pressure resistance of 0.6kgf / cm ² or more. We succeeded in obtaining a wet waterproof fabric.

[0006] However, in order to smoothly release sweat caused by exercise to the outside of the clothes, it is preferable that the moisture permeability is large.
On the other hand, in order to wear underwater or heavy rain, it is preferable that the waterproof property is high. Therefore, a moisture-permeable waterproof cloth with higher performance is desired.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and achieves both high waterproof performance and high moisture permeability, thereby providing high-performance moisture-permeable waterproof with excellent wearing comfort. The purpose is to obtain a fabric.

[0008]

The present invention attains the above object and has the following constitution. That is, the present invention provides a porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin on a fiber cloth, and an adhesive layer made of a polyurethane-based resin and a polyamide-based resin provided on the resin layer via a non-overlapping surface. And "a moisture-permeable and waterproof laminated fabric characterized by having a polyamide-based fiber fabric", and "a porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin on the fiber fabric. A hollow portion and a fine hollow portion of the honeycomb skin core structure exist in the cross-sectional direction, the major axis of the hollow portion of the honeycomb skin core structure is 1 to 40 μm, the area ratio is 50 to 70%, and the number is (2 to 10) × 10. ³ pieces / mm
² , the major axis of the fine cavity is 1 μm or less, the area ratio is 1 to 20%, and the number is (1 to 30) × 10 ⁵
Pieces / mm ² , having a polyamide-based fiber cloth on the above-mentioned perforated resin layer via an adhesive layer made of a polyurethane-based resin and a polyamide-based resin on the entire non-surface, and having a 0.6-2.5 kgf
/ Cm ² water resistance and 8000 to 12000 g / m ² · 2
"A moisture-permeable and waterproof laminated fabric characterized by having a moisture permeability of 4 hrs""Consisting of a perforated resin layer composed of a polyurethane resin-based synthetic polymer on a fiber fabric and a polyurethane resin-based synthetic polymer" A moisture-permeable and water-proof property characterized by having a non-porous resin layer, and having a polyamide fiber cloth over an adhesive layer made of a polyurethane-based resin and a polyamide-based resin over the entire surface of the resin layer. Laminated fabric ",
A honeycomb skin core having a perforated resin layer composed of a polyurethane resin-based synthetic polymer and a non-porous resin layer composed of a polyurethane resin-based synthetic polymer on a fiber cloth in a cross-sectional direction of the perforated resin layer. There is a cavity and a fine cavity of the structure, and the major axis of the cavity of the honeycomb skin core structure is 1 to 40.
μm, the area ratio is 50 to 70%, and the number is (2 to 1
0) × 10 ³ pieces / mm ² , the major axis of the fine cavity is 1 μm or less, the area ratio is 1 to 20%, and the number is (1).
30) × 10 ⁵ / mm ² , comprising a polyamide fiber cloth on the non-porous resin layer with an adhesive layer composed of a polyurethane resin and a polyamide resin interposed over the entire non-porous layer. and water pressure of ~2.5kgf / cm ^2, 8000~12
Moisture-permeable waterproof laminated fabric having a moisture permeability of 000 g / m ² · 24 hrs ”,“ Adsorption amount of N, N-dimethylformamide having an average particle size of 1 μm or less on fiber fabric and Is a synthetic resin mainly composed of a polyurethane resin containing 1% by weight or more of inorganic fine powder of 200 ml / 100 g or more, and a mixed resin solution of a synthetic polymer mainly composed of a polyurethane resin having a different coagulation value from the synthetic polymer mainly composed of the polyurethane resin. A wet-formed film, and then apply an adhesive solution comprising a polyurethane-based resin and a polyamide-based resin over the entire surface, and bond a polyamide-based fiber cloth to the adhesive solution to produce a moisture-permeable waterproof laminated fabric. Method "," Inorganic fine particles having an average particle size of 1 μm or less and a N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more on the fiber cloth. A polyurethane resin-based synthetic polymer containing 1% by weight or more of powder and a mixed resin solution of the polyurethane resin-based synthetic polymer and a polyurethane resin-based synthetic polymer having a different coagulation value are applied and wet-formed. A substantially non-porous resin solution composed of a polyurethane resin-based synthetic polymer is applied thereon to form a dry film, and then an adhesive solution composed of a polyurethane-based resin and a polyamide-based resin is applied over the entire surface. "A method for producing a moisture-permeable and waterproof laminated fabric characterized by being laminated with a polyamide-based fiber fabric".

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The fiber cloth used in the present invention includes polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, and polyacrylonitrile synthetic fibers.
Fabrics and knits made of semi-synthetic fibers such as polyvinyl alcohol synthetic fibers and triacetate, or mixed fibers of nylon 6 / cotton, polyethylene terephthalate / cotton, etc.
Nonwoven fabrics and the like can be mentioned.

In the present invention, the above-mentioned fiber cloth which has been subjected to a water repellent treatment may be used. This is one means for preventing the penetration of the resin solution into the inside of the fabric during the production of the moisture-permeable waterproof fabric. 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, for example, Asahi Guard 730
(Asahi Glass Co., Ltd., fluorinated water repellent emulsion) padded with 5% aqueous dispersion (35% squeezing rate)
The heat treatment may be performed at 160 ° C. for one minute.

The synthetic polymer mainly composed of a polyurethane resin referred to in the present invention is a polymer containing 50 to 100% by weight of a polyurethane component. Examples of other synthetic polymers include polyacrylic acid, polyvinyl chloride, polystyrene, and polybutadiene. , Polyamino acids and their copolymers
It may be contained in a range of less than% by weight, and of course, a compound 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.
As the isocyanate component, an aromatic diisocyanate, an aliphatic diisocyanate and an alicyclic diisocyanate alone or a mixture thereof are used.
-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, tri- or higher functional polyisocyanate 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, propylene glycol, or the like is used. Reaction products of diols with dibasic acids such as adipic acid and sebacic acid and ring-opening polymers such as caprolactone are used.

In the present invention, a coating resin layer is formed by using the above resin. At this time, a hollow portion and a fine hollow portion having a honeycomb skin core structure are present in a cross-sectional direction of the resin layer.
The long diameter of the hollow part of the honeycomb skin core structure is 1 to 40μ
m, the area ratio is 50 to 70%, and the number is (2 to 10)
× 10 ³ pieces / mm ² , and the long diameter of the fine cavity is 1μ
m, the area ratio is 1 to 20%, and the number is (1 to 3
0) a perforated resin layer of × 10 ⁵ / mm ²
And a water pressure resistance of 0.6 to 2.5 kgf / cm ² and 8000 to 12
000 g / m ² · 24 hrs, in order to exhibit the excellent performance of moisture permeability, the average particle size is 1 μm or less, and N,
Synthesis of a polyurethane resin-based synthetic polymer containing 1% by weight or more of an inorganic fine powder having an adsorption amount of N-dimethylformamide of 200 ml / 100 g or more, and synthesis of a polyurethane resin-based synthetic polymer different from the polyurethane resin-based synthetic polymer in coagulation value The solution of the polymer is mixed, applied to the fiber cloth, and subjected to wet film formation.

The inorganic fine powder used in the present invention includes:
Inorganic fine powder pulverized by ordinary wet pulverization method or ball mill pulverization method, and metal oxide fine powder obtained by dry method such as vapor phase oxidation method of metal halide, electric arc method, combustion hydrolysis method Among them, fine powder of silicon dioxide produced by these methods can be mentioned as a representative. The fine powder obtained by these methods generally has a particle size of 0.05 μm or less, has a very large amount of adsorbed N, N-dimethylformamide, and can be added to a synthetic polymer resin solution. It is suitable as a fine powder. Further, the use of a fine powder whose surface is modified to be hydrophobic is more preferable from the viewpoint of water leakage, and the fine powder is preferably substantially non-porous.

The amount of N, N-dimethylformamide adsorbed here means that 5 g of inorganic fine powder is placed on a glass plate,
Each time one drop of N, N-dimethylformamide was added, the kneading operation using a stainless steel spatula was repeated, and the N, N-dimethyl needed immediately before the mixture was rapidly softened with one drop of N, N-dimethylformamide. It means the volume of formamide (unit: milliliter)
SK-5101 is obtained by using N, N-dimethylformamide instead of oil in the boiled linseed.

The inorganic fine powder used in the present invention must be used in an amount of 1% by weight or more, preferably 3% by weight or more, based on the above-mentioned synthetic polymer mainly composed of a polyurethane resin. If the amount is less than 1% by weight, the number of pores in the fine hollow portion of the obtained coated fabric is reduced, and high moisture permeability cannot be obtained.

The inorganic fine powder need not necessarily be of high purity, and may contain other inorganic substances such as pigments and fillers as impurities.

In the present invention, at least two different coagulation values are used.
Coagulation value is a coagulation liquid in 100 g of a resin solution obtained by diluting the synthetic polymer mainly composed of the polyurethane resin 4 times with a solvent (N, N-dimethylformamide). It means the volume of water required just before the start of gelation by adding water while stirring little by little. By mixing and using resins with different coagulation values, the number of pores in the microcavities can be reduced. Although the moisture permeability increases, the moisture permeability improves, but care must be taken because if the solidification value is too small, the water pressure will decrease as the moisture permeability improves. The difference in coagulation value should be within 1.5 (high coagulation value / low coagulation value).

When a mixed solution of the above-mentioned synthetic polymer mainly composed of a polyurethane resin containing the inorganic fine powder and the synthetic polymer mainly composed of a polyurethane resin having a different coagulation value is applied to the fiber cloth, a usual coating method such as a knife is used. The coating may be performed appropriately using a coater, comma coater, reverse coater, or the like. The coating amount is 0.6 g / water pressure.
To obtain m ² or more, the resin dry film weight of 10 g /
m ² or more, preferably may be performed by adjusting the coating amount to be 15 g / m ² or more.

In the present invention, in order to improve the peeling resistance between the resin layer and the fiber cloth, it is desirable to use a compound having a high affinity for the resin and the fiber cloth in combination, and as the compound, an isocyanate compound is preferably used. it can.

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 in a form in which an isocyanate group is liberated, or in 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 properly used depending on workability, application, and the like.

The isocyanate compound is preferably used in an amount of 0.1 to 10% by weight based on the mixed solution of the above-mentioned polyurethane resin-based synthetic polymer. 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.

In the present invention, the coated fabric may be subjected to a water-repellent treatment after the wet coating in order to further improve the waterproofness. For the water-repellent treatment, a well-known water-repellent treatment that is generally performed as described above may be employed.

In the film-formed resin film of the wet-coated fabric thus obtained, a hollow portion having a honeycomb skin core structure and a fine hollow portion exist in a cross-sectional direction of the resin layer, and a hollow portion having a honeycomb skin core structure exists. The major axis is 1 to 40
μm, the area ratio is 50 to 70%, and the number is (2 to 1
0) × 10 ³ pieces / mm ² , the major axis of the fine cavity is 1 μm or less, the area ratio is 1 to 20%, and the number is (1).
30) × 10 ⁵ / mm ² It has a perforated resin layer.

In the present invention, the area ratio and the number of the cavity are
First, a sample of 1 m ^{2 was} prepared, sampled randomly at three points in each of the vertical and horizontal directions, frozen and cut in each direction, and then Au / Pd.
Evaporation was performed, and then a 1000 × and 10000 × cross-sectional photograph was taken using a scanning electron microscope. The former was measured for the honeycomb core structure, and the latter was measured for the number and area ratio of microcavities having a major axis of 1 μm or less. And expressed as an average value at six locations.

In the present invention, a substantially non-porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin is provided on the resin layer of the wet-coated fabric obtained as described above, if necessary. It is possible to obtain a moisture-permeable and waterproof coated fabric with further improved waterproofness.

The synthetic polymer mainly composed of polyurethane resin is
It is obtained by the same method as the resin containing 50 to 100% by weight of the above-mentioned polyurethane, and is subjected to dry coating using the above-mentioned coating apparatus. By performing the dry coating, a substantially non-porous resin layer can be formed.

Regarding the coating amount, the water pressure resistance is 2.5 to 8 kgf /
In order to obtain cm ² , the coating amount is adjusted so that the dry resin film weight becomes 2 g / m ² or more, preferably 3 g / m ² or more.

Of course, the above-mentioned isocyanate compound can be used in combination with the resin, and the amount of the isocyanate compound used is preferably within the above-mentioned range.

In the present invention, an adhesive made of a polyurethane-based resin and a polyamide-based resin is uniformly applied on the non-porous resin layer, and when the non-porous resin layer is formed, on the non-porous resin layer. Apply to.

The polyurethane resin used for the adhesive is as follows.
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-mentioned isocyanate compound. In the present invention, a low-molecular polyol having a molecular weight of 1,000 or less, for example, ethylene glycol , Diethylene glycol, 1,4
A method of directly combining a polyol component such as butanediol and 1,6-hexanediol with an isocyanate compound, or a method of combining a polyol component or an isocyanate compound with a polymer polyol such as the aforementioned polyether diol, polyester diol, or polycaprolactone diol, and tolylene 2,4. A copolymer obtained by a method of combining with a urethane prepolymer modified with isocyanate groups at both ends or a hydroxyl group at both ends by reacting with an isocyanate compound such as diisocyanate or 4,4′-diphenylmethane diisocyanate, the tag property of the resin, It is preferably used because it has excellent adhesion to the polyamide fiber cloth described later, and when the terminal group of the obtained resin is a hydroxyl group, the resin may be used in combination with the above-mentioned isocyanate compound. The aforementioned range is preferred, the adhesive force and the durability is improved by using both.

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 terminals 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.

The polyamide resin used for the adhesive is a resin having an amide bond in the main chain, and is a known polymerization method, for example, a dibasic acid such as adipic acid or sebacic acid and a diamine such as hexamethylenediamine or isophoronediamine. With ring-opening polymerization of lactams such as ε-caprolactam and ω-laurolactam, and 11-aminoundecanoic acid and 12
Nylon 6, nylon 66, nylon 610, obtained by polycondensation of aminocarboxylic acids such as aminododecanoic acid, etc.
Nylon 6/66, Nylon 6/66/11, Nylon 6/66/11/12 made of a homopolymer such as Nylon 11, Nylon 12, or a combination of the above nylons
Of course, the above-mentioned amide-based polymer and other polymers, for example, a polymer blend of polyester or polyolefin or an amide-modified polyester resin are also included in this.

In the present invention, the above polyamide resin is
In particular, a hot-melt adhesive having a melting point in the range of 60 to 150 ° C. is preferably used, and specifically, commercially available Grilltec 1P2 (manufactured by Emser Werke), Platamide H103 and H104 (Elf Atochem)・ Japan Co., Ltd.), Alamine 842P48
And GOLP48 (manufactured by Toray Industries, Inc.).

In the present invention, an adhesive comprising the above-mentioned polyurethane resin and polyamide resin is used. The polyamide resin is used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on the polyurethane resin. It is desirable to use it. If the amount used is less than 1% by weight, the adhesion to the fabric does not improve much, and the amount used is 15% by weight.
If the value exceeds, it is not preferable because no further improvement in the adhesive strength is observed and the tendency of the hand to harden is recognized.

In the present invention, the adhesive layer made of the above-mentioned polyurethane resin and polyamide resin is uniformly applied to the entire non-surface, and laminated with the polyamide fiber cloth.

The polyamide fiber fabric used here is mainly composed of polyamide synthetic fibers represented by nylon 6 and nylon 66, as described above. However, polyester synthetic fibers, polyacrylonitrile synthetic fibers, A cloth made of semi-synthetic fiber such as polyvinyl alcohol-based synthetic fiber and triacetate, or a mixed fiber containing cotton and the like may be used. Examples of the form of the cloth include a woven fabric, a knitted fabric, and a nonwoven fabric.

When the above-mentioned adhesive is of a solvent type or an aqueous type,
Using a well-known gravure coater, rotary screen, flat screen, etc., or using a hot melt type applicator, etc., use the applicator, etc., to form a desired shape such as a dot, line, checkerboard, or turtle pattern on the entire surface. When laminating, a known method such as ordinary pressure bonding or thermocompression bonding may be employed.

The term "non-entire surface" as used herein means that the adhesive occupied area ratio is 20 to 60%, preferably 30 to 50%, and if the occupied area ratio is less than 20%, the resistance between the adhesive layer and the laminating fabric is low. The peeling performance is poor, and if it is 60% or more, the moisture permeability deteriorates, which is not preferable.

[0044]

The average particle size is 1 μm or less and the amount of N, N-dimethylformamide adsorbed is 200 ml / 100 g.
A polyurethane resin-based synthetic polymer in which the above inorganic fine powder is uniformly dispersed and a polyurethane resin-based synthetic polymer having a different coagulation value are uniformly dispersed, coated on a fabric, and subjected to wet coagulation. Certain water is mixed with N, N-dimethylformamide as a resin solvent, and the solvent is quickly separated from the resin liquid to start coagulation of the resin. At this time, the average particle diameter is 1 μm or less, and N, N
-When inorganic fine powder having an adsorption amount of dimethylformamide of 200 ml / 100 g or more is uniformly dispersed,
The surface of the inorganic fine powder has a higher concentration of N, N-dimethylformamide in the resin solution than other parts, in other words, N, N- of a synthetic polymer mainly composed of a polyurethane resin.
Since the concentration of dimethylformamide is low, in the wet coagulation process, water, which is the coagulating liquid, is first replaced by N, N-dimethylformamide on the surface of the inorganic fine powder, and coagulation starts rapidly around the inorganic fine powder. After that, the solidification of the resin with a low solidification value starts, and finally the solidification of the resin with a high solidification value starts, so that the number of cavities in the honeycomb skin core structure peculiar to urethane resin increases, and countless 1 μm or less. Since the micropores are formed around the inorganic fine powder, they have a very porous form, and because of the solidified form as described above, they have sufficient moisture permeability and high waterproofness. It is presumed.

By adopting a method of coating a thin, non-porous, moisture-permeable urethane resin on a resin having such a solidified form, a moisture-permeable, waterproof-coated fabric that maintains good moisture permeability while further improving waterproofness Can be obtained.

Further, a polyamide-based resin having a high affinity with the resin layer of the coated fabric having the above-mentioned excellent moisture permeability and waterproofness as a main component, and having a high affinity with the polyamide-based fiber fabric. By using an adhesive containing a mixture of the above, the adhesive force between the resin layer and the polyamide-based fiber fabric for lamination is improved, and the effect of the hydrogen bond caused by the amide bond contained in the polyamide resin is also contributed. Strong adhesion can be obtained.

Since the adhesive layer is applied to the entire surface, excellent moisture permeability is maintained, and since the polyamide fiber cloth is present on the adhesive layer, the wearing comfort is excellent. Thus, a moisture-permeable and waterproof laminated fabric is obtained.

[0048]

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) Peel strength Peel strength in the longitudinal direction according to JIS L-1089 method Measure.

Example 1 Nylon multifilament 110 was used for both the warp and the weft.
Using a denier / 24 filament, weaving a ripstop taffeta with a warp density of 76 yarns / inch and a weft density of 76 yarns / inch, scouring and dyeing according to the usual method (Kayaanol Navy Blue R 3%, manufactured by Nippon Kayaku Co., Ltd.) owf), followed by padding (aperture ratio: 40%) with a 6% aqueous dispersion of Asahigard LS-317 (manufactured by Asahi Glass Co., Ltd., emulsion type fluorine water repellent), drying, and drying.
Heat treatment was performed at 1 ° C. for 1 minute. Next, using a calendering machine with a mirror roll, the temperature was 170 ° C and the pressure was 30 kg.
Calendering was performed under the conditions of f / cm ² and a speed of 20 m / min to obtain a base fabric for coating.

A 28 gauge tricot fabric was knitted using nylon filament 20 denier / 7 filaments, and scoured by a usual method to obtain a fabric for lamination.

Further, a fluorine-modified polyurethane resin (hereinafter referred to as F-PU resin) was produced by the following method.

Polytetramethylene glycol (OH value: 5
6.9) 1970 g and 504 g of 1,6-hexamethylene diisocyanate are reacted at 90 ° C. for 5 hours to produce 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 dimethylamine having a concentration of 2% is stirred while stirring. 47 g of the solution was added, and the reaction was carried out at 30 ° C. for 5 hours. The viscosity was 39000 mPa · s (25 ° C.) and the coagulation value was 7.5.
cc of a light yellow-brown F-PU resin having good flowability was obtained.

Next, rack skin 1740-29B (ester type polyurethane resin manufactured by Seiko Chemical Co., Ltd.)
100 parts 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-dimethyl After uniformly dispersing 50 parts of formamide with a three-roll machine, 900 parts of the above-mentioned rack skin 1740-29B and 200 parts of N, N-dimethylformamide were uniformly mixed, and the viscosity was set at 19000 mPa · s (25 ° C.). Price 9.
A polyurethane resin containing 8 cc of inorganic fine powder (hereinafter referred to as S-PU resin) was obtained.

Here, as a first step, a polyurethane resin solution having a composition shown in the following formulation 1 and having a solid content of 25% was applied to the calender surface of the above-mentioned base cloth by a knife over roll coater as a first step. 80 g / m ²
Immediately after coating, the resin was wet-coagulated by dipping in water at 15 ° C for 40 seconds, and then dried in warm water at 50 ° C for 1 second.
Washing was performed for 0 minutes, followed by drying to form a resin layer.

Formulation 1 S-PU resin 80 parts F-PU resin 20 parts Resamine X-100 1 part (Isocyanate compound manufactured by Dainichi Seika Kogyo Co., Ltd.) Using a gravure roll of 25 mesh, 250 μm depth, 40% adhesive occupied area ratio, circular dot shape (dot width 0.7 mm, dot-dot interval 0.35 mm), with the composition shown in Formula 2 below An adhesive composed of a polyurethane resin and a polyamide resin for 40% by
After drying at 0 ° C. for 2 minutes, the above-mentioned tricot for lamination was pressed at a pressure of 3 kgf / cm ² , and then aged at 50 ° C. for 3 days to obtain a moisture-permeable waterproof laminated fabric of the present invention.

Formulation 2 100 parts of UD-108 (ester urethane resin, manufactured by Seiko Chemical Co., Ltd.) 5 parts of Platamide H-103 (5 parts, manufactured by Elf Atochem Japan K.K., particle size: 80 μm)
m and a melting point of about 90 ° C, polyamide hot melt adhesive) Coronate-HL 10 parts (Nippon Polyurethane Industry Co., Ltd., isocyanate compound) UY-5 1 part (Seiko Chemical Co., Ltd., organotin-based accelerator) N, N-dimethylformamide 10 parts Methyl ethyl ketone 20 parts For comparison with the present invention, F-
A comparative moisture-permeable and waterproof laminated fabric (Comparative Example 1) was obtained in exactly the same manner as in this example except that the PU resin was replaced with 100 parts of S-PU resin.

For comparison with the present invention, except that the S-PU resin was omitted in Formulation 1 of this example, and instead, 80 parts of rack skin 1740-29B and 25 parts of N, N-dimethylformamide were added. , A moisture-permeable waterproof laminated fabric for comparison (Comparative Example 2)
And ) Got.

Further, for comparison with the present invention, the S-PU resin and the F-PU resin were omitted in the prescription 1 of the present example, and instead, a rack skin 1740-29B was added for 10 minutes.
A moisture-permeable and waterproof laminated fabric for comparison (Comparative Example 3) was obtained in exactly the same manner as in this example except that 0 part and 25 parts of N, N-dimethylformamide were added.

For comparison with the present invention, the F-PU resin was omitted in Formulation 1 of this example, and instead, a rack skin 1740-29A (manufactured by Seiko Chemical Co., Ltd., polyamino acid urethane copolymer resin, coagulation value) was used. 5.8 cc) A comparative moisture-permeable waterproof laminated fabric (Comparative Example 4) was obtained in exactly the same manner as in this example except that 20 parts were added.

Further, for comparison with the present invention, a moisture-permeable waterproof laminated fabric for comparison (Comparative Example 2) was prepared in exactly the same manner as in this example except that platamide H-103 was omitted in Formulation 2 of this example. Example 5) was obtained.

The performances of the present invention and the comparative laminated fabric were measured, and the results are shown in Table 1.

[0063]

[Table 1]

As is apparent from Table 1, the moisture-permeable and waterproof laminated fabric of the present invention has a large area ratio between the hollow portion and the fine hollow portion of the honeycomb skin core structure, the number of hollow portions, and the water pressure resistance and the moisture permeability are high. It can be seen that the use of a polyurethane-based resin mixed with a polyamide-based hot-melt type adhesive as the adhesive has high peeling resistance between the coating resin layer and the fabric for lamination.

Examples 2 to 4 A rack skin 14 having a solid content of 30% was applied to the coated surface of the coated fabric obtained in the first step in Example 1.
4 (polyurethane resin manufactured by Seiko Chemical Co., Ltd.) using a knife over roll coater to apply 1
0 g, 17 g, and 33 g, and then immediately dried at 100 ° C. for 2 minutes to form 3 g, 5 g, and 10 g of the moisture-permeable waterproof coating fabric, respectively. Lamination was performed in exactly the same manner as in the second step in Example 1 to obtain a moisture-permeable and waterproof laminated fabric of the present invention (referred to as Examples 2, 3, and 4, respectively).

For comparison with the present invention, in each of Examples 2 to 4, except that platamide H-103 was omitted from Formulation 2,
By the exactly same method as in Examples 2 to 4, a moisture-permeable and waterproof laminated fabric for comparison (Comparative Examples 6, 7, and 8 respectively) was obtained.

The performances of the present invention and the comparative laminated fabric were measured, and the results are shown in Table 2.

[0068]

[Table 2]

As is clear from Table 2, the moisture-permeable and waterproof laminated fabric of the present invention has a high balance between the water pressure resistance and the moisture permeability, and has good peeling resistance.

[0070]

According to the present invention, it is possible to produce a moisture-permeable and waterproof laminated fabric having high moisture permeability while having high waterproofness. This fabric is a moisture-permeable and waterproof laminated fabric having little unpleasant sensation, high adhesive strength between the coating resin layer and the lining, and unprecedented wearing comfort.

Claims (6)

[Claims] 1. A fibrous fabric having a perforated resin layer made of a synthetic polymer mainly composed of a polyurethane resin, and an adhesive layer made of a polyurethane-based resin and a polyamide-based resin interposed over the entire surface of the nonwoven fabric. A moisture-permeable and waterproof laminated fabric comprising a polyamide fiber fabric. 2. A honeycomb structure comprising a porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin on a fiber cloth, and a hollow portion having a honeycomb skin core structure and a fine hollow portion existing in a cross-sectional direction of the resin layer. The major axis of the cavity of the skin core structure is 1 to
40 μm, the area ratio is 50 to 70%, and the number is (2
-10) × 10 ³ / mm ² , the major axis of the fine cavity is 1 μm or less, the area ratio is 1-20%, and the number is (1-30) × 10 ⁵ / mm ² , A polyamide-based fiber fabric is provided on the perforated resin layer with an adhesive layer made of a polyurethane-based resin and a polyamide-based resin interposed on the entire non-surface, and has a water pressure of 0.6 to 2.5 kgf / cm ^{2 and} a water resistance of 8000. ~ 1
A moisture-permeable waterproof laminated fabric having a moisture permeability of 2000 g / m ² · 24 hrs. 3. A fibrous cloth comprising a perforated resin layer made of a synthetic polymer mainly composed of a polyurethane resin and a non-porous resin layer composed of a synthetic polymer mainly composed of a polyurethane resin, wherein a polyurethane resin is formed on the resin layer. A moisture-permeable and waterproof laminated fabric comprising a polyamide-based fiber fabric and an adhesive layer made of a polyamide-based resin on the entire non-surface. 4. A cross-sectional direction of a perforated resin layer having a perforated resin layer composed of a polyurethane resin-based synthetic polymer and a non-porous resin layer composed of a polyurethane resin-based synthetic polymer on a fiber cloth. There is a hollow portion having a honeycomb skin core structure and a fine hollow portion, the major axis of the hollow portion having a honeycomb skin core structure is 1 to 40 μm, the area ratio is 50 to 70%, and the number is (2 to 10) × 10 ^3. Pieces / mm ² , and the major axis of the fine cavity is 1 μm or less, the area ratio is 1 to 20%,
The number is (1 to 30) × 10 ⁵ / mm ² , and a polyamide-based fiber cloth is provided on the non-porous resin layer with an adhesive layer made of a polyurethane-based resin and a polyamide-based resin interposed over the entire non-porous layer. , 0.6-2.5 kgf / cm ² water pressure and 800
Breathable waterproof laminated fabric, characterized in that it has a moisture permeability of 0~12000g / m ² · 24hrs. 5. The method according to claim 5, wherein the average particle size on the fiber cloth is 1 μm or less,
A polyurethane resin-based synthetic polymer containing 1% by weight or more of an inorganic fine powder having an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more; and a polyurethane having a coagulation value different from that of the polyurethane resin-based synthetic polymer. After applying a mixed resin solution of a resin-based synthetic polymer and performing wet film formation, an adhesive solution composed of a polyurethane-based resin and a polyamide-based resin is applied over the entire non-surface, and a polyamide-based fiber cloth is bonded thereto. A method for producing a moisture-permeable and waterproof laminated fabric. 6. The method according to claim 6, wherein the average particle size on the fiber cloth is 1 μm or less,
A polyurethane resin-based synthetic polymer containing 1% by weight or more of an inorganic fine powder having an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more; and a polyurethane having a coagulation value different from that of the polyurethane resin-based synthetic polymer. After applying a mixed resin solution of a resin-based synthetic polymer and performing wet film formation, a resin solution composed of a polyurethane resin-based synthetic polymer is applied thereon to form a dry film formation, and then a polyurethane-based resin and a polyamide-based film are formed. A method for producing a moisture-permeable and waterproof laminated fabric, characterized in that an adhesive solution made of a resin is applied to a non-entire surface and bonded to a polyamide fiber fabric.