JPH03213582A - Moisture-permeable waterproof cloth having excellent wear resistance - Google Patents

Abstract

PURPOSE:To obtain the subject cloth having excellent wear resistance by forming a porous moisture-permeable film of a polyamino acid urethane resin on a piece of cloth and forming a non-porous moisture-permeable film comprising a polyurethane resin containing reaction product powder of L-lysine and an organic acid, etc. CONSTITUTION:A solution of a polyamino acid urethane resin is applied on fiber cloth composed of a synthetic fiber or a semi-synthetic fiber, etc., and coagulated to form a moisture-permeable film having fine pores. Then, a solution of a polyurethane resin or a polyamino acid urethane resin containing >=0.1wt.% flake powder as a reaction product of L-lysine and an organic acid (preferably N<epsilon>-lauroyl-L-lysine) is applied on said film, thus a moisture-permeable film of non-porous character is formed by a dry method to afford the objective moisture-permeable waterproof cloth having excellent wear 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. A moisture-permeable waterproof fabric with a non-porous membrane on the surface of the fabric has excellent waterproof performance, but low moisture permeability; on the other hand, a moisture-permeable waterproof fabric with a porous membrane on the surface of the fabric has poor moisture permeability. Good, but not waterproof enough. In addition, those with non-porous moisture permeable membranes have pores with a diameter of 1 to 3 on the membrane surface.
Washing resistance is better than that using a porous membrane with continuous fine pores that allow microscopic water vapor to escape.

It is known as a moisture-permeable waterproof fabric with excellent abrasion resistance.

However, when a windbreaker was sewn using such a moisture-permeable waterproof fabric and a two-wear test was conducted, it was discovered that the film was abraded by underwear, damaging the film. For this reason, attempts have been made to make the film thicker, but it has been found that in this case, good moisture permeability cannot be obtained and the improvement in abrasion resistance is insufficient.

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 that has excellent moisture permeability and waterproof performance, and also 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 provides ``a porous moisture-permeable membrane made of a synthetic polymer mainly composed of polyamino acid urethane resin on a fiber fabric, and a flat plate-like membrane made of a reaction product of L-lysine and an organic acid on the moisture-permeable membrane. A moisture-permeable waterproof fabric with excellent abrasion resistance characterized by having a non-porous moisture-permeable membrane made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin containing 0.1% by weight or more of powder. The main points are as follows.

The present invention will be explained in detail below.

The moisture-permeable waterproof fabric of the present invention has a porous moisture-permeable membrane made of a synthetic polymer mainly composed of polyamino acid urethane resin as a first resin layer on a fiber fabric.

The fiber fabric used here is polyamide synthetic fiber represented by nylon 6 and nylon 66.

A two-knit fabric made of polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, polyvinyl alcohol synthetic fibers, semi-synthetic fibers such as triacetate, or blended fibers such as nylon 6/cotton and polyethylene terephthalate/cotton. ,
Examples include nonwoven fabrics.

In the present invention, these fiber fabrics may be treated with a water repellent agent. In this case, the water repellency of the fabric is determined by JIS
It is desirable to have a water repellency of 90 or more by the L-1096 spray method. The water repellent used may be a known one such as a paraffin-based water repellent, a polysiloxane-based water repellent, or a fluorine-based water repellent, and the treatment may be carried out by a commonly used known method. . If particularly good water repellency is required, use a fluorine-based water repellent.
% aqueous solution (squeezing ratio 35%), 160℃
This may be carried out by a method of performing heat treatment for 1 minute at .

Polyamino acid urethane resin (hereinafter referred to as P) used in the present invention
It is called AD resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine and L-aspartic acid.

Examples include L-cystine, L-glutamic acid, glycine, tolylene, L-methionine, L-leucine and their derivatives. When synthesizing polyamino acids, amino acid N-carboxylic acid anhydride obtained from amino acids and phosgene ( N-carboxylic acid anhydride (hereinafter referred to as NCA) is generally used, but optically active γ-alkyl glutamate-NCA is particularly preferred from the viewpoint of film performance. L-glutamate NCA or T-methyl-D-glutamate NCA is often advantageously selected as the amino acid component of the PAU resin.

On the other hand, the polyurethane used is a urethane prepolymer having an isocyanate group at the end, which is obtained by reacting an isocyanate and a polyol under conditions where the equivalent ratio NGO10H>1.

As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in mixtures thereof. For example, tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate. , 4-cyclohexane diisocyanate, and the like. Further, as the polyol component, polyether polyol, polyester polyol, etc. are used. Polyether polyols include polyethylene glycol and polypropylene glycol.

Examples of polytetramethylene glycol include polyester polyols such as ethylene glycol,
Examples include reaction products of diols such as propylene glycol and dibasic acids such as adipic acid and cepatic acid, and ring-opening polymers such as caprolactone.

The amines used in the copolymerization of amino acids and polyurethane include hydrazine, ethylenediamine, diethylamine, and triethylamine.

Ethanolamine etc. are used.

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.

As the polymerization solvent used in the synthesis of PAUI fat, a solvent was selected that satisfies two points: it is a polymerization solvent for the amino acid NCA and does not contain active hydrogen, and it can dissolve the urethane prepolymer having terminal isocyanate groups. Examples of such solvents include cyclic ethers such as dioxane and tetrahydrofuran, acetate esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, and polar amide solvents such as dimethylformamide and N-methylpyrrolidone. These can be used as a single solvent or as a mixed solvent. Particularly preferred among these solvent systems are those that dissolve or uniformly disperse the polymer composition to be produced, such as dimethylformamide alone, a mixed solvent of dimethylformamide and dioxane, or a mixed solvent of methyl ethyl ketone and dimethyl formamide. can be mentioned. These solvents are also excellent in terms of stability and coatability of the resin solution when producing a urethane resin film or PAU resin film by coating.

In the present invention, in order to form a porous moisture-permeable membrane as the first resin layer on a fabric, the above-mentioned PAU resin is coated on a fiber fabric using a conventional coating method 1, such as a knife coater, comma coater, reverse coater, etc. After coating, it is preferable to solidify the resin by immersing it in an aqueous solution, followed by washing in warm water and drying to form a moisture-permeable membrane having micropores. This is a so-called wet coagulation method.

The moisture-permeable waterproof fabric of the present invention contains 0.1% by weight or more of a tabular powder that is a reaction product of L-IJ amine organic acid on the porous moisture-permeable membrane thus formed. It has a non-porous moisture permeable membrane made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin. In order to form a non-porous resin film, a method may be adopted in which a solution of the above-mentioned resin is applied by a conventional coating method and the solvent is removed.

The polyurethane resin used here is a reactant containing a polyol having a hydroxyl group at both ends, an organic diisocyanate, and a chain extender.

Examples of the polyol component include polyether polyols, polyester polyols, and mixtures or copolymers thereof.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of polyester polyols include diols such as ethylene glycol, propylene glycol, and hexamethylene glycol, and adipic acid and cepatic acid.

Examples include polycondensates of dibasic acids such as maleic acid and terephthalic acid, and ring-opening polymers such as caprolactone and lactonic acid.

As the organic diisocyanate component, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in mixtures thereof. For example, tolylene-2,4-diisocyanate, 4,4°-
Examples include diphenylmethane diisocyanate, 1.6-hexane diisocyanate, and 1.4-cyclohexane diisocyanate.

Examples of the chain extender include compounds having active hydrogen, such as diols such as ethylene glycol, propylene glycol, and hexamethylene glycol, and diamines such as ethylene diamine, metaphenylene diamine, and naphthylene diamine.

The synthetic polymer mainly composed of polyamino acid urethane resin used here is the same as the synthetic polymer used in the first resin layer described above.

Furthermore, the reaction product of L-lysine and an organic acid used in the present invention is L-! J Lysine Organic Acids 9 For example, propionic acid, acetic acid, isoacetic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, succinic acid, adipic acid, fumaric acid,
maleic acid, phthalic acid, myristic acid, palmitic acid,
stearic acid, oleic acid, linoleic acid, lauric acid,
It is a reactant with lyric acid, etc., and L-lysine-alkyl acid-based reactants are preferable in view of its performance. Among them, the effect of Nε-lauroyl-lysine is particularly remarkable.

The above-mentioned 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 1 in the thickness direction.
Powder with a particle diameter of 0 μ or less is preferably used.

Also, L-! The amount of the flat powder, which is a reaction product of the J-lysine organic acid, may be appropriately selected depending on the intended use of the fabric. Bye. In particular, in order to efficiently develop wear resistance, it is preferable to concentrate the above-mentioned tabular powder on the surface layer of the moisture-permeable resin film.

More preferably, a moisture permeable resin not containing the above powder is applied onto a fabric, a moisture permeable film is formed by a wet method, and then the above powder is contained on the moisture permeable film. Coat with resin,
The best method is to form a thin film using a dry method to obtain 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. Furthermore, the reaction product of L-lysine and an organic acid also has antibacterial properties due to its chemical structure.

The present invention has nine or more configurations, 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) In the moisture permeable waterproof fabric of the present invention, a microporous moisture permeable membrane made of PAU resin (polyamino acid urethane resin) is formed as a first resin layer on a fiber fabric. This moisture permeable membrane has very good moisture permeability due to its porosity and the moisture permeability inherent to PAU resin, but its water pressure resistance is insufficient (approximately 0.2 kg/c/c). It is. Therefore, in one aspect of the present invention, a non-porous moisture permeable membrane made of polyurethane resin or PAU resin is formed as a second resin layer on the moisture permeable membrane.

With this structure, the water pressure resistance can be dramatically improved due to the non-porous property of the moisture permeable membrane, and the moisture permeability of the non-porous membrane itself can be improved simply by adjusting the membrane thickness to be thin. By doing so, moisture permeability can be maintained at a good level without significantly reducing the overall moisture permeability.

Furthermore, in the present invention, since the non-porous membrane is mixed with powder which is a reaction product of L-lysine and an organic acid, the abrasion resistance is very good. Why is it possible to obtain excellent wear resistance by incorporating a tabular powder made of a reaction product of L=lysine and an organic acid? The present inventors speculate as follows regarding the reason.

The above-mentioned powder is flat and easily intersects between walls.

When dispersed and mixed in a resin solution for moisture-permeable membranes, it peels off thinly.

When a resin solution is applied, the powder lines up parallel to the coated surface.

And it becomes multi-layered. The reaction product of L-lysine and an organic acid has excellent lubricity, so when it is included in a resin film, the surface of the resin film has good lubricity and wear resistance is reduced. Furthermore, since the above-mentioned flat powder itself is a reaction product of amino acids and organic acids, it should be compatible with moisture permeable membrane resins, especially PAU resins.

It is presumed that excellent wear resistance can be obtained by the synergistic effect of these.

(Example) Next, the present invention will be explained in more detail with reference to an example, in which the performance of the fabric in the example was measured.

Evaluation was performed using the first method.

(1) Moisture permeability According to JIS z-0208.

(2) Water pressure resistance Based on JIS L-1092 (high water pressure method).

(3) Abrasion resistance Measured and evaluated using the following method in accordance with JIS L-1084 (A, -1 method).

Cotton cloth (JISL-0803
Lay two sheets of attached white cloth for color fastness specified in 4) on top of each other and place the nails on the arc surface.

Next, a sample (5 cm x 5 cm) was attached to the 45R friction element with the resin film side facing out, and the change in appearance was observed after rubbing it 5000 times at a speed of 30 times per minute on a cotton cloth with a total load of 200 gf. The following 4-level evaluation was performed.

◎: No change in appearance ○: Almost no peeling due to wear △: Slight peeling due to wear ×: Total peeling due to wear Example 1 In this example, N was used as the reactant of L-IJ lysine organic acid.
A moisture permeable waterproof fabric of the present invention was produced using 8-lauroyl-cyo-lysine in the following manner.

First, a plain woven fabric (tuck) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch using nylon 70 denier/34 filament for both the warp and weft was prepared as a base fabric. After dyeing, pat with a 5% aqueous solution of Fluorine Repellent 15 and water emulsion Azahi Guard 710 (manufactured by Asahi Glass Co., Ltd.) (squeezing ratio 35%) L
, heat treatment was performed at 160° C. for 1 minute. Next, calendering was performed using a calendering machine with mirror-finished rolls at a temperature of 160° C., a pressure of 30 kg/cm, and a speed of 20 m/min. Subsequently, a PAU resin solution with a resin solid content concentration of 23% in Formulation 1 below was applied onto the above-mentioned base fabric using a knife over roll coater at a coating amount of 100 g/m', and then soaked in an aqueous solution at 15°C for 60 seconds. After soaking to solidify the resin and subsequently washing in 50°C warm water for 5 minutes,
By drying (wet method), a moisture permeable membrane having micropores was formed on the base fabric.

[Formulation 1] 20 parts of MF Next, on the formed moisture-permeable membrane having the above-mentioned micropores, treatment liquids shown in Formulations 2 to 4 in Table 1 below (urethane resin or polyamino acid urethane resin with L-lysine A coating amount of 40 g/m was applied using a knife-over roll coater.
'After applying.

It was dried at 70° C. for 5 minutes to form a non-porous moisture permeable membrane (film thickness: 5 μm) using a dry method. The three obtained moisture-permeable waterproof fabrics of the present invention were each treated with Invention 1 (Formulation 2) 1
Present invention 2 (formulation 3) 1 Present invention 3 (formulation 4).

(The following is a blank space) = 17 Table 9 Prescriptions 2 and 3 used in this example for comparison with the present invention. Three comparative moisture-permeable waterproof fabrics (Comparative Examples 1, 2, and 3, respectively) were prepared in exactly the same manner as in Example 2, except that Nε-lauroyl-L-1 gin was omitted from Formulation 4.
shall be. ) was manufactured.

Performance of the moisture permeable waterproof fabrics of the present invention and comparative examples 8- Measure and evaluate.

The results are shown in Table 2.

Table 2 In Table 2, 1 Invention 1. 2. Comparative Example 1. 2. As is clear from comparison with the performance of No. 3, all of the moisture permeable waterproof fabrics of the present invention have excellent moisture permeability and waterproof properties, and without impairing their performance.
It can be seen that it also has good wear resistance.

(Effects of the Invention) The moisture permeable waterproof fabric of the present invention has excellent moisture permeability and waterproof properties, and also has good abrasion resistance without impairing its performance.

Due to its excellent performance, the moisture permeable waterproof fabric of the present invention is a material particularly suitable for raincoats, mountain climbing clothes, and various other sports clothing.

Claims (1)

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