JP2001003272A - Production of moisture-permeable and water-proof fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production process for moisture-permeable and water- proofing laminated fabric that has excellent water-proofing performance and high moisture permeability and shows excellent wearing comfortability. SOLUTION: Fiber fabric is coated with a synthetic polymer solution mainly containing polyurethane resin including >=1 wt.% of inorganic fine powder and having an average particle size of <=1 μm and N,N-dimethylformamide adsorption of >=200 ml/100 g and they are subjected to the wet film formation. In the meantime, a release paper is coated with a synthetic polymer solution mainly containing a polyurethane resin and is subjected to the dry film formation. Then, these film layers are laminated so that their resin layer faces may opposed to each other, then the release paper is peeled off to give the objective moisture-permeable and water-proofing laminated fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art A moisture-permeable waterproof fabric having both moisture permeability and waterproofness has a function of discharging water vapor caused by sweating from the body out of clothes and a function of preventing rain from entering clothes. In order to provide these functions, high-density woven fabric in which yarns are woven at high density, or a polyurethane resin, a polyamino acid resin, a polyester resin, a polyamide resin, a polytetrafluoroethylene resin, etc. are coated or laminated on a fabric. What is well known. These are used for sports clothing, winter clothing, etc., and among them, they are often used in sports and outdoor clothing fields where the amount of sweat caused by exercise is relatively large, such as skiing, athletic,
It is an indispensable material in the field of mountaineering.

[0003] Among the conventional moisture-permeable waterproof fabric, although high density fabric type has sufficient moisture permeability soft, waterproof performance is about 0.1 kgf / cm ^2, the resin layer Of the types with a resin layer, the coating type with a perforated resin layer is generally easy to obtain excellent moisture permeability, but the waterproof performance is 0.2 to 0.3.
kgf / cm ² approximately obtained only while the waterproof performance resin layer excellent those imperforate easy to obtain, but do moisture permeability is little, at most 4000g / m ² · 24hrs about only those Not obtained. In order to compensate for such a defect, a perforated high moisture permeable resin layer is first formed on the fiber cloth, and a non-porous resin layer is formed thereon to obtain excellent moisture permeability and waterproof performance. A method has been tried, and although this method can provide excellent waterproof performance, it has only obtained a moisture permeability of about 3000 to 5000 g / m ² · 24 hrs. In order to smoothly release the sweat caused by exercise to the outside of the clothes, it is preferable to have a high moisture permeability, and to wear it in water or heavy rain, it is preferable to have a high waterproof property. There is a need for a wet waterproof fabric.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has both excellent waterproof performance and excellent moisture permeability, as well as good texture and excellent wearing comfort. It is intended to produce a waterproof laminated fabric.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has been described in detail.
below μm, the adsorption amount of N, N-dimethylformamide is 2
A wet polymer film is formed by applying a synthetic polymer solution mainly composed of a polyurethane resin containing 1% by weight or more of inorganic fine powder of 100 ml / 100 g or more, and a synthetic polymer solution mainly composed of a polyurethane resin is applied to release paper and dried. A method for producing a moisture-permeable waterproof laminated fabric, which comprises forming a film, bonding a wet film-forming resin film surface to the dry resin film surface, and then releasing the release paper.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the fiber cloth used in the present invention include polyamide synthetic fibers represented by nylon 6, nylon 66, polyester synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile synthetic fibers or polyvinyl alcohol synthetic fibers, and triacetate. Woven fabrics, knitted fabrics, nonwoven fabrics, etc. comprising semi-synthetic fibers such as Nylon 6 or mixed fibers such as nylon 6 / cotton and polyethylene terephthalate / cotton.

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 cloth. As the water repellent in this case, a known substance such as a paraffin-based water repellent, a fluorine-based water repellent, or a polysiloxane-based water repellent may be used. A known method such as a method may be used. If particularly good water repellency is required, use a fluorinated water repellent, for example, padding (squeezing) Asahigard 730 (a fluorinated water repellent emulsion from Asahi Glass Co., Ltd.) with a 5% aqueous dispersion. Rate of 40%) and after drying, 160
The heat treatment may be performed at a temperature of 1 ° C. for 1 minute.

In the present invention, an inorganic fine powder having an average particle diameter of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more is added to the fiber cloth.
A so-called wet film formation is performed in which a synthetic polymer solution mainly containing a polyurethane resin containing at least% by weight is applied, immersed in water to solidify the resin component, and dried to form a resin film.

As the synthetic polymer solution mainly composed of a polyurethane resin used in the present invention, a synthetic polymer solution containing 50 to 100% by weight of a polyurethane resin as a resin component is suitably used. As resin components other than polyurethane resin,
Polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, polycarbonate, and the like, and a copolymer thereof may be contained in a range of less than 50% by weight, and of course, a polymer modified with fluorine, silicon, or the like is included. You may go out. As the solvent in the synthetic polymer solution, any organic solvent capable of dissolving the polyurethane resin can be used. Generally, a polar organic solvent such as N, N-dimethylformamide is used. Is preferred.

The polyurethane resin used in the present invention is a polymer obtained by reacting an isocyanate with a polyol. Examples of the isocyanate component include an aromatic diisocyanate, an aliphatic diisocyanate, and an alicyclic diisocyanate alone or a mixture thereof. Specifically, tolylene 2,4-diisocyanate, 4,4′-diphenylmethane Diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, or the like is used as a main component, and trifunctional or higher functional isocyanate may be used.

Examples of the polyol component include polyether polyols and polyester polyols. Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As a reaction product of a diol such as ethylene glycol or propylene glycol with a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used. Of course, an oxyacid monomer or a prepolymer is used. You can also.

In the present invention, 1% by weight of an inorganic fine powder having an average particle diameter of 1 μm or less and an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more is contained in the above-mentioned synthetic polymer solution mainly composed of a polyurethane resin. More than that. As the inorganic fine powder used here, any inorganic substance having the above performance can be used. A known method may be used to pulverize the inorganic substance. Specifically, inorganic fine powder pulverized by a wet pulverization method or a ball mill pulverization method, or a metal oxide fine powder obtained by a dry method such as a vapor phase oxidation method of a metal halide, a combustion hydrolysis method, and an electric arc method. Among them, it is preferable to use anhydrous silicon dioxide fine powder produced by these methods.

The fine powder obtained by these methods generally has a particle size of 0.05 μm or less and has a very large amount of adsorbed N, N-dimethylformamide, and is added to a synthetic polymer solution. It is suitable as an inorganic fine powder. The amount of N, N-dimethylformamide adsorbed here means that 5 g of inorganic fine powder is placed on a glass plate, and each time one drop of N, N-dimethylformamide is added, kneading using a stainless steel spatula is repeated. , N, N-
It means the volume (unit: milliliter) of N, N-dimethylformamide required until immediately before softening with one drop of dimethylformamide, and is defined by JIS K-51.
The measurement is carried out in accordance with the method for measuring oil absorption in No. 01, in which N, N-dimethylformamide is used instead of oil in boiled linseed.

The inorganic fine powder used in the present invention needs to have an average particle diameter of 1 μm or less and an N, N-dimethylformamide adsorption amount of 200 ml / 100 g or more. In addition, it is more preferable that the amount of N, N-dimethylformamide adsorbed is 300 ml / 100 g or more from the viewpoint of the effects of the present invention.
When the average particle size exceeds 1 μm, the pore size of the micropores of the obtained resin film becomes too large, and the waterproof performance is deteriorated, which is not preferable. When the N, N-dimethylformamide adsorption amount is less than 200 ml / 100 g, the resin This is not preferable because the number of micropores in the membrane is reduced and the moisture permeability is not significantly improved.

The amount of the inorganic fine powder must be 1% by weight or more, preferably 3% by weight or more, based on the synthetic polymer mainly composed of polyurethane resin. If it is less than 1% by weight, the number of pores in the fine hollow portion of the obtained coated fabric will be small, and the moisture permeability will not be much improved. Also, the inorganic fine powder does not necessarily need to be of high purity,
Other inorganic substances such as pigments and fillers may be contained as impurities without any problem.

As a method of applying the above-mentioned synthetic polymer solution mainly composed of a polyurethane resin containing the inorganic fine powder to one surface of the fiber cloth, a commonly used coating method may be used. For example, a knife coater, a comma coater, The coating may be appropriately performed using a reverse coater or the like. The coating amount may be arbitrarily selected, but it is preferable that the dry resin film weight is preferably 10 g / m ² or more, more preferably 15 g / m ² or more. After the application, the resin is solidified by dipping in water at 5 to 30 ° C., then washed with hot water at 40 to 60 ° C., and dried to form a resin film, so-called wet film formation.

In the present invention, at the time of coating, a compound having a high affinity for the resin and the fiber cloth may be used in combination with the resin solution for the purpose of improving the peeling resistance between the resin layer and the fiber cloth. An isocyanate compound can be suitably used. Examples of the isocyanate compound include tolylene 2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, or a compound containing 3 mols of these diisocyanates and active hydrogen (for example, trimethylol Propane, glycerin, etc.)
Triisocyanates obtained by addition reaction with 1 mole can be used. The above-mentioned isocyanates may be in a form in which an isocyanate group is released, or may be 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 the application. The amount of the isocyanate compound used is preferably 0.1 to 10% by weight based on the mixed solution of the polyurethane resin-based synthetic polymer, and the used amount is 0.1% by weight. If it is less than 10%, the adhesive strength of the resin layer to the fabric is low, and if it exceeds 10% by weight, the hand becomes hard, which is not preferable.

In the present invention, in order to further improve the waterproof performance, the coated fabric after the wet film formation may be subjected to a water-repellent treatment. When performing the water-repellent treatment, a known water-repellent treatment method that is generally performed as described above may be employed.

Next, in the present invention, a synthetic polymer solution mainly composed of a polyurethane resin is applied onto release paper, and dry film formation is performed. The release paper used here is generally used, and for example, release paper obtained by laminating a polyethylene film or a polypropylene film on paper or release paper coated with a silicone resin may be used. In the present invention, a so-called dry film forming method of forming a substantially non-porous resin layer by applying the above-mentioned polyurethane polymer-based synthetic polymer solution on release paper using the same coating apparatus as described above and drying it. I do. The coating amount may be appropriately determined depending on the desired water pressure resistance and moisture permeability, but is preferably adjusted so that the dry resin film weight becomes 1 g / m ² or more, more preferably 3 g / m ² or more. Just do it.

In the present invention, after forming a resin film on release paper,
Immediately, the above-mentioned wet resin film surface is bonded, and the release paper is peeled off. As a method of laminating the dry resin film surface and the wet resin film surface, a commonly used method may be adopted, for example, a method of bonding the two via an adhesive or a thermocompression bonding method. However, in order to obtain high moisture permeability, it is preferable to use a pressure bonding method.

[0021]

According to the present invention, a synthetic resin solution mainly composed of a polyurethane resin in which an inorganic fine powder having an average particle diameter of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more is uniformly dispersed in a fiber. When one side of the fabric is coated and wet coagulation is performed, water as a coagulation liquid and N, N-dimethylformamide as a solvent of the resin are mixed, and the solvent is quickly released from the resin liquid to coagulate the resin. Begins, but at this time, if the inorganic fine powder having an average particle size of 1 μm or less and having a very large N, N-dimethylformamide adsorption amount 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 other parts, in other words, N, N-dimethylformamide in a polyurethane resin-based synthetic polymer corresponding to other parts. In the wet coagulation process, water, which is a coagulating liquid, is first replaced with N, N-dimethylformamide on the surface of the inorganic fine powder, starts quickly around the inorganic fine powder, and has a characteristic characteristic of polyurethane resin. In addition to the honeycomb skin core structure, a very porous form having countless micropores of several μm or less is obtained. Since it has these innumerable micropores, very excellent moisture permeability can be obtained.

Further, in the present invention, since a dry resin film is laminated on the above-mentioned wet resin film, a dry resin solution is used in a dry resin solution as compared with a general direct method in which a resin is applied directly on the wet resin film to form a dry resin film. The solvent does not erode in the wet resin layer and does not impair the microporous form.In addition, when a fiber fabric with strong irregularities is used, the amount of the dry resin film applied to the convex portions by the direct method is smaller than that of the concave portions. While it tends to be less and it is difficult to obtain uniform waterproof performance, uniform and extremely excellent waterproofness can be obtained.

[0023]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The measurement and evaluation of the performance of the fabrics in the examples were performed by the following methods. Water resistance JIS L-1092 (high water pressure method) The water resistance was measured when water came out from one place and when water came out from the third place. Moisture permeability JIS L-1099 (A-1 method)

Example 1 A ripstop taffeta having a warp density of 80 yarns / inch and a weft yarn density of 75 yarns / inch was woven using 110 denier / 48 filament nylon nylon for both the warp and the weft. After dyeing (Kayanol Navy Blue R 3% owf, manufactured by Nippon Kayaku Co., Ltd.), padding (squeezing) with 6% aqueous dispersion of Asahigard LS-317 (manufactured by Asahi Glass Co., Ltd., fluorine-based water repellent emulsion). After drying, a heat treatment was performed at 170 ° C. for 30 seconds. Next, at a temperature of 170 ° C and a pressure of 30 kgf /
Perform a calendering process under the conditions of cm ² and speed of 30 m / min.
A base fabric for coating was obtained. Then, with the composition shown in the following formula 1, the solid content concentration is 24% and the viscosity is 11000 mPa · s.
(25 ° C.) using a knife over roll coater to coat the above-mentioned calender surface with a coating amount of 1
Immediately after application at 30 g / m ² ,
Dipped for 5 seconds to solidify the resin, then washed in warm water at 50 ° C for 5 minutes, and dried to form a microporous resin film mainly composed of polyurethane resin on one side of nylon taffeta did. The resin film contains 1 inorganic fine powder.
2% by weight was contained.

Formulation 1 Lac Skin 1740-29B 100 parts (Seiko Kasei Corporation, ester type polyurethane resin) Resamine X 1 part (Dainichi Seika Industries Co., Ltd., isocyanate compound) N, N-dimethylformamide 35 parts Aerosil R # 972 4 parts (Nippon Aerosil Co., Ltd., hydrophobic silicon dioxide fine powder, average particle size 0.016 μm, N, N-dimethylformamide adsorption amount 350 ml / 100 g)

Next, on the release surface of EV130TPO (release paper manufactured by Lintec Co., Ltd.), a solid content concentration of 20% and a viscosity of 3000 mPa · s (25 ° C.) with a composition shown in the following formulation 2 were applied.
Was applied at a coating amount of 25 g / m ² using a comma coater, followed by drying at 100 ° C. for 2 minutes to form a dry resin film. The dry resin film and the wet resin film are thermocompression-bonded between the dry resin film surface and the wet resin film surface at a temperature of 80 ° C. and a pressure of 3 kgf / cm ² , and the release paper is peeled off. A waterproof laminated fabric was obtained.

Formulation 2 100 parts of Samprene HMP-17A (polyurethane resin manufactured by Sanyo Chemical Co., Ltd.) 50 parts of methyl ethyl ketone

For comparison with the present invention, a comparative moisture-permeable waterproof laminated fabric was obtained in exactly the same manner as in this example except that Aerosil R # 972 of the prescription 1 was omitted in this example 1.
(Comparative Example 1)

For comparison with the present invention, Example 1 was used.
The amount of Aerosil R # 972 in Formula 1 was reduced to 0.
In place of 2 parts, except that a wet resin film having an inorganic fine powder content of 0.7% by weight was formed, the same method as in this example was used.
A moisture-permeable waterproof laminated fabric for comparison was obtained. (Comparative Example 2)

For comparison with the present invention, Example 1 was used.
In Formula 1, Aerosil R # 972 was added to Crystallite VX-X (manufactured by Shiraishi Calcium Co., Ltd., average particle size 1.8
μm, N, N-dimethylformamide adsorption amount 60 ml / 100 g silicon dioxide fine powder)
A moisture-permeable waterproof laminated fabric for comparison was obtained in exactly the same manner as in Example 1. (Comparative Example 3)

Further, for comparison with the present invention, this embodiment
Using a knife coater, apply the resin solution of formulation 2 in 1
A moisture-permeable waterproof laminated fabric for comparison was obtained in exactly the same manner as in this example except that it was applied directly on the wet resin film surface. (Comparative Example 4) The performances of the present invention and a comparative fabric were measured, and the results are shown in Table 1.

[0032]

[Table 1]

As is evident from Table 1, the moisture-permeable waterproof laminated fabric of the present invention had excellent moisture permeability and high-order stable waterproofness.

[0034]

Example 2 Aerosil R of Formulation 1 in Example 1
─ 972 parts were replaced by 3 parts of alumina AKP-G015 (manufactured by Sumitomo Chemical Co., Ltd., hydrophobic dialuminum trioxide fine powder having an average particle size of 0.03 μm and N, N-dimethylformamide adsorption amount of 310 ml / 100 g). A moisture-permeable waterproof fabric of the present invention was obtained in exactly the same manner as in Example 1 except that a wet resin film having an inorganic fine powder content of 9% by weight was formed. (Invention 2)

For comparison with the present invention, the alumina AKP-G015 in the present example was converted to alumina A-42-6 (manufactured by Showa Denko KK, average particle size 5 μm, adsorption amount of N, N-dimethylformamide 32 ml / 100 g). The same procedure as in Example 2 was carried out, except that dialuminum trioxide fine powder was used to obtain a comparative moisture-permeable waterproof laminated fabric. (Comparative Example 5)

Further, for comparison with the present invention, the resin solution of Formulation 2 in Example 2 was prepared using a knife coater.
A moisture-permeable and waterproof laminated fabric for comparison was obtained in exactly the same manner as in Example 2 except that it was applied directly on the wet resin film surface. (Comparative Example 6) The performances of the present invention and the comparative fabric were measured, and the results are shown in Table 2.

[0037]

[Table 2]

As is clear from Table 2, the moisture-permeable waterproof fabric of the present invention was excellent in that the moisture-permeable waterproof laminated fabric of the present invention had excellent moisture permeability and also had high-order stable waterproofness. .

[0039]

According to the present invention, a moisture-permeable waterproof laminated fabric having excellent water pressure resistance and excellent moisture permeability can be manufactured.

Continued on the front page F-term (reference) 4F100 AA01B AA01H AA20H AK17 AK48 AK51B AK51C BA03 BA07 BA10A BA10C CA23B DE01B DE01H DG11A DG12 DJ10 EC182 EG001 EH461 EJ011 EJ172 EJ422 EJ811 J041J87 EJ861B07J04 EJ4 CA50 CA69 CA70 DA06

Claims (1)

[Claims] 1. A synthetic resin mainly composed of a polyurethane resin containing 1% by weight or more of an inorganic fine powder having an average particle diameter of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more on one surface of a fiber cloth. After applying a coalescing solution to perform wet film formation, applying a synthetic polymer solution mainly composed of a polyurethane resin to release paper to perform dry film formation, and after laminating the wet film forming resin film surface to the dry resin film surface, A method for producing a moisture-permeable waterproof laminated fabric, comprising releasing a release paper.