JPH0754277A - Production of moisture-permeable water-proofing coated cloth - Google Patents

Abstract

PURPOSE:To obtain a coated cloth having excellent moisture-permeability and water-proofness by coating a fiber cloth with a polar organic solvent solution of a urethane resin containing fine powder of wool and/or silk and inorganic fine powder. CONSTITUTION:This moisture-permeable water-proofing coated cloth having a moisture-permeability of >=7,000g/m<2>.24hr, a water-penetration pressure of >=0.5kgf/cm<2> and dry-touch feeling is produced by coating a fiber cloth such as synthetic fiber or semi-synthetic fiber cloth with a polar organic solvent solution (e.g. dimethylformamide solution) of mainly a polyurethane containing fine powder of wool and/or silk obtained by enzymatic treatment and having an average particle diameter of <=20mum and inorganic fine powder (especially silicon dioxide powder) having an averagle particle diameter of <=1mum and an N,N-dimethylformamide adsorption of >=200mL/100g by a knife-coater, etc., and coagulating the coating layer by wetcoagulation method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an excellent water absorption property, a dry touch feeling even in a wet state, and 7,000 g.
The present invention relates to a method for producing a moisture-permeable and water-proof coated fabric having a moisture permeability of / m ² · 24 hrs or more and a water pressure resistance of 0.5 kgf / cm ² or more.

[0002]

2. Description of the Related Art A breathable waterproof cloth having both breathability and waterproofness has a function of releasing water vapor caused by perspiration from the body to the outside of clothes and preventing rain from entering the clothes. It is well known that a cloth is coated or laminated with a polyamino acid urethane resin, a polyurethane resin, a polytetrafluoroethylene resin or the like in order to impart a function. These are used for sports clothing, winter clothing, etc. Among them, they are often used in the field of sports clothing, where the amount of sweat associated with intense exercise is relatively large, and are indispensable materials in the fields of skiing and athletics. . As such a conventional moisture-permeable and waterproof fabric, one having a resin layer with a hole and one having a non-hole resin layer are known. Generally, when the resin layer has a hole, excellent moisture permeability is easily obtained, Yields only 0.2-0.3 kgf / cm ² at the most, while on the other hand, when the resin layer is non-porous, it is easy to obtain excellent waterproof performance, but there is almost no moisture permeability, or at most 4000 g / m ² · 2
Only about 4 hrs have been obtained.

In order to make up for such drawbacks, a highly moisture-permeable resin layer having pores is first formed on a fiber cloth, and a resin layer having no pores is thinly formed thereon to obtain excellent moisture permeability and waterproof performance. Although the method of obtaining the above has been tried, this method can also obtain excellent waterproof performance, but the moisture permeability is at most 3000-5000g.
Only about / m ² · 24hrs is obtained.

Further, the moisture-permeable waterproof cloth is often used for windbreaker applications, and when exercising while wearing a windbreaker without a lining, there is a high possibility that the coated surface or the laminate film will come into direct contact with the skin. The moisture-permeable waterproof fabric of No. 3 did not easily slip on the skin and was sticky due to perspiration, which tended to increase discomfort during wearing. As a measure against the above, mesh and the like are often used for the lining of the windbreaker, but in addition to the complicated sewing, the lining is necessary, which is also a factor of cost increase.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and there is no feeling of discomfort even when the skin and the coating surface directly contact with each other during wearing, that is, the coating surface is wet. It has a dry feel even in a wet condition, and has a water vapor transmission rate of 7,000 g / m ² · 24 h.
The purpose of the present invention is to obtain a moisture-permeable and water-resistant coated cloth having a performance of rs or more and a water pressure resistance of 0.5 kgf / cm ² or more.

[0006]

The present invention achieves the above object and has the following structure. That is, the present invention provides "wool fine powder and / or silk fine powder having an average particle size of 20 µm or less and an inorganic particle having an average particle size of 1 µm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more. A moisture-permeable waterproof coating fabric characterized in that a polar organic solvent solution of a polyurethane polymer-based synthetic polymer containing fine powder is applied onto a fiber fabric and then immersed in water to coagulate the resin component. The manufacturing method is the gist.

The present invention will be described in detail below.

In the method of the present invention, fine wool powder and / or fine silk powder having an average particle diameter of 20 μm or less and an average particle diameter of 1
A polar organic solvent (dimethylformamide etc.) solution of a synthetic polymer mainly composed of a polyurethane resin containing an inorganic fine powder having an adsorption amount of N, N-dimethylformamide of not more than μm and 200 ml / 100 g or more is used.

Here, the term "and / or" means
It means either or both of them.

The fine wool powder or fine silk powder used in the present invention is obtained by pulverizing wool fibers or silk fibers into fine particles. As a method of atomizing wool fibers and silk fibers,
For example, it can be obtained by a method in which fibroin or keratin constituting the fiber is subjected to an enzyme treatment or the like to cut the molecule, and then pulverized and made into fine particles. Wool fibers and silk fibers have a high water absorbency by nature, but even if they contain 20% by weight of wool fibers and 30% by weight of silk fibers, they do not feel moist and appear to be dry. It has the characteristics described above, and it has the above characteristics even after it is pulverized. Further, as a method of strongly imparting this feature, for example,
There is a method of reducing the enzymatic decomposition rate to a low level and then pulverizing.

The size of the fine powder of wool or silk used in the present invention is required to have an average particle size of 20 μm or less.
If the average particle size is 20 μm or more, the thickness of the coating resin film must be more than the particle size, which not only reduces the moisture permeability, but also makes it easier for fine wool or silk powder to fall off from the resin film. Therefore, the waterproof performance is likely to be deteriorated, and if the resin film is thickened to compensate for it, the moisture permeability is deteriorated, which is not preferable.

The fine wool powder and / or fine silk powder used here must be used in an amount of 5% by weight or more, preferably 10% by weight or more, based on the synthetic polymer mainly composed of the polyurethane resin described below. If the amount is less than 5% by weight, a dry and dry feel in a wet state cannot be obtained, which is not preferable.

The inorganic fine powder used in the present invention includes
Inorganic fine powder pulverized by usual wet pulverization method or ball mill pulverization method, and metal oxide fine powder obtained by dry method such as gas-phase oxidation method of metal halide, combustion hydrolysis method, electric arc method, etc. Among them, silicon dioxide fine powder 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 and at the same time has a very large amount of N, N-dimethylformamide adsorbed, and can be added to a synthetic polymer resin solution. It is suitable as an inorganic fine powder. Further, if the surface of the fine powder is modified to be hydrophobic, it is more preferable from the viewpoint of water leakage, and the fine powder is preferably substantially non-porous.

As used herein, the amount of N, N-dimethylformamide adsorbed means that 5 g of inorganic fine powder is placed on a glass plate,
Every time one drop of N, N-dimethylformamide was dropped, the work of kneading was repeated using a spatula made of stainless steel, and N, N-dimethyl required until just before one drop of N, N-dimethylformamide suddenly became soft. It means the volume of formamide (unit: milliliter).
This is the one in which N, N-dimethylformamide was used instead of the oil of SK-5101 boiled linseed.

The inorganic fine powder used in the present invention is required to have an average particle size of 1 μm or less, and N, N-
Adsorption amount of dimethylformamide is 200ml / 1
It is necessary to be more than 00g, and the average particle size is less than 0.1μm and 250ml / 1
A substance having an adsorption amount of N, N-dimethylformamide of 00 g or more is more preferable from the viewpoint of the effect of the present invention. If the average particle size exceeds 1 μm, the fine pore size of the moisture-permeable membrane of the resulting coated fabric becomes too large and the waterproof performance deteriorates.
If it is less than 0 g, the number of fine pores of the moisture permeable membrane is small, and high moisture permeability cannot be obtained, which is not preferable.

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 synthetic polymer mainly composed of the polyurethane resin described later. If it is less than 1% by weight, the number of fine pores of the moisture permeable membrane of the coated fabric obtained is small, and high moisture permeability cannot be obtained.

The fine inorganic powder does not necessarily have to be highly pure, and may contain other inorganic substances such as pigments and fillers as impurities.

The polyurethane resin-based synthetic polymer of the present invention means one containing 50 to 100% by weight of a polyurethane component, and other synthetic polymers include, for example, polyacrylic acid, polyvinyl chloride, polystyrene and polybutadiene. , Polyamino acid and the like and copolymers thereof are included in the range of less than 50% by weight, and of course, compounds modified with fluorine or silicon can be used in the present invention.

The polyurethane resin itself is a copolymer obtained by reacting a polyisocyanate and a polyol, and aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate are used alone or a mixture thereof as an isocyanate component. Tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexanediisocyanate, 1,4-cyclohexanediisocyanate, etc. are used.
As the polyol component, polyether polyol or polyester polyol is used, the polyether polyol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like, and the polyester polyol is ethylene glycol, propylene glycol or the like diol and adipic acid. , A reaction product with a dibasic acid such as sebacic acid or a ring-opening polymer such as caprolactone is used.

In the method of the present invention, a polar organic solvent solution of a polyurethane resin-based synthetic polymer containing fine wool powder and / or fine silk powder and fine inorganic powder as described above is applied onto a fiber cloth.

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

In the present invention, the above-mentioned fiber cloth treated with a water repellent may be used. This is one means for preventing the penetration of the resin solution into the fabric during manufacturing. In this case, the water repellent may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment thereof is also a commonly used padding method, spray method, or the like. The known method may be used. When particularly good water repellency is required, a fluorine-based water repellent is used. For example, Asahi Guard 730 (Asahi Glass Co., Ltd., fluorine-based water repellent emulsion) is padded (squeezed) with a 5% aqueous dispersion. The heat treatment at 160 ° C. for 1 minute, and the like.

When the above-mentioned synthetic polymer solution mainly composed of polyurethane resin is applied to the fiber cloth, it may be appropriately coated by using a usual coating method, for example, a knife coater, a comma coater, a reverse coater or the like.
In order to obtain the desired water pressure resistance of 0.5 kgf / cm ² or more, the smoothness and air permeability (JI
Depending on the SL-1096 method), it is generally preferable to adjust the coating amount so that the resin film weight is 5 g / m ² or more, preferably 10 g / m ² or more.

In the present invention, for the purpose of improving the peeling resistance between the resin layer and the fiber cloth, a compound having a high affinity with the resin or the fiber cloth may be used together, and an isocyanate compound may be used together as the compound. .

As the isocyanate compound, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or a compound containing 3 mol of these diisocyanates and active hydrogen (eg, trimethylolpropane, glycerin, etc.) Triisocyanates obtained by addition reaction with 1 mol can be used. The above isocyanates may be in a form in which the isocyanate group is free, or may be in a form in which the block is dissociated by the subsequent heat treatment, which is stabilized by adding phenol, methylethylketoxime and the like, It may be properly used depending on workability and purpose.

The amount of the isocyanate compound used is preferably 0.1 to 10% by weight based on the synthetic polymer mainly composed of the polyurethane resin.
If the amount used is less than 0.1% by weight, the adhesive strength of the resin layer to the fabric is low, and if it exceeds 10% by weight, the texture tends to harden, which is not preferable.

In the present invention, after the resin liquid composed of the synthetic resin mainly composed of the polyurethane resin as described above is applied to the fiber cloth, it is immersed in water at 0 to 30 ° C. for 0.5 to 10 minutes to wet-solidify the resin portion. I do. Below, 5 in warm water of 40-60 ℃
After washing for -15 minutes, dry in the usual way.

In the present invention, for the purpose of further improving waterproofness, the coated fabric may be subjected to a water repellent treatment after wet coating. For the water repellent treatment, the well-known water repellent treatment method that is generally carried out as described above may be adopted. Further, when it is desired to further improve the waterproof performance, a dry film thickness of 0.5 on the wet coating layer of the present invention.
A non-porous polyurethane resin layer or the like having a thickness of about 2 μm may be formed. Since the wet coating layer has high water pressure resistance, the waterproof performance is synergistically improved even with a thin film, and the moisture permeability is not significantly reduced.

[0029]

[Operation] The average particle size is 1 μm or less and the adsorption amount of N, N-dimethylformamide is 200 ml / 100.
Polyurethane resin-based synthetic polymer solution in which at least g of inorganic fine powder is uniformly dispersed is coated on a cloth and wet coagulation is performed. As a result, water as a coagulating liquid and N, N as a resin solvent are obtained.
-Dimethylformamide is mixed and the resin is solidified by the rapid release of the solvent from the resin liquid. At that time, the average particle size is 1 μm or less, and the adsorption amount of N, N-dimethylformamide is 200 ml. / 100 g or more of the inorganic fine powder is uniformly dispersed in the resin solution, the surface of the inorganic fine powder has a higher concentration of N, N-dimethylformamide in the resin solution than the other parts. , The concentration of the synthetic polymer mainly composed of polyurethane resin is low, so that in the wet coagulation process, water as the coagulating liquid first replaces N, N-dimethylformamide on the surface of the inorganic fine powder, and around the inorganic fine powder. Solidification starts quickly, and then the entire resin solidifies.
As a result, it is presumed that the solidification rate will be high, and in addition to the honeycomb structure peculiar to urethane resin, it will be a very porous morphology with countless micropores of 1 μm or less.

In the present invention, excellent waterproofness is exhibited due to the fineness of the formed fine pores, and high moisture permeation performance is exhibited due to the innumerable minute pores, which is characteristic of the high moisture-permeable waterproof fabric. However, it is also very effective for water leakage, which tends to cause problems when pressure is applied during wearing.

When forming a coating resin layer of such a moisture-permeable and waterproof coating cloth, if a fine powder of wool or silk having an average particle size of 20 μm or less is contained in the coating resin solution, wool fibers or silk fibers will be formed. Originally hydrophilic,
It has the ability to adsorb water and sweat, and also has the property of obtaining a dry feel even when adsorbing water and sweat, so it also exhibits its performance in the formed resin layer, and as a result, It is a moisture-permeable, water-proof coated fabric that does not have a sticky feel and has a dry and dry feel.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to examples. The measurement and evaluation of the performance of the coated fabrics in the examples were carried out by the following methods. (1) Water absorption performance (water absorption rate) For a coated cloth of 20 cm x 20 cm sample, after measuring the dry weight A, soak it in water for 20 minutes, and then remove the water droplets adhering to the surface of the sample taken out. The weight B of the sample after being wiped off with a filter paper was measured, and the water absorption rate was calculated by the following formula. Water absorption rate (%) = (BA) / A × 100 (2) Dry feeling of coating surface The feeling of the coating surface after leaving the coated fabric for 1 hour in an environment of temperature 40 ° C. and humidity 90% by handling The following three grades were used for the evaluation. ○ ─── Very dry touch △ ───Slightly damp touch × ───Sticky feel (3) Friction coefficient ASTM D1894 (However, the wet condition should be such that the sample and the metal plate are completely wet. (4) Water vapor transmission rate JIS L-1099 (A-1 method) (5) Water pressure resistance JIS L-1096 (low water pressure resistance method)

Example 1 Nylon high multifilament 7 for both warp and weft
Weaving a plain woven fabric using 0 denier 68 filaments with a warp density of 120 yarns / inch and a weft yarn density of 90 yarns / inch,
After performing scouring and dyeing (manufactured by Mitsubishi Kasei Co., Ltd., acid dye DiacidFast Red 3BL 2% owf) by the usual method, Asahi Guard 710, a fluorine-based water repellent emulsion.
(Asahi Glass Co., Ltd.) After padding with a 5% aqueous solution (drawing ratio 35%) and drying, heat treatment was performed at 160 ° C. for 1 minute. Next, using a calendering machine having a mirror surface roll, calendering was performed under conditions of a temperature of 170 ° C., a pressure of 30 kg / cm ² , and a speed of 20 m / min to obtain a base fabric for coating.

Here, the resin solid content concentration of 2 on the above-mentioned base cloth.
A resin solution of the following formulation 1 in which 10 parts of inorganic fine powder and 10 parts of silk fine powder having a particle size of 10 μm were added to 100 parts of polyurethane resin at 8% was applied using a knife over roll coater at a coating amount of 20 g / m 2. Immediately after applying in ² 15
The resin component is solidified by immersing it in water at 60 ° C for 60 seconds, followed by washing in warm water at 50 ° C for 10 minutes and then drying to form a coating resin layer containing fine silk powder on the base cloth. Formed. Prescription 1 Resamine CU-4550 100 parts (ester type polyurethane resin, product of Dainichiseika Kogyo Co., Ltd.) Resamine X 1 part (isocyanate compound, product of Dainichiseika Kogyo Co., Ltd.) Dimethylformamide 25 parts Aerosil R-974 3 parts (average) SiO _{2 with} a particle size of 0.012 μm, a product of Nippon Aerosil Co., Ltd.) 10 parts of fine silk fiber powder (particle size of 10 μm, a product of Tosco Co., Ltd.)

Then, in order to make the coated surface water-repellent, padding was carried out with an aqueous solution of 5% Asahi Guard 710 (a fluorine-based water repellent manufactured by Meisei Chemical Co., Ltd.) (squeeze ratio 35%).
Then, it was dried and heat-treated at 150 ° C. for 1 minute to obtain a moisture-permeable and waterproof coating fabric of the present invention.

Formulation 1 of this Example for comparison with the present invention
A moisture permeable and waterproof coated fabric for comparison was obtained by the same method as in this example except that the fine silk fiber powder was omitted.

The performances of the present invention and the moisture-permeable waterproof coating fabric for comparison were measured and evaluated, and the results are shown in Table 1 together.

[Table 1]

As is clear from the results shown in Table 1, the moisture-permeable and waterproof coating fabric of the present invention has an excellent water-absorbing performance, and by applying the fine silk fiber powder,
The touch is dry touch even in a high humidity environment, the coated surface has a dry feel, the coated surface has a good sliding property, and the moisture permeability is 9000 g / m ² · 24 hrs or more. Water pressure resistance 0.5kgf / cm
It can be seen that it is as good as ² or more.

Example 2 The same as Example 1 except that 10 parts of the fine silk powder of Formula 1 was used instead of 10 parts of the fine silk powder of Formula 1 and 10 parts of fine wool fiber powder (product of Tosco Corp.) was used. The same method was used to obtain the moisture-permeable waterproof coating fabric of the present invention.

For comparison with the present invention, a moisture-permeable waterproof coating fabric for comparison was obtained in the same manner as in this example except that the fine wool fiber powder was omitted from the above formulation in this example.

The performance of the present invention and the moisture-permeable waterproof coating fabric for comparison were measured and evaluated, and the results are shown in Table 2 together.

[Table 2]

As is clear from Table 2, the moisture-permeable and waterproof coating fabric of the present invention has an excellent water-absorbing property, and because the fine powder of wool fiber is applied, the feel thereof is high even in a high humidity environment. With dry touch, the coated surface has a dry feel, and the coated surface has a good sliding property in terms of friction coefficient, and also has a moisture permeability of 9
000g / m ² · 24hrs or more, water pressure resistance 0.5kgf / cm ²
It can be seen that the above is very good.

[0043]

EFFECTS OF THE INVENTION According to the present invention, a moisture permeable and waterproof coated fabric having excellent water absorption performance, a dry and dry feel of the coating surface in a wet state, and high performance of moisture permeability and water pressure resistance is obtained. be able to. The windbreaker or the like made of the moisture-permeable and waterproof coating fabric of the present invention is comfortable to wear because it does not cause the skin and the coated surface to be entangled when worn. Due to these characteristics, the moisture-permeable and waterproof coating fabric of the present invention is a material particularly suitable for sports clothing, rain clothing, and mountaineering clothing.

Claims (1)

[Claims] 1. Wool fine powder and / or silk fine powder having an average particle size of 20 μm or less, and inorganic fine particles having an average particle size of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more. Manufacture of a moisture-permeable waterproof coating fabric characterized by applying a polar organic solvent solution of a polyurethane resin-based synthetic polymer containing powder to a fiber fabric and then dipping it in water to solidify the resin component. Method.