JP2003119673A - Production of moisture-permeable and waterproof coated fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of production for a moisture-permeable and waterproof-coated fabric excellent in visual effect or the like of a coating. SOLUTION: This method of production for the moisture-permeable and waterproof-coated fabric, forming the coating on the fabric in a wet coating method coating a synthetic polymer solution principally comprising a polyurethane resin and imparting concavo-convex shape on the surface of the coated resin in resin coagulating process or washing process and then drying, uses the synthetic polymer solution principally comprising a polyurethane resin including 1-30% of inorganic fine powder having an average particle size of <=1 μm and N,N-dimethylformamide adsorption of >=200 ml/100 g in production of the fabric having highly moisture-permeable and water-proofing properties.

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 and waterproof coated fabric which is used for various clothing such as sports clothing and winter clothing and has excellent moisture permeable and waterproof performance and a visual effect of a coating film. .

[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 a function of preventing rain from entering the clothes. To impart these functions, the fabric is coated or laminated with high-density woven fabric in which threads are woven in high density, polyurethane-based resin, polyamino acid-based resin, polyester-based resin, polyamide-based resin, polytetrafluoroethylene resin, etc. What you have done is well known. These are used for sports clothing, winter clothing, etc., and are often used in the field of sports and outdoor clothing, where the amount of sweat associated with exercise is relatively large, among them, skiing, athletic,
It is an indispensable material in the mountain climbing field. The high density woven fabric type is advantageous in terms of moisture permeability due to its constitution, but is disadvantageous in terms of waterproof performance, and the coating type and laminate type have excellent moisture permeability when the resin layer is perforated. It is easy to obtain, but it is difficult to obtain sufficient waterproof performance, and on the other hand, a resin layer with no pores has excellent general waterproof performance, but it is difficult to obtain sufficient moisture permeability. There is.

The laminate type has an advantage that it can be applied to a wide range of materials. However, in order to prevent extreme deterioration of moisture permeability, the adhesive occupying area is usually 50% or less and the resin is adhered. It has drawbacks such as poor adhesion strength and abrasion of the film. On the contrary, the coating type is
Although there are restrictions on the applicable materials because the resin is directly applied to the materials, it has the advantage that it is easy to obtain excellent adhesive strength of the resin film. In recent years, from the background of material weight reduction, cost reduction, etc., there is a strong need to use these breathable waterproof cloths as so-called one-piece products that are sewn without a lining, and for that reason the resin film on the back side also looks great. With the demand for excellent visual effects, it is becoming unacceptable with flat coating surfaces. Therefore, in the present situation, after forming a moisture-permeable waterproof cloth by a coating method or a laminating method, pattern-shaped gravure coating such as dots or screen printing is performed on the resin film to meet these requirements. However, in the above method, due to abrasion during wearing, the pattern obtained by gravure coating or screen printing is likely to fall off,
Moreover, there is a problem that the number of processes is increased, which leads to an increase in cost.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a moisture-permeable waterproof coating fabric excellent in the visual effect of a resin film and the like. .

[0005]

Means for Solving the Problems The present invention achieves the above-mentioned object. "When a film is formed on one side of a fiber cloth by a wet coating method, a synthetic polymer solution mainly composed of a polyurethane resin is applied. A method for producing a moisture-permeable waterproof coating fabric, which comprises imparting an uneven shape to the resin film surface during any one of the resin coagulation process and the hot water washing process, and then drying it "and" fiber fabric When a film is formed by a wet coating method on one surface of, the polyurethane resin-based synthetic polymer solution is applied, and then an uneven shape is formed on the resin film surface during either the resin coagulation step or the hot water washing step. A moisture-permeable and waterproof coating characterized by applying, then drying, and further forming a film on the obtained resin film having an uneven shape by a dry coating method using a synthetic polymer solution mainly composed of a polyurethane resin. In the synthetic polymer mainly composed of a polyurethane resin which is formed into a film by a wet coating method, the average particle diameter is 1 μm or less and the amount of N, N-dimethylformamide adsorbed is 200 ml / The above-mentioned method for producing a moisture-permeable waterproof coating fabric is characterized by containing 1 to 30% of an inorganic fine powder of 100 g or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 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, polyvinyl alcohol synthetic fibers, triacetate and the like. The semi-synthetic fibers, or the woven or knitted fabric made of a yarn in which synthetic fibers such as nylon 6 / cotton, polyethylene terephthalate / cotton and the like and natural fibers are mixed, and the non-woven fabric made of these fibers.

In the present invention, the above-mentioned fiber cloth treated with a water repellent may be used. This is one means for preventing the permeation of the resin solution into the cloth during the production of the moisture-permeable waterproof cloth. As the water repellent in this case, known ones such as a paraffin water repellent, a polysiloxane water repellent, and a fluorine water repellent may be used, and the treatment is also performed by a commonly used padding method, A known method such as a spray 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. After 35%), 160 ℃
It may be performed by a method of performing heat treatment for 1 minute.

In the present invention, a film is formed on one surface of the above-mentioned fiber cloth by a wet coating method using a solution of a synthetic polymer mainly composed of a polyurethane resin. The term “polyurethane resin-based synthetic polymer” as used in the present invention means one consisting of only a polyurethane resin or one containing 50% or more of a polyurethane component. Examples of the synthetic polymer containing a synthetic polymer other than the polyurethane resin include: , Polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid and the like and copolymers thereof, and of course, compounds modified with fluorine or silicon can be used.

The polyurethane resin itself is a copolymer obtained by reacting a polyisocyanate and a polyol, and aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates are used alone or as a mixture thereof as an isocyanate component. Tolylene 2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexanediisocyanate, 1,4-cyclohexanediisocyanate, etc. may be used as a main component, and a trifunctional or higher functional isocyanate may be used if necessary. Further, as the polyol component, polyether polyol or polyester polyol is used, as the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like is used, and as the polyester polyol, for example, ethylene glycol or propylene glycol. A reaction product of a diol such as the above with a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone is used.

In the present invention, for the purpose of improving the peeling resistance between the resin layer and the fiber cloth, it is desirable to use a compound having a high affinity with the resin and the fiber cloth, and an isocyanate compound is preferably used as the compound. it can. As the isocyanate compound, tolylene 2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or 3 mol of these diisocyanates and a compound containing active hydrogen (eg, trimethylolpropane, glycerin, etc.) 1 mol Triisocyanates obtained by addition reaction with can be used. The above isocyanates may be in a form in which an isocyanate group is free, or may be in a form in which an addition block body is formed with phenol, lactam, methyl ketone or the like and dissociated by heat treatment. It may be properly used depending on the application.

The above-mentioned isocyanates may be in a form in which an isocyanate group is free, 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 and purpose.
The amount used when using the isocyanate compound,
0.1 to the above polyurethane resin-based synthetic polymer
It is desirable to use it in a ratio of 10%, and when the amount used is less than 0.1%, the adhesive force of the resin layer to the fabric does not improve so much, and when it exceeds 10%, the texture tends to harden. It will be recognized, which is not preferable.

In the present invention, the polyurethane polymer-based synthetic polymer solution used in the wet coating method is a polyurethane polymer-based synthetic polymer containing a polar organic solvent such as N, N-dimethylformamide or N-methylpyrrolidone. It is a resin solution that is dissolved in a solvent as a main component.
If a filler such as titanium oxide, calcium carbonate, aluminum fine powder, a color pigment, a pearl pigment and the like are used in combination with this resin solution, it becomes easier to obtain a resin film having excellent visual effects and touch feeling.

Further, this polyurethane resin-based synthetic polymer solution has an average particle size of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 10.
When the inorganic fine powder of 0 g or more is contained in an amount of 1% or more, more excellent moisture permeation and waterproof performance can be obtained. The amount of N, N-dimethylformamide adsorbed here means N, N instead of oil for boiled linseed according to JIS K-5101.
Using N-dimethylformamide, 5 g of inorganic fine powder was placed on a flat glass plate, and kneading was repeated using a spatula made of stainless steel every time one drop of N, N-dimethylformamide was dropped. One drop of dimethylformamide required N, N until just before it suddenly became soft
-Volume of dimethylformamide (unit: milliliter)
Is a numerical value converted per 100 g of the inorganic fine powder.

As such inorganic fine powder, inorganic fine powder pulverized by a usual wet pulverizing method or a ball mill pulverizing method, a gas phase oxidation method of a metal halide, a combustion hydrolysis method, an electric arc method, or the like is used. The metal oxide fine powder obtained by the method can be mentioned, and the silicon dioxide fine powder produced by these methods can be mentioned as a representative.
The amount of the inorganic fine powder used is preferably 1% or more, more preferably 3% or more, based on the synthetic polymer mainly composed of the polyurethane resin. If it is less than 1%, the number of pores in the fine hollow portions of the obtained coated cloth is small, and it becomes difficult to obtain high moisture permeability. Further, the inorganic fine powder does not necessarily need to be highly pure, and may contain other inorganic substances or the like.

Examples of the method for applying the synthetic polymer solution mainly composed of polyurethane resin to the fiber cloth include a comma coater, a knife coater and a reverse coater. The coating amount is
In order to obtain excellent moisture permeability and waterproofness and three-dimensional visual effect, the resin dry film weight is 10 g / m ² or more, preferably 15
The coating amount may be adjusted so as to be g / m ² or more.

According to the present invention, when a film is formed by a wet coating method, a solution of a synthetic polymer mainly composed of a polyurethane resin is applied to one side of a fiber cloth, and then, during the step of either resin coagulation or hot water washing, The resin film surface is provided with an uneven shape and then dried. A film is formed by a normal wet coating method by applying a resin solution, introducing the resin solution into water at 10 to 30 ° C., and allowing it to stay for 30 seconds to 2 minutes to coagulate the resin component, and then to remove the solvent 40 to completely remove the solvent. 5 at a temperature of 80 ° C
The resin layer is formed by washing with hot water for 10 minutes and drying, but in the present invention, when the coating resin film is still in a wet state before the drying step, that is, between the solidifying step and the hot water washing step, The resin film surface is provided with an uneven shape.

The concavo-convex shape referred to in the present invention means a shape such as a dot shape, a linear shape or a lattice type, a slanted type, a pyramid type, a hexagonal shape, a patterned character, a design, etc., and imparts an irregular shape. As a method, any of ordinary methods capable of imparting an uneven shape, such as a screen mesh and a mold, may be used.
A method using a gravure roll engraved in a desired shape or an engraving roll is preferable in operation.

The unevenness may be imparted to the resin film before the resin film is formed by drying as described above.
In the present invention, it is preferable to carry out during the solidification process of forming a resin film after applying the resin solution, for example, in a coagulating water bath, while rotating the resin coated surface on a roll engraved into a desired shape, The concavo-convex shape can be easily imparted without requiring a large pressure or heat energy to the film. If an uneven shape is applied after drying, a great amount of pressure and energy are required, the uneven shape is poor in durability, and the resin film is likely to be damaged.

In the present invention, a synthetic polymer solution containing a polyurethane resin as a main component may be formed on the resin film having the uneven shape as described above by a dry method. The polyurethane resin-based synthetic polymer used here may be the same as that used in the above-mentioned wet method, but the polymer solution mainly contains a polar organic solvent such as N, N-dimethylformamide or N-methylpyrrolidone. It is not a resin solution dissolved in a solvent, but a solution mainly composed of a nonpolar solvent such as toluene, methyl ethyl ketone, ethyl acetate, and water. If a large amount of polar organic solvent is used, the surface of the microporous film formed by the wet method is dissolved by the polar organic solvent, which lowers the moisture permeability, which is not preferable. The form of the resin solution may be any of a solvent type, a water-in-oil emulsion, an oil-in-water emulsion and a water-soluble type. It is more effective if silica powder is used together for the purpose of improving the property. In this case, the resin coating amount is preferably 0.5 to 10 g / m ² of the dry resin amount,
It is more preferably 1 to 5 g / m ² . Film formation by this dry method is performed by a coating device such as a knife coater or a reverse coater or a gravure roll. As the gravure roll, it is preferable to use a gravure roll which has a dot shape and a small depth of 100 μm or less and has a high mesh of 80 mesh or more for overall application.

In the present invention, for the purpose of further improving waterproofness and water repellency durability, the coated cloth may be subjected to water repellency treatment after wet coating. For the water repellent treatment, a publicly known well-known water repellent treatment method as described above may be adopted.

[0021]

In the present invention, when a synthetic polymer solution mainly composed of a general polyurethane resin is subjected to wet film formation, the resin film is formed before the step of making the resin film dry, that is, between the coagulation step and the hot water washing step. In the wet state, the uneven shape such as the dot shape, the linear shape, the lattice type, the oblique line shape, the pyramid shape, and the hexagonal shape is given, so the uneven shape can be easily given to the resin surface due to the pressure difference, which is very expensive in terms of processing cost. In addition, the obtained resin film has an appearance excellent in visual effects and the like. Further, if the fine aluminum powder and the color pigment or pearl pigment are uniformly dispersed in the resin, the unevenness formed forms various reflection colors, so that a resin film having a more three-dimensional visual effect is obtained. It becomes possible.

When a high degree of moisture permeation and waterproof performance is required in the present invention, an inorganic fine powder 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 is uniformly added to the resin solution. When dispersed and wet coagulated, water as a coagulating liquid and N, N-dimethylformamide as a resin solvent are mixed, and the solvent is promptly released from the resin liquid to start coagulation of the resin. In this case, the average particle size is 1 μm or less, and the amount of N, N-dimethylformamide adsorbed is 200 ml / 1.
If the inorganic fine powder of at least 00 g is evenly dispersed,
The surface of the fine powder has a higher concentration of N, N-dimethylformamide in the resin solution than the other portions, in other words, a state in which the concentration of N, N-dimethylformamide of the polyurethane resin-based synthetic polymer is low. Therefore, in the wet coagulation process, water as a coagulating liquid is first replaced with N, N-dimethylformamide on the surface of the fine powder, solidification is rapidly started around the water, and thereafter, a honeycomb skin core structure peculiar to the urethane resin is formed. Besides the cavity of
Innumerable minute pores of 1 μm or less are formed around the uniformly dispersed fine powder, resulting in a very porous form, so that it is possible to improve moisture permeability while maintaining high waterproof performance. . In addition, since the resin film is an ultrafine porous layer, the whiteness and volume of the resin film are improved, so that it is possible to obtain a more three-dimensional and milder visual effect of the resin film. it can.

When a dry resin film is further formed on the wet resin film having an uneven shape, the uneven shape given to the wet resin film is further fixed, and the durability against friction during wearing or washing. By further coloring the wet resin film and the dry resin film with different colors, providing a difference in shade, and giving a different glossy feeling,
The visual effect can be further enhanced.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples. The measurement and evaluation of the performance of the fabrics in the examples were carried out by the following methods. (1) Water pressure resistance JIS L-1092 High water pressure method (2) Water vapor transmission rate JIS L-1099 A-1 method (3) Appearance of coating film appearance and friction according to JIS L-1096 D method (accelerator type method) With respect to the sample after the treatment, the visual effect and touch feeling of the coating film were evaluated by visual feeling and touch feeling.

Example 1 Nylon 6 multifilament 78 for both warp and weft
Using decitex / 68 filament, warp density 12
After weaving taffeta with 0 yarns / 2.5 cm and weft density of 95 yarns / 2.5 cm, after scouring and dyeing (Kyanol Navy Blue R 3% omf manufactured by Nippon Kayaku Co., Ltd.) by a usual method,
Emulsion type fluorinated water repellent Asahi Guard A
G-970 (manufactured by Asahi Glass Co., Ltd.) was padded with a 6% aqueous dispersion (squeeze ratio: 35%), dried, and then heat-treated at 170 ° C. for 30 seconds. Next, using a calendering machine having a mirror surface roll, calendering was performed under the conditions of a temperature of 170 ° C., a pressure of 250 kPa and a speed of 30 m / min to obtain a base fabric for coating. Here, with the composition shown in the following prescription 1, the solid content concentration is 22
%, A polyurethane resin solution having a viscosity of 13000 mPa · s (25 ° C.) was applied to the above-mentioned calendar surface using a comma coater at a coating amount of 120 g / m ^{2 and} immediately after being applied in water at 15 ° C. 4
When the resin component is solidified by immersion for 0 seconds, the coating resin surface and dot-shaped gravure roll (14.5 mesh, dot diameter 0.75 mm, dot interval 1 mm, depth 100 μ) after 10 seconds
m) is rotatively contacted, followed by washing with hot water at 50 ° C. for 5 minutes and then drying to form a resin film, and the moisture permeability of Example 1 according to the present invention having dot-shaped irregularities on the resin film surface. A waterproof coating fabric was obtained.

<Prescription 1> 1740-29B 100 parts (wet polyurethane resin manufactured by Seiko Kasei Co., Ltd.) Resamine X 1 part (isocyanate compound manufactured by Dainichi Seika Chemicals Co., Ltd.) Seika Seven BS-7692 Blue 3 parts ( Dainichi Seika Chemicals Co., Ltd. cyanine colorant) ・ Sap210EA 2 parts (Showa Aluminum Powder Co., Ltd. aluminum paste) ・ N, N-dimethylformamide 35 parts

Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1 except that the normal wet coating was carried out by omitting the rotary contact between the coating resin film and the gravure roll during the resin component solidification. A moisture-permeable and waterproof coating fabric of was obtained.

Comparative Example 2 A polyurethane resin solution having the composition shown in the following prescription 2 was applied onto the moisture-permeable and waterproof coating fabric resin film of Comparative Example 1 in the form of a dot gravure roll (14.5 mesh, dot diameter 0.75 mm,
After dot printing with a dot spacing of 1 mm and a depth of 100 μm), drying was carried out at 80 ° C. for 2 minutes to obtain a moisture-permeable waterproof coating fabric of Comparative Example 2 having a dot-like convexity on the resin film surface.

<Prescription 2> 50 parts of rack skin U2524 (solvent type polyurethane resin manufactured by Seiko Kasei Co., Ltd.) 50 parts of rack skin U2525M (polyurethane matting agent for rack skin U2525 manufactured by Seiko Kasei Co., Ltd.) Seika Seven BS- 7692 Blue 3 parts (Dainichi Seika Chemicals Co., Ltd. cyanine colorants) Sap210EA 2 parts (Showa Aluminum Powder Co., Ltd. aluminum paste) ・ Isopropyl alcohol 5 parts ・ Toluene 5 parts ・ N, N-dimethylformamide 5 parts

Example 2 On the resin surface of the moisture-permeable waterproof coating fabric of Example 1,
Furthermore, with the composition shown in the following formulation 3, the viscosity at a solid content concentration of 22%
5000mPa · s (25 ℃) polyurethane resin solution
After coating at a coating amount of 20 g / m ² using a knife coater, 80 ° C
Was dried for 3 minutes to form a resin film to obtain a moisture-permeable and waterproof coating fabric according to the present invention.

<Prescription 3> 50 parts of rack skin U2524 (solvent type polyurethane resin manufactured by Seiko Kasei Co., Ltd.) 50 parts of rack skin U2525M (polyurethane matting agent for rack skin U2525 manufactured by Seiko Kasei Co., Ltd.) 10 parts of isopropyl alcohol Toluene 10 parts The performances of the coated fabrics of Examples 1 and 2 and Comparative Examples 1 and 2 were measured, and the results are also shown in Table 1.

[0032]

[Table 1]

As is clear from Table 1, the moisture-permeable waterproof coating fabric of Example 1 according to the present invention in which unevenness was imparted during film formation by the wet method did not impair moisture-permeable waterproof performance and had a good film appearance and the like. And has no change with respect to friction. In Example 2 in which a film was further formed on the resin film obtained in Example 1, the state after rubbing was more stable. On the other hand, in Comparative Example 2 in which the convex shape was provided after the film formation, the convex portion was deformed by friction and the appearance was disturbed.

Example 3 Preparation of Example 1 was repeated except that AEROSIL R-974 was used.
(Nippon Aerosil Co., Ltd., average particle size is about 0.012μ
3 parts of silicon dioxide fine powder having m, N, N-dimethylformamide adsorption amount of 350 ml / 100 g) was uniformly dispersed (resin solid content was 24%), and the gravure roll used in Example 1 was replaced with a diagonal engraving roll ( The angle of 60 degrees, the number of lines / ^2.5 cm, the cross-section is mountain-like, the depth is 100 μm, and the volume of the concave portion is 56 cm ³ / m ² ). A moisture-permeable waterproof coating fabric was obtained.

Comparative Example 3 Comparative Example 3 was carried out in the same manner as in Example 3, except that the rotary contact between the coating resin film and the engraving roll was omitted during the resin component coagulation process in Example 3, and ordinary wet coating was carried out. A moisture-permeable waterproof coating fabric was obtained.

Comparative Example 4 A polyurethane solution having the composition shown in Formula 2 used in Comparative Example 2 was printed on the moisture-permeable waterproof coating fabric resin film of Comparative Example 3 by the diagonal engraving roll used in Example 3. After the processing, drying was carried out at 80 ° C. for 2 minutes to obtain a moisture-permeable waterproof coating fabric of Comparative Example 4 having diagonal convex portions on the resin film surface. The performances of the coated fabrics of Example 3 and Comparative Examples 3 to 4 were measured, and the results are shown together in Table 2.

[0037]

[Table 2]

As is clear from Table 2, the moisture-permeable waterproof coating fabric of Example 3 according to the present invention has a high moisture-permeable waterproof performance, but also has a good film appearance and the like.
On the other hand, in Comparative Example 4 in which the convex shape is provided after the film formation,
The protrusion was deformed by friction and the appearance was disturbed.

[0039]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a moisture-permeable waterproof coated cloth having excellent moisture-permeable waterproof performance and visual effects of the coating film.

Claims (3)

[Claims] 1. When a film is formed on one side of a fiber cloth by a wet coating method, a solution of a synthetic polymer mainly composed of a polyurethane resin is applied, and then, during one of a resin coagulating step and a hot water washing step, A method for producing a moisture-permeable waterproof coating fabric, which comprises providing a resin film surface with an uneven shape and then drying. 2. When a film is formed on one side of a fiber cloth by a wet coating method, a solution of a synthetic polymer mainly composed of a polyurethane resin is applied, and then, during one of a resin coagulating step and a hot water washing step, It is characterized in that the resin film surface is provided with an uneven shape, then dried, and then a film is formed on the obtained resin film having the uneven shape by a dry coating method using a polyurethane polymer-based synthetic polymer solution. And a method for producing a moisture-permeable waterproof coated fabric. 3. An average particle size of 1 μm in a synthetic polymer mainly composed of polyurethane resin which is formed into a film by a wet coating method.
The moisture-permeable waterproofing according to claim 1 or 2, which contains 1 to 30% of an inorganic fine powder having an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more. Of producing a hydrophilic coating fabric.