JPS61679A - Production of moisture permeable water-proof cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a fabric that simultaneously has three functions: waterproofness and moisture permeability. Generally, breathability and waterproofness are contradictory functions.

Waterproof fabrics with excellent moisture permeability are obtained by forming numerous continuous fine pores that allow water vapor to escape in the coating resin film during dry or wet coating. Polyurethane elastomer is generally preferably used as the coating resin during these dry or wet coating processes in terms of strength, rubber elasticity, and flexibility. However, in the case of a breathable waterproof fabric made of polyurethane elastomer, it is made based on a balance between waterproof performance and moisture permeability, so its waterproof performance is 1.1 in the JIS +, L1o96 water pressure measurement.
For fabrics with a length of 500 mm (below the water column) or more, the moisture permeability is 4,000 to 5. OOh / rd ・24hrs
(JIS Z-0208 measurement) is currently available. This moisture permeability level is 7,
If it can be improved to 000g/rrr・24hrs or more, it will have almost the same moisture permeability as a non-coated fabric that is simply made by applying water repellency and calendaring to a high-density fabric that uses ultra-fine filaments for warp and warp yarns. This makes it easier to control the humidity inside the clothes due to sweating when working in the rain or exercising.

This has made it possible to perform even more strenuous exercise and work in comfort, but to this day, fabrics with a water pressure resistance of 1,500 or higher and a moisture permeability of 7,000g/rJ/24hrs or higher are still available. The reality is that this has not yet been achieved. The present invention was made in view of the current situation, and aims to obtain a highly moisture permeable waterproof fabric that has a water pressure resistance of 1,500 mm or more and a moisture permeability of 7,000 g/rrr/24 hrs or more. It is something. In order to achieve this object, the present invention has the following configuration.

That is, the present invention is directed to ``after applying a resin solution consisting of a polyamino acid urethane resin, a polyurethane resin, and a polar organic solvent to one or both sides of a fiber base material.

A method for producing a moisture-permeable waterproof fabric, which comprises immersing the fiber base material in water at 0°C to 30°C, then washing with hot water, and after drying, applying a water repellent and further applying a polysiloxane resin. ” is the gist.

The present invention will be explained in detail below.

The fiber base materials used in the present invention include polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, polyvinyl alcohol synthetic fibers, and polyvinyl alcohol synthetic fibers. Examples include woven and two-knit fabrics made of semi-synthetic fibers such as triacetate and mixed fibers such as nylon 6/cotton and polyethylene teracrate/cotton.

In the method of the present invention, first of all, polyamino acid urethane resin,
Apply a resin solution consisting of polyurethane resin and polar organic solvent.

Polyamino acid urethane resin (hereinafter referred to as PAU) used in the present invention
It's called resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine and L-alanine.
-Aspartic acid, L-cystine, L-glutamic acid,
Glycine, L-lysine.

■7-Methionine, L-leucine and their derivatives are mentioned, and when synthesizing polyamino acids, the amino acid N-carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride) obtained from amino acids and phosgene
-Carboxylic acid anhydride is called NCA. ) is commonly used. Polyurethane uses aromatic diisocyanate as its isocyanate component.

Aliphatic diisocyanates and cycloaliphatic diisocyanates may be used alone or in mixtures thereof.1 For example, toluene2
Examples include 4-diisocyanate, 4,4°-diphenylmethane diisocyanate, 1-6-hexane diisocyanate, 1,4-cyclohexane diisocyanate-1, and the like. In addition, the polyol component is polyether polyol.

Polyester polyols are used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols include ethylene glycol. Examples include reaction products of diols such as propylene glycol and dibasic acids such as adipic acid and sebadinic acid, and ring-opening polymers such as caprolactone. The amines used in the copolymerization of the amino acid and the amino acid include ethylenediamine, diethylamine, ethylamine, ethanolamine, and the like.

As described above, PAU resins are obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymers having isocyanate groups at the terminals. The PAU
Optically active γ-alkyl glutamate-NCA is preferably used as the amino acid component constituting the resin from the viewpoint of film performance, and among the optically active T-alkyl glutamates, T-methyl-glutamate is preferred from the viewpoint of price and film properties. NCA or γ-methyl-D-glutamate is often advantageously selected as the amino acid component of the PAD resin. In order to obtain the porous membrane of the present invention, it is advantageous to use a uniform resin composition made of a water-soluble solvent system from the viewpoint of both coating properties and wet film forming properties. As such a resin composition, a reaction product of an optically active γ-alkyl-glutamate-NCA and a urethane prepolymer among PAU resins is preferably used, but this is because the above-mentioned reaction product is a solvent system mainly composed of a polar organic solvent. For example, in a mixed solvent system of dimethylformamide and dioxane, the weight ratio of amino acid to urethane is 90:10-10:
This is because the above weight ratio can be freely selected while taking into consideration the physical properties of the film required to obtain a uniform resin solution over a wide range of 90%.

The amount of PA (I resin) attached to the fiber base fabric is 5g in pure form.
It is desirable that the amount of adhesion is less than 5 g/J, and it is difficult to obtain a water pressure resistance of 1,500 mm or more.

On the other hand, in the case of a conventional moisture permeable waterproof fabric having a porous urethane resin film, when the water pressure resistance is 150 On+m or more, the moisture permeability is at most 5000 g/rd・24 hrs.
On the other hand, when applying moisture coating to PAU resin, the water pressure resistance is 1500n.
v or more and moisture permeability 7000g/rrr ・24h
It is possible to obtain the surprising result of exhibiting moisture permeable and waterproof performance of RS or higher. The reason why high water pressure resistance and high moisture permeability can be obtained by wet coating processing of PAU resin is not obvious, but when observing the cross section of the membrane of the obtained moisture-permeable waterproof fabric, compared to polyurethane membrane, P
In the case of the AU resin film, the microcells are small, many in number, and uniformly distributed, which is thought to be a factor in providing high moisture permeability and high water pressure resistance. Furthermore, the high affinity of PAU resin itself for water vapor may be one of the driving forces behind its high moisture permeability.

Next, the polyurethane resin according to the present invention is a polymer obtained by reacting a polyisocyanate and a polyol. As the polyisocyanate, known aliphatic and aromatic polyisocyanates can be used. For example, hexamethylene diisocyanate, toluene diisocyanate, etc. Mention may be made of xylene diisocyanates and the reaction products of their excess with polyhydric alcohols. As the polyol, known polyethers, polyesters, and other polyols used in the production of ordinary polyurethane resins can be used. Examples of polyesters include reaction products of polyhydric alcohols such as ethylene glycol, diethylene glycol or 1,4-butanediol and polybasic carboxylic acids such as adipic acid, oxalic acid or sebacic acid.

Examples of polyether include polyhydric alcohols such as ethylene glycol and propylene glycol to which one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added (-1).

The amount of polyurethane resin used is preferably 1% to 200% based on the PAU resin.

If the amount used is less than 1%, moisture permeability will be poor, and if it is more than 200%, waterproofness will be poor.

The method of the present invention is to obtain a fabric with excellent water pressure resistance and moisture permeability, and its principle is to create numerous pores large enough to prevent water from passing through in the PAU resin film, which has relatively good moisture permeability. This is due to

When polyurethane resin and PAU resin are immersed in water at the same time, PAII resin solidifies faster than polyurethane resin, so a space is created at the boundary between PAU resin and polyurethane resin, and this space determines the size of the pores in the resin film. do. If the amount of polyurethane resin is small, the pores will be small and the moisture permeability will be poor.

Moreover, if the amount of polyurethane resin is large, the pores will become large and the water pressure resistance will be poor.

In the present invention, the above-mentioned PAII resin and polyurethane resin are used in combination with a polar organic agent. Polar organic solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylenephosphonamide. These substances are highly soluble in water,
When a polar organic solvent solution of a water-insoluble resin is immersed in water, only the polar organic solvent dissolves in the water, and the resin solidifies in the water.

A resin coagulation method using such a method is generally called a wet coagulation method. When a resin is coagulated by a wet coagulation method, a trace amount of the polar organic solvent present in the resin is eluted into water, so a resin having countless micropores can be obtained.

The resin solution consisting of 1'A[I resin, polyurethane resin, and polar organic solvent may be applied to the fiber base fabric by a conventional coating method. Generally, the coating thickness of the resin is 10 to 300 μm due to machine performance.

After applying the resin solution to the fiber substrate, the fabric is immersed in water. As mentioned above, this process makes it possible to form a PAU resin film with countless pores, and the action of the polyurethane resin makes it possible to obtain pores of an appropriate size that provide good moisture permeability and water pressure resistance. can.

When immersing the fabric in water, the water temperature should be in the range of 0 to 30℃; if the water temperature exceeds 30℃, dimethylformamide will diffuse into the water faster and the pores of the resin film will become larger, resulting in lower water resistance. becomes defective. Also, the soaking time is 3
0 seconds or more is required, and if it is less than 30 seconds, the solidification of the resin will be insufficient and a satisfactory PAtl resin film will not be obtained.

After coagulating the PAU resin in water, the fabric is washed with hot water to remove any remaining solvent. The hot water washing conditions vary depending on the amount of PAU resin and polyurethane resin used, but
It is sufficient to carry out the treatment at a temperature of 0° C. for 3 minutes or more.

After washing with hot water and drying, a water repellent agent is applied to the fabric, and a polysiloxane resin is further applied to the fabric. By applying a water repellent, the surface of the fabric can be made water repellent, and a moisture permeable waterproof fabric with a water pressure resistance of 1.500 or more can be obtained. There are various types of water repellents such as paraffin-based, silicon-based, and fluorine-based water repellents, and in the present invention, they may be selected as appropriate depending on the application. If particularly good water repellency is required, use a fluorine-based water repellent.
After applying a water repellent and drying, heat treatment is performed.

Further, in order to increase the durability of water repellency, a resin such as melamine resin may be used in combination. The water repellent may be applied by a commonly used padding method, coating method, spraying method, or the like. The polysiloxane applied after water repellent treatment includes dimethylpolysiloxane, phenyl group-containing polysiloxane, modified silicone oil such as amino-modified or olefin-modified polysiloxane, methylhydrogen polysiloxane, or a mixture of dimethylpolysiloxane and methylhydrogen polysiloxane. However, in the present invention, the molecular weight of dimethylpolysiloxane is 5,
000 to 30,000 is preferably used. This polysiloxane treatment first of all imparts smoothness to the fabric and coating, and can reduce abrasion damage to the coating due to friction between the fabrics. This smoothing effect also has the advantage of making it easy to put on and take off without using a lining. Second, the silicone resin adheres between the fabric structures and reduces the friction between the threads that make up the fabric, resulting in a softer texture. Since this polysiloxane treatment is performed after water repellent treatment, it may be applied in the form of an aqueous dispersion or emulsion, but in order to prevent treatment spots from occurring, 1.1.
1. -) Application with a chlorinated hydrocarbon such as dichlorethane, trichlorethylene, perchlorethylene, etc., and a solvent such as toluene, hexane mineral tarpe, etc. is preferably used.

The polysiloxane resin may be applied by a commonly used banding method, coating method, spraying method, or the like. The amount of polysiloxane attached is preferably 0.1% or more in terms of solid content based on the weight of the fibers.The present invention has the above configuration.1According to the present invention, the water pressure resistance is 1500 m.
m or more, yet has a moisture permeability of 7,000 g/n (・
A waterproof fabric with high moisture permeability of 24 hours or more can be obtained. The moisture-permeable waterproof fabric of the present invention is a material suitable for sports clothing and the like.

The present invention will be further explained below with reference to Examples.

The present invention is not limited to these.

Example 1 First, the polyamino acid urethane resin used in the two examples was manufactured by the following method.

Polytetramethylene glycol (01 (value 56.9) 1
970g and 1-6-hexamethylenecyisocyanate 1-
504 g was reacted at 90° C. for 5 hours to obtain a urethane prepolymer (NGO equivalent: 2340) having isocyanate 1 groups at the terminals. 85g of this urethane prepolymer,
! : Dissolve 485 g of r-methyl-L-glutamate-NG in 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio -7/3), add 50 g of 2% 1-ethylamine solution while stirring, and react at 30°C for 5 hours. When this was carried out, a polyamino acid urethane resin solution having a viscosity of 32,000 cps (25° C.) and a yellowish brown emulsion with good fluidity was obtained. This polyamino acid urethane resin is used in Formulation 1 described below. Here, the warp is nylon 70 denier/24 filament.

A plain woven fabric (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch using nylon 70 denier/34 filament as the weft was prepared, and after scouring and dyeing with acid dye using the usual method. .

Temperature 170 using a calendaring machine with a mirror roll
℃, pressure 30 kg/cm, and speed 20 m/min, calender processing was performed, and then a coating solution with a resin solid content concentration of 20% shown in the following recipe 1 was applied using a knife over roll coater at a f=190 g/port. After coating, the resin was immersed in a 20°C water bath for 1 minute to solidify the resin.

Formulation 1 Polyamino acid urethane resin 100 parts CRISV
ON AW-7810 parts (polyurethane resin.

Dainippon Ink Chemical Co., Ltd.) Dimethylformamide 20 parts Here 60
After immersing in warm water at ℃ for 10 minutes, and then drying, pa-noting (squeezing ratio 30%) was performed with a 5% aqueous solution of Asahi Guard 710 (a product of Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion. Heat treatment was performed at 160°C for 1 minute, followed by punting with a mineral turpentine solution containing 4% dimethylpolysiloxane-based Shin-Etsu silicone oil KF-96 (product of Shin-Etsu Chemical Co., Ltd.) (squeezing ratio 30%).
) and heat-treated at 130° C. for 3 minutes to obtain a moisture-permeable waterproof fabric of the present invention.

For comparison with the method of the present invention, a comparative sample was prepared according to the comparative example described below, and the performance was compared with one product of the present invention. The results are shown in Table 1 together with the performance of the product of the present invention.

The performance was measured and evaluated using the following method.

Water pressure resistance is JIS-L-1041 low water pressure method, moisture permeability is J
Peeling resistance was determined according to IS-Z-0208, and the peeling resistance was evaluated using a Gakushin type friction fastness tester by rubbing 1000 times at a load of 200 g, observing the appearance of the fabric, and performing the following two-stage evaluation.

0---1 No peeling at all×---1～・Peeling observed As is clear from Table 1, 1 The moisture permeable waterproof fabric produced by the method of the present invention has a water pressure resistance of 2.000 mm or more. Despite this, its moisture permeability is 10,500g/rrr・hr
It can be seen that it has both excellent moisture permeability and waterproof performance, and has excellent peeling resistance.

Table 1 Comparative Examples A nylon tack fabric of the same specifications as Example 1 was prepared, and after scouring and calendering was performed in the same manner as in Example 1, a coating solution shown in the following formulation 2 was applied with a knife over roll. The coating was applied using a coater at a coating amount of 90 g/bottom. The polyamino acid urethane resin in Formulation 2 was the same as that used in Example 1.

Formulation 2 Polyamino acid urethane resin 100 parts Dimethylbormamide 20 parts After coating, coagulation was performed in the same manner as in Example 1.

Washing, drying, and water repellent treatment using a fluorine fiber water repellent were performed.

As shown in Table 1, the obtained one-fabric structure had good waterproof performance, but poor moisture permeability. Furthermore, the peeling resistance was poor, with the coating on friction areas completely peeling off and the base fabric being exposed.

Claims (1)

[Claims] (1) Polyamino acid urethane resin, polyurethane resin,
After applying a resin solution consisting of and a polar organic solvent to one or both sides of the fiber base material, the fiber base material is immersed in water at 0 ° C to 30 ° C., then washed with hot water, and after drying, a water repellent is applied, A method for producing a moisture-permeable waterproof fabric, which further comprises adding a polysiloxane resin.