JPH04194082A - Moisture-permeable water-proofing cloth having excellent abrasion resistance - Google Patents

Abstract

PURPOSE:To obtain a moisture-permeable water-proofing cloth having excellent abrasion resistance by forming a porous moisture-permeable membrane, composed of a fluorine-modified polyurethane resin containing flaky powder consisting of a reaction product of L-lysine and an organic acid on a textile cloth. CONSTITUTION:A water-repellent is impregnated in a textile cloth made of synthetic fiber. The obtained cloth is coated with a solution of a fluorine- modified polyurethane resin containing >=0.1wt.% of flaky powder produced by reacting an L-lysine (preferably Nepsilon-lauroyl-L-lysine) with an organic acid (e.g. propionic acid or butyric acid) and the coating layer is coagulated in wet state to obtain the objective cloth having high moisture-permeability and water- proofing property and exhibiting excellent abrasion resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a moisture-permeable waterproof fabric having excellent abrasion resistance.

(Prior Art) Conventionally, moisture permeable waterproof fabrics having a moisture permeable membrane on the surface of the fabric have been known to have either porous or non-porous moisture permeable membranes. In particular, those with non-porous moisture-permeable membranes have superior washing resistance and abrasion resistance compared to porous membranes with continuous micropores with a pore size of 1 to 3 μm on the membrane surface that are large enough to allow water vapor to escape. It is known as a moisture-permeable waterproof fabric. however.

Windbreaker using such moisture-permeable waterproof fabric
When the garment was sewn and a wearing test was conducted, there was a problem in that the film was abraded by underwear, damaging the film and significantly reducing its waterproof properties.

Attempts have been made to make the film thicker in order to improve this drawback, but in this case good moisture permeability cannot be obtained.

It has also been found that the improvement in wear resistance is not sufficient.

Silicon-containing compounds are also used as wear resistance improvers, but their effects are not sufficient, and so far they have excellent wear resistance and good moisture permeability.

At present, a moisture-permeable waterproof fabric with waterproof performance has not been obtained.

(Problem to be solved by the invention) The present invention was made in view of the above-mentioned current situation.

The object of the present invention is to obtain a moisture-permeable waterproof fabric using a nonporous membrane, which has excellent moisture permeability and waterproof performance, and has excellent abrasion resistance that prevents film damage due to abrasion during wear.

(Means for Solving the Problems) The present invention achieves the above-mentioned objects and has the following configuration.

That is, 1 the present invention is a moisture-permeable waterproof fabric having a porous moisture-permeable membrane made of a synthetic polymer mainly composed of fluorine-modified polyurethane resin on a fiber fabric, wherein the moisture-permeable membrane contains L-lysine and an organic acid. A moisture-permeable waterproof fabric with excellent abrasion resistance characterized by containing 0.1% by weight or more of a flat plate-shaped powder as a reactant.''

The present invention will be explained in detail below.

The fiber fabrics 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 triacetate synthetic fibers. Synthetic fiber or nylon 6/cotton, polyethylene terephthalate/
Examples include woven fabrics, knitted fabrics, non-woven fabrics, etc. made of mixed fibers such as cotton.

In the present invention, the above-mentioned fiber fabric may be treated with a water repellent, and this is effective as a means for preventing the resin solution from penetrating into the fabric during coating, which will be described later. The water repellent used may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment may be carried out by a commonly used known method. Especially when good water repellency is required.

Using a fluorine-based water repellent9 For example, Asahi Guard 730
(Fluorine water repellent emulsion, manufactured by Asahi Glass) at 5%
After padding with an aqueous dispersion (squeezing ratio 35%), 160℃
This may be carried out by a method of performing heat treatment for 1 minute at .

In the present invention, a porous moisture-permeable membrane made of a synthetic polymer mainly composed of fluorine-modified polyurethane resin is formed on the above-mentioned fiber fabric, and the moisture-permeable membrane contains a reaction product of L-lysine and an organic acid. It contains 0.1% by weight or more of tabular powder.

The synthetic polymer mainly composed of fluorine-modified polyurethane resin as used herein refers to one containing 50 to 100% of fluorine-modified polyurethane resin as one synthetic polymer.

Other synthetic polymers include generally known polyurethane resins that are not fluorine-modified, polyacrylic acid, polyvinyl chloride, polystyrene, polyamino acid urethane, polyamino acids, or copolymers thereof, etc., in a range of less than 50%. May contain.

Fluorine-modified polyurethane resins can be obtained by copolymerizing polyurethane and a fluorine-containing synthetic polymer through a polymer reaction, or by introducing a functional group into polyurethane in advance and causing it to undergo a chemical reaction with a fluorine compound. can. The fluorine content of the fluorine-modified polyurethane resin may be appropriately selected depending on the intended use, but is usually preferably 5 to 50%.

Here, as the polyurethane, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used singly or as a mixture thereof as the isocyanate component.
6-hexanes diisocyanate, 1,4-cyclohexane diisocyanate, etc., and as a polyol component.

Polyether polyols and polyester polyols are used. Polyether polyols are made of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols are made of diols such as ethylene glycol and propylene glycol and dibases such as adipic acid and cepatic acid. A reaction product with an acid or a ring-opening polymer such as caprolactone is used.

Examples of fluorine-containing synthetic polymers include polyfluorinated ether polyols obtained from 2-hydroperfluoroethyl vinyl ether, 2-hydroperfluoroallyl ether, 2-hydroperfluoroethyl glycidyl ether, hexafluoropropylene oxide, etc.
Other polyvinyl fluoride, polyvinylidene fluoride, polyhexafluoropropylene, polytrifluoroethylene.

polytetrafluoroethylene, polyfluorinated acrylic acid,
Polyfluorinated methacrylic acid, polyfluorinated amino acid, etc. are used.

As a method for copolymerizing polyurethane and a fluorine-containing synthetic polymer9, for example, when reacting the isocyanate group (-NGO) of polyurethane with a fluorine-containing synthetic polymer, active hydrogen is added to the terminal of the fluorine-containing synthetic polymer. It is sufficient to introduce a functional group having the following, and the functional group is a hydroxyl group.

An amino group, a carboxyl group, etc. are used.

In the present invention, for the purpose of improving wear resistance, a solution of a synthetic polymer mainly composed of the above-mentioned fluorine-modified polyurethane resin contains a tabular powder which is a reaction product with an L-'J lysine organic acid.

In producing the moisture-permeable waterproof fabric of the present invention, this solution is applied onto a fiber fabric by a conventional coating method 1, for example, using a knife coater, comma coater, reverse coater, etc., and then wet-coagulated. A so-called wet method is used, or a synthetic polymer mainly composed of fluorine-modified polyurethane resin is modified in advance into a system that is easily foamable mechanically or a W/○ type emulsion system, and this modified solution is applied onto a fiber fabric and dried. This is done using a so-called dry method.

What is the reaction product of lysine and organic acid used in the present invention? lj
1 and organic acids such as propionic acid.

Butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, succinic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, myristic acid.

It is a reactant with palmitic acid, stearic acid, oleic acid, linoleic acid, lauric acid, linuric acid, etc., and an L-lysine-alkyl acid-based reactant is preferable from its performance. Among them, the effect of Nε-lauroyl-lysine is particularly remarkable.

The above flat powder has a ratio of length direction to thickness direction of 3:1.
It is a white crystalline powder, which can be made into a fine powder by pulverization, but it is usually less than 50μ in the length direction and 1μ in the thickness direction.
Powders with a particle diameter of 0 μ or less are preferably used.

Also, L-! The amount of the flat powder, which is a reaction product of the J-lysine organic acid, may be determined as appropriate depending on the intended use of the fabric, but it is usually sufficient to uniformly disperse 0.1% by weight or more in the moisture-permeable resin. . In particular, in order to efficiently develop wear resistance,
It is preferable to concentrate the flat powder on the surface layer of the moisture-permeable resin film. More preferably, a moisture-permeable resin not containing the powder is applied onto a fabric, a moisture-permeable film is formed by a wet method or a dry method, and then the powder is contained on the moisture-permeable film. A good method is to apply a moisture-permeable resin and form a thin film using a wet or dry method to create a two-layer structure.

In this case, it is desirable that the content be 1% by weight or more of the moisture permeable resin for forming the second layer, and 0.1% by weight or more of the total moisture permeable resin. Also, L-! The reactant of J-lysine organic acid also has antibacterial properties due to its chemical structure.

The present invention has the above configuration, and according to the present invention, a moisture permeable waterproof fabric having high moisture permeability, waterproof performance, and excellent abrasion resistance can be obtained.

(Function) The moisture-permeable waterproof fabric of the present invention has excellent abrasion resistance by containing tabular powder, which is a reaction product of L-lysine and an organic acid, in a synthetic polymer mainly composed of fluorine-modified polyurethane resin. This gives it performance. Furthermore, the plate-shaped powder, which is a reaction product of L-lysine and an organic acid, hardly reduces the performance of the moisture permeable membrane, and therefore has excellent moisture permeability and waterproof performance.

Why is it possible to obtain excellent wear resistance by containing a tabular powder made of a reaction product of L-lysine and an organic acid?1 The present inventors speculate as to the reason as follows. .

The above powder is in the form of a flat plate with a space between the walls.

When dispersed and mixed in a resin solution for a moisture-permeable membrane, it peels off thinly, and when the resin solution is applied, the powder is arranged parallel to the coated surface and becomes multilayered. Since the reaction product of L-lysine and an organic acid has excellent lubricity, when this is included in a resin film, the surface of the resin film has good lubricity.

Therefore, it is presumed that excellent wear resistance can be obtained.

In addition, in the present invention, a synthetic polymer mainly composed of fluorine-modified polyurethane resin is used as the resin for the porous moisture-permeable membrane. In addition to the oil action, it also has excellent abrasion durability due to the action of the flat powder, and there is little loss of waterproof performance due to washing.

(Example) Next, the present invention will be specifically explained with reference to 9 Examples, and the measurement and evaluation of the performance of the fabric in the Examples will be explained below.

This was done using the following method.

[1) Water pressure resistance JIS L-1096 (low water pressure method) and JIS
By L-1092 (high water pressure method).

Before washing and home washing (JIS L-0217゜103
Method) Measure the sample after 10 washes.

(2) Moisture permeability JIS L-1099A-1 method (3) Abrasion resistance JIS L-1084 (A-1 method) Example 1 First, fluorine-modified polyurethane resin (hereinafter referred to as F-PU resin) was prepared using the following method. Manufactured.

Polytetramethylene glycol (OH value 56.9) 19
70g and 1,6-hexamethylene diisocyanate) 50
4g was reacted at 90°C for 5 hours to obtain urethane brepoly7- (NCO equivalent: 23
40) was obtained. 85 g of this urethane prepolymer and 21 g of a vinyl fluoride polymer with a hydroxyl group introduced at the end were dissolved in 415 g of a mixed solvent of dimethylformamide/dioxane (weight ratio 7/3), and 47 g of a 2% dimethylamine solution was added while stirring. The reaction was carried out at 30°C for 6 hours to obtain a yellow-brown F-PI resin solution with good fluidity and a viscosity of 52.0 DOcps (25°C).

Next, as a base fabric, nylon high multifilament 70 denier/68 filament was used for both the warp and weft, and the warp density was 120 threads/inch.

A plain woven fabric (taffeta) with a weft density of 90 threads/inch,
Prepare the product after scouring and dyeing with acid dye, and coat it with Asahi Guard 710, a fluorine-based water repellent emulsion.
(manufactured by Asahi Glass (6)) Padded with 5% aqueous solution (squeezing ratio 40%) L, dried at 100℃ for 2 minutes, then heated to 160℃ for 1
Heat treatment was performed for 1 minute.

Subsequently, using a calendar processing machine with mirror-finished rolls, the temperature was 170°C and the pressure was 35 kg/cl! , speed 30m/
Calendar processing was carried out under the conditions of 10 minutes.

Here, the resin solution shown in the following formulation 1 (solid content concentration 20%
) Using a knife over roll coater, apply 1 coat amount.
After coating at 00g/111'', the resin layer was immediately immersed in an aqueous solution at 15°C for 40 seconds to solidify the resin layer.

[Formulation 1] F-PU resistant resin 100 parts Nε-lauroyl-lysine 3B dimethylformamide
Subsequently, 15 parts of the fabric were washed in warm water at 50°C for 10 minutes, dried, and finished with a tenter at 170 tons for 1 minute to obtain a moisture-permeable waterproof fabric of the present invention.

For comparison with the present invention, formulations 1 to N in this example
A comparative moisture-permeable waterproof fabric (Comparative Example 1) was obtained in exactly the same manner as in this example except that ε-lauroyl-L-1 gin was used.

In addition, for comparison with the present invention, in 9 examples, formulation 1
Two comparative moisture-permeable waterproof fabrics (Comparative Example 2 and Comparative Example 3, respectively) were obtained in exactly the same manner as in this Example, except that the following formulations 2.3 were used instead of 0.

[Formulation 2] Dimethylformamide 20 parts [Formulation 3] Dimethylformamide 20 parts The performance of the moisture permeable waterproof fabrics of the present invention and comparative examples was measured and evaluated, and the results are shown in Table 1.

Table 1 As is clear from the results shown in Table 1, the moisture permeable waterproof fabric of the present invention has not only high waterproof performance and moisture permeability, but also excellent abrasion resistance. .

Example 2 After forming a moisture permeable membrane on a fabric according to the method of Comparative Example 1 above,
Further, a resin solution shown in the following formulation 4 was applied onto the moisture permeable membrane using a comma coater so that the dry film thickness was 4 μm, and dried at 80°C for 3 minutes. I got it.

[Formulation 4] Nε-lauroyl-cy-lysine 3 parts methyl ethyl ketone 15 parts toluene
15 parts water
30 parts 9 for comparison with the present invention 9 A comparative moisture-permeable waterproof fabric (Comparative Example 4) was prepared in the same manner as in this Example except that Nε-lauroyl-cysine was removed from Formulation 4 in this Example. I got it.

The performance of the moisture permeable waterproof fabrics of the present invention and comparative examples was measured and evaluated, and the results are shown in Table 2.

Table 2 As is clear from the results shown in Table 2, the moisture permeable waterproof fabric of the present invention has not only high waterproof performance and moisture permeability, but also excellent abrasion resistance. Even if a fluorine-modified polyurethane resin is applied first and then a resin containing a lysine compound is applied on top of that, good moisture permeability and
It was found that waterproof and wear-resistant performance can be obtained.

(Effects of the Invention) The moisture-permeable waterproof fabric of the present invention has a surface made of a synthetic polymer mainly composed of a fluorine-modified polyurethane resin containing tabular powder that is a reaction product of L-lysine and an organic acid. It is composed of a porous moisture permeable membrane, and the moisture permeable waterproof fabric of the present invention having such a structure not only satisfies high waterproof performance and moisture permeability, but also has excellent abrasion resistance. can be satisfied.

The moisture-permeable waterproof fabric of the present invention is a material particularly suitable for sports clothing and rainwear due to its excellent performance.

Claims (1)

[Claims] (1) A moisture-permeable waterproof fabric having a porous moisture-permeable membrane made of a synthetic polymer mainly composed of a fluorine-modified polyurethane resin on a fiber fabric, wherein the moisture-permeable membrane contains a reaction product of L-lysine and an organic acid. A moisture-permeable waterproof fabric with excellent abrasion resistance, characterized by containing 0.1% by weight or more of a certain tabular powder.