JPH03213581A - Moisture-permeable waterproof cloth having excellent wear resistance - Google Patents

Abstract

PURPOSE:To obtain the subject cloth having excellent wear resistance by laminating a moisture-permeable film comprising a synthetic polymer such as polyurethane resin containing at least a specific amount of flake powder of a reaction product of L-lysine and an organic acid to cloth through an adhesive. CONSTITUTION:For instance, a solution of a synthetic polymer of a polyurethane resin or a synthetic polymer mainly composed of polyamino acid urethane resin containing >=0.1wt.% flake powder as a reaction product of L-lysine and an organic acid (preferable example; N<epsilon>-lauroyl-L-lysine) is applied onto a piece of releasing paper to form a moisture-permeable film. Next, a solution of a polyurethane-based adhesive, etc., is applied on said moisture-permeable film and the resultant film is dried, then subjected to contact bonding with cloth made of nylon, etc., to afford the objective moisture-permeable waterproof cloth having excellent wear resistance. Said cloth is a material suitable for sports clothing or a raincoat.

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) Polyurethane resins, polyamino acid urethane resins, tetrafluoroethylene resins, and the like have been commonly used as materials for moisture permeable membranes for obtaining laminate type moisture permeable waterproof fabrics.

Regarding processing methods depending on the type of fabric, coating or laminating methods are used for woven and non-woven fabrics, and laminating methods are used for knitted fabrics.

Further, in order to increase moisture permeability, it is advantageous to employ a permeable membrane with pores (micropores), and in order to increase water pressure resistance, it is advantageous to employ a moisture permeable membrane without pores.

It is also known that the latter is superior in terms of washing resistance and abrasion resistance.

However, when a windbreaker was sewn using such a moisture-permeable waterproof fabric and a one-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 having excellent abrasion resistance that prevents film damage due to abrasion during wearing without impairing excellent moisture permeability and waterproof performance.

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

That is, 1 the present invention is rI, -! A 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 tabular powder, which is a reaction product of J-gin and an organic acid, is attached to a fabric through an adhesive. The gist is a moisture-permeable waterproof fabric with excellent abrasion resistance characterized by being laminated with

The present invention will be explained in detail below.

The synthetic polymer mainly composed of polyurethane resin used in the present invention is 60 to 10% polyurethane resin as one synthetic polymer.
Other synthetic polymers include polymers such as polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, and polyamino acids; It may contain a polymer or the like in an amount less than 40%.

The polyurethane resin used in the present invention is a reaction product containing a polyol having a hydroxyl group at both ends, an organic diisocyanate, and a chain extender. Examples of the polyol component include polyether polyol, polyester polyol, or a mixture or copolymer thereof, and examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. ,Also.

Examples of polyester polyols include polycondensates of diols such as ethylene glycol, propylene glycol, and hexamethylene glycol and dibasic acids such as adipic acid, cepatic acid, maleic acid, and terephthalic acid, and ring-opening polymers of caprolactone and lactonic acid. Things can be mentioned.

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 thereof include diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, and the like.

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 in the present invention includes not only one synthetic polymer containing 70 to 10% of polyamino acid urethane resin, but also 100% polyamino acid urethane resin. ) and other synthetic polymers such as block copolymers of poly γ-alkyl glutamate and butadi-5-ene, block copolymers of poly r-alkyl glutamate and leucine, etc., in a range of less than 30%. May contain.

Polyamino acid urethane resin used in the present invention (hereinafter referred to as
It is called PAU 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, and when synthesizing polyamino acids, 1r-mino acid N-carboxylic acid obtained from amino acids and phosgene. Anhydride (hereinafter N-carboxylic acid anhydride is referred to as NCA)
are generally used, but optically active γ-alkylglutamate-NCA is preferably used, particularly from the viewpoint of film performance.

Among them, T-methyl-L
-Glutamate-NCA or γ-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 incyanate 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.

Examples include 1,6-hexane diisocyanate and 1,4-cyclohexane diisocyanate.

Further, as the polyol component, polyether polyol, polyester polyol, etc. are used. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Examples of polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol and dibasic acids such as adipic acid and sepatic 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 ends.

The polymerization solvent used in the synthesis of the PAU resin is a polymerization solvent for the amino acid NCA that satisfies the following two requirements: it does not contain active hydrogen, and it can dissolve the urethane prepolymer having an incyanate group at the end. Examples of such solvents include cyclic ethers such as dioxane and tetraε-drofuran, 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 resulting polymer composition, such as Dimethy JL/9.
* Jl/A A single solvent of amide, a mixed solvent of dimethylformamide and dioxane, a mixed solvent of methyl ethyl ketone and dimethylformamide, etc. can be mentioned. These solvents are also excellent as solvents in terms of stability and coatability of resin solutions during the production of polyurethane resin films or PAU resin films by coating.

In the present invention, for the purpose of improving wear resistance, a tabular powder, which is a reaction product of L-lysine and an organic acid, is contained in the above-mentioned polyurethane resin or PAU resin, and a sheet-like material is formed by a wet method or a dry method. A moisture-permeable membrane is formed on top.

The reactant of I, IJ lysine organic acid used in the present invention is L
- Lysine and organic acids 9 e.g. propionic acid.

Butyric acid, isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, succinic acid, adipic acid, fufur-9,7-leic acid, phthalic acid, myristic acid.

Among the reactants such as palmitic acid, stearic acid, oleic acid, linoleic acid, lauric acid, and lyric acid, L-lysine-alkyl acid-based reactants are preferred from the viewpoint of their 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.
Powders with a particle diameter of 0 μ or less are preferably used.

In addition, the amount of the plate-shaped powder that is a reaction product of LIJ resin and an organic acid may be appropriately selected depending on the intended use of the fabric.9 Usually, it is uniformly dispersed in the moisture-permeable resin at 0.1% by weight or more. Just let it happen. 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.

When forming a moisture-permeable membrane, 1) the above-mentioned film is placed on a sheet-like material such as fabric, film, paper, etc., which has a smooth surface and has been treated with fluororesin, silicone-based resin, polypropylene, etc. to lower the solubility parameter. A resin solution of a polyurethane resin or PAU resin containing a tabular powder that is a reaction product of L-lysine and an organic acid is applied by a wet method or a dry method,
Solidify to obtain a moisture permeable membrane.

Coating is performed using a known coating method such as a knife coater, comma coater, reverse coater, etc., and the thickness is appropriately determined depending on the thickness of the moisture permeable membrane to be obtained from 3 to 50 μm.

Considering the workability during coating, the resin solution was adjusted to have a resin viscosity of 2000 to 30.0 OOcp (25°C), and in order to produce a uniform moisture-permeable film without pinholes or foreign matter on the resin film, the resin solution was mixed with a resin solution of 50 to 20. It is desirable to perform filtration using a mesh filter cloth and defoaming treatment.

After applying the resin solution to the sheet material, the dry method
Dry in a gas atmosphere at 0°C. Regarding the drying conditions at this time, it is desirable to consider the boiling point of the solution and dry under conditions that suppress evaporation as much as possible without causing bumping.

On the other hand, in the wet method, after a resin solution is applied to a sheet-like object, it is immersed in a solvent-removal solution that can remove the solvent in the solution, solidifying the resin together with the solvent-removal agent, and removing residual solvent in the resin film. After most of the solvent is removed, the solvent is dried at a temperature above the boiling point of the desolvent solution.

By the above method, a moisture permeable membrane having excellent abrasion resistance for use in the present invention can be obtained.

In the present invention, the moisture permeable membrane on the sheet-like article thus obtained is laminated with a fiber fabric using an adhesive.

The fiber fabrics used here include polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, and polyvinyl alcohol synthetic fibers.

Semi-synthetic fibers such as triacetate or nylon 6/
Examples include woven fabrics, non-woven fabrics, etc. made of cotton, blended fibers such as polyethylene terephthalate/cotton, and mixed fibers.

Examples of the adhesive used in the present invention include polyurethane adhesives, polyamide adhesives, polyester adhesives, etc., and they may be appropriately selected and used depending on the intended use of the fabric.

For lamination, apply the above-mentioned adhesive solution onto the sheet using a knife-over-roll coater.

Using a coating machine such as a roll-over coater or a gravure coater, the coating amount is appropriately set so that the dry film is 5 to 60 g/m'.

Dry at 50-100°C for 0.5-10 minutes,
Next, a fiber cloth is layered on top of this and 80 to 150 tons, 0.5
Thermocompression bonding is performed under conditions of ~20 kg/c++f.

When applying the adhesive, apply the adhesive in dots or lines.

If it is applied in the form of a combination of dots and lines, a product with even higher moisture permeability can be obtained.

After laminating, by peeling off the sheet material, 9
A moisture permeable waterproof fabric of the present invention is obtained.

Furthermore, if necessary, water-repellent treatment may be performed using a silicon-based water repellent by a known method.

The present invention has the above configuration.

(Function) The laminated moisture permeable waterproof fabric of the present invention has L-! By containing tabular powder which is a reaction product of J-lysine organic acid, excellent wear resistance performance is imparted. Also, the tabular powder is a reaction product of LIJ gin and organic acid.

Moisture permeable as it hardly reduces the performance of the moisture permeable membrane.

It also has excellent 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-mentioned powder has a flat plate-like shape and is easily separated between walls, so when it is dispersed and mixed in a resin solution for a moisture-permeable membrane, it peels off thinly.

When a moisture-permeable membrane is formed using this resin solution, the powder is arranged parallel to the membrane surface and becomes multilayered. Since the reaction product of L-lysine and an organic acid has excellent lubricity, if this is contained in the resin film, the surface of the resin film will have good lubricity and the abrasion resistance will be reduced. Furthermore, since the above-mentioned tabular powder itself is a reaction product of amino acids and organic acids, it has good compatibility with resins for moisture-permeable membranes, especially PAU resins, and due to their synergistic effect.

It is presumed that excellent wear resistance can be obtained.

4 (Example) Next, the present invention will be explained in more detail with reference to two examples.Measurement of the performance of the fabric in the example.

Evaluation was performed using the following method.

(1) Moisture permeability According to JIS-2-0208.

(2) Water pressure resistance According to J　5-L-1096 (low water pressure method).

(3) Abrasion strength J 5000 according to l5-L-1084 (A-1 method)
After rubbing twice, changes in the appearance of the moisture-permeable membrane were visually judged on a 5-level scale.

5. No change was observed in the moisture permeable membrane.

4. Some changes can be seen in the moisture permeable membrane.

3. The surface of the moisture permeable membrane is slightly worn.

2. The moisture permeable membrane is slightly peeled off.

1. All moisture permeable membranes are peeled off.

Example 1 In this example, Nε was used as a reaction product of L-lysine and an organic acid.
EXAMPLE 1 A moisture-permeable waterproof fabric of the present invention was produced using -lauroyl-cys-lysine by the following method.

First, a release paper laminated with a polypropylene film is prepared, and a knife-over roll coater is used to coat the resin solution shown in formulations 1 to 3 in Table 1 below, so that the dry film thickness of the moisture-permeable membrane becomes 15 μm. After coating with the coating amount adjusted as appropriate, drying was performed at 60° C. for 3 minutes.

Table 1 (Note 1) Seiko Kasei ■, PA [I resin (Note 2) Dainichiseika Chemical ■, polyurethane resin Next, on the formed moisture permeable film, a polyurethane adhesive shown in the following formulation 4 was applied. Apply the solution to 6 coats using a knife-over roll coater.
After coating at 0 g/m', drying was performed at 50°C for 3 minutes.

Add to this a nylon tricot half [nylon (FD) 40d/10f is used for both the front and back threads,
The number of courses was 53 per liter and the number of wales was 44 per liter] and thermocompression bonding was performed at 90°C and 3 kg/cut.

[Formulation 4] 10 parts of dimethylformamide toluene 40 parts After this, the release paper was peeled off, and then padded with a 5% aqueous solution of Asahi Guard AC, 710 (Asahi Glass 7 ■ product), a fluorine-based water repellent emulsion (squeezing ratio 55). %)L
A heat treatment was performed at 30° C. for 1 minute, and three pieces of the moisture-permeable waterproof fabric of the present invention were prepared as Invention 1 and 2.3, respectively. ) was obtained.

For comparison with the present invention, in this example, the formulation 1
Three comparative moisture-permeable waterproof fabrics (referred to as Comparative Examples 1 and 2.3, respectively) were obtained in exactly the same manner as in Example 1, except that Nε-lauroyl-L-lysine was omitted from Examples 1 to 3.

The performance of the moisture permeable waterproof fabrics of Inventions 1 to 3 and Comparative Examples 1 to 3 was measured and evaluated, and the results are shown in Table 2.

(The following is a blank space) 8 2 Table 3 If you compare the performance of Invention 1 and Comparative Example 1, Invention 2 and Comparative Example 2, and Invention 3 and Comparative Example 3, it is clear that one of the invention's transparency is It can be seen that all of the wet waterproof fabrics have good abrasion resistance without impairing their moisture permeability and waterproof properties.

Example 2 Release paper processed with silicone resin was prepared, and a resin solution with a resin solid content of 20% shown in the following formulation 5 was applied to it in an amount of 30% using a knife over roll coater.
After coating to 0g/m', S degree 0.1% by weight
10 in an aqueous solution (liquid temperature 15°C) of anionic surfactant.
Soak for a minute and remove solvent.

After solidifying the resin, drying at 130°C for 2 minutes,
A moisture-permeable membrane with a thickness of 40 μm was obtained on release paper.

[Formulation 5] PAU 200 100 parts Rezashin After coating with a coating amount of 60 g/m' using a roll coater, 5
Dry for 2 minutes at 0°C, then add a nylon tricot half [front and back yarns are both nylon (
FD) 40d/10r used, 53 courses/! 44 wales per 1 inch], and
Thermocompression bonding was performed under the conditions of 0°C and 3 kg/cffl.

[Formulation 6] Heimlen-2031 100 parts (Polytle emulsion resin, Dainichiseika Chemical Product) Rezamin x
2 parts (isocyanate compound, Dainichiseika Chemical Industry ■ product) 2 parts of Rezamin HI-215 (crosslinking catalyst, Dainichiseika Chemical Industry ■ product) After this, the release paper was peeled off, and then Asahi Guard AC, a fluorine-based water repellent emulsion ,-710 (Asahi Glass product)
Padding with 5% aqueous solution (squeezing ratio 55%) L130℃
A heat treatment was carried out for 1 minute to obtain two moisture-permeable waterproof fabrics of the invention.

When the performance of the moisture permeable waterproof fabric of the present invention was measured and evaluated,
It has excellent abrasion resistance of 5th grade vertically and 5th grade horizontally, and other performance features include moisture permeability of 6440g.
/ m' ・24 hr, water pressure resistance of 2000 mm or more without any problems, and had excellent performance.

(Effects of the Invention) The laminated moisture permeable waterproof fabric of the present invention can satisfy excellent abrasion resistance without impairing high moisture permeability and waterproof performance. 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 membrane made of a polyurethane resin containing 0.1% by weight or more of a tabular powder that is a reaction product of L-lysine and an organic acid or a synthetic polymer mainly composed of a polyamino acid urethane resin is attached to a fabric with an adhesive. A moisture-permeable waterproof fabric with excellent abrasion resistance, characterized by being laminated with .