JPH03213583A - Production of moisture-permeable waterproof cloth having soft feeling - Google Patents

Abstract

PURPOSE:To obtain the subject soft cloth by forming a first resin layer in applying with a resin solution containing a water-soluble polymer onto a piece of fiber cloth, forming a second resin layer of a polyurethane resin, etc., on the first resin layer and removing said polymer from the first layer with elution. CONSTITUTION:A solution of a coating resin containing a water-soluble polymer is applied onto a piece of fiber cloth composed of a synthetic fiber or semi- synthetic fiber, etc., to form a first resin layer. Then, a coating resin solution composed of a solution of a polyurethane resin or a polyamino acid urethane resin is applied on the first resin layer and dried to form a second resin layer. Thus, the water-soluble polymer is removed from the first resin layer with elution by a suitable method corresponding to the used water-soluble polymer to afford the objective moisture-permeable waterproof cloth having soft feeling. Besides, as the water-soluble polymer, CMC or PVA, etc., is exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a moisture permeable waterproof fabric having a soft texture.

(Conventional technology) Conventionally, as a manufacturing method for moisture-permeable waterproof fabric.

Manufacturing methods using a laminating method and a manufacturing method using a coating method are well known.

Among these, moisture-permeable waterproof fabrics made using the lamination method are obtained by bonding a moisture-permeable and waterproof resin membrane to a fiber fabric using an adhesive. It is also known that moisture-permeable waterproof fabrics with texture can be obtained. However, moisture permeable waterproof fabrics produced by the lamination method have only low moisture permeability due to a reduction in moisture permeability caused by the adhesive used during lamination.

On the other hand, methods for obtaining moisture-permeable waterproof fabrics by coating include wet coagulation and semi-dry wet coagulation.

There is a dry method, and in both methods, methods for manufacturing moisture-permeable waterproof fabrics that have both excellent moisture permeability and waterproof performance have been proposed, and some have actually been manufactured, but they have a soft texture. There are very few. Especially moisture-permeable waterproof fabric made by dry method.

Due to the high modulus of the coating resin itself and the low viscosity of the coating resin, the resin tends to get into the grains of the fabric, hindering the movement of the fabric's structure, and making the fabric feel hard.

(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 a soft feel while being produced by a dry method.

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

That is, the present invention provides the following methods: ``A first resin layer is formed by applying a coating resin solution containing a water-soluble polymer compound onto a fiber fabric, and then a coating resin mainly composed of a polyurethane resin or a polyamino acid urethane resin is applied on the resin layer. Moisture permeability with a soft texture characterized by applying a coating resin liquid made of a synthetic polymer to form a second resin layer, and then eluting and removing a water-soluble polymer compound from the first resin layer. The gist of this paper is ``Method for manufacturing waterproof fabric.''

=3- 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 and knitted fabrics, non-woven fabrics, etc. made of blended fibers such as cotton.

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 water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment may be carried out by a commonly used known method. When particularly good water repellency is required, a fluorine-based water repellent is used.9 For example, Asahi Gart 730 (fluorine yarn water repellent emulsion) manufactured by Asahi Glass Co., Ltd. is padded with a 5% aqueous solution (squeezing ratio). 35%) followed by heat treatment at 160° C. for 1 minute.

In the present invention, a first resin layer is formed by applying a coating resin solution containing a water-soluble polymer compound onto the above-mentioned fiber fabric.

The coating resin used in the present invention may be selected from known thermoplastic resins depending on the intended use of the fabric. Specific examples include silicone resin, acrylic resin, polyamide resin, polyester resin, polyurethane resin,
Examples include polyamino acid urethane resin, but need not be limited thereto.

Another water-soluble polymer compound used in the present invention is:

Any substance may be used; for example, starch, dextrin, polysaccharides such as sodium alginate, cellulose esters such as cellulose butyrate and cellulose acetate acetate, methyl cellulose, and ethyl cellulose.

Cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, chitin.

Amino sugars such as chitosan and heparin, and gelatin.

Natural water-soluble polymer compounds such as water-soluble proteins such as albumin and globulin, and derivatives thereof;
Examples include synthetic water-soluble polymer compounds such as polyvinyl alcohol and polyacrylamide.

A coating resin solution containing a water-soluble polymer compound can be prepared using a known method, and the resin viscosity is set to 2.0 in consideration of workability during coating.
It is desirable to adjust the temperature to 0.000 to 40.0OOcp (25° C.) and to perform filtration using a 20 to 200 mesh filter cloth in order to remove resin particles.

Examples of methods for applying the above-mentioned coating resin liquid to the fiber fabric include 1. Ordinary coating method 2.

This is done by a coating method using a knife coater, comma coater, reverse coater, etc.

The amount of coating resin to be applied on the fiber fabric depends on the intended use of the fabric and the thickness of the resin film from 1 to 100 μm.
It may be determined appropriately according to m, etc.

Further, any known method may be used to form the film, but it is preferable to introduce a drying step, especially from the viewpoint of operational efficiency. Regarding the drying conditions in this drying step, the temperature and time are appropriately selected in consideration of the boiling point of the solvent used, etc.

In the present invention, a second resin layer is formed by applying a coating resin liquid made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin onto the above-mentioned coating resin layer.

Here, the synthetic polymer mainly composed of polyurethane resin refers to one containing 60 to 100% polyurethane resin as one synthetic polymer (of course, 100% polyurethane resin may be used), and other synthetic polymers such as polyacrylic acid ,PVC.

It may contain polymers such as polystyrene, polybutadiene, polyamino acids, copolymers thereof, etc. in an amount of less than 30%.

The polyurethane resin used in the present invention is a reaction product containing a polyol having hydroxyl groups at both nine 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 with 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, resinous 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.

What is a synthetic polymer mainly composed of polyamino acid urethane resin? 1 Synthetic polymer contains 70 to 100% of polyamino acid urethane resin.
% (of course, 100% polyamino acid urethane resin may be used).Other synthetic polymers include, for example, block copolymers of poly T-alkylglutamate and butadiene, and block copolymers of polyT-alkylglutamate and leucine. It may contain a polymer or the like in an amount of less than 30%.

Polyamino acid urethane resin (hereinafter referred to as P) used in the present invention
It is called AU 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 from the viewpoint of film performance, optically active r-
Alkylglutamate-NCA is preferably used, and among them, T-methyl L-glutamate-NCA or T-methyl-D-glutamate-NCA is advantageously selected as the amino acid component of the PAU resin from the viewpoint of price and film properties. There are many cases. on the other hand.

As the polyurethane, 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 NC○10H>1, is used. The isocyanate component is aromatic diisocyanate.

Aliphatic diisocyanates and alicyclic diisocyanates may be used alone or in mixtures thereof.

For example, tolylene 2,4-diisocyanate, 40,4'-diphenylmethane diisocyanate, ■,6-
Examples include hexane diisocyanate and 1,4-cyclohexane diisocyanate. Also.

As the polyol component, polyether polyol, polyester polyol, etc. are used. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and examples of polyester polyols include reactions between diols such as ethylene glycol and propylene glycol and dibasic acids such as adipic acid and cepatic acid. Examples include products 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.

=11 The polymerization solvent used during the synthesis of P A U resin satisfies two points: it is a polymerization solvent for amino acid NCA, does not contain active hydrogen, and can dissolve the urethane prepolymer having terminal isocyanate groups. A solvent is selected which contains 1 such solvent, for example dioxane,
Examples include cyclic ethers such as tetrahydrofuran, acetate esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, polar amide solvents such as dimethylformamide and N-methylpyrrolidone, etc. These can be used as sole solvents, Alternatively, it can be used as a mixed solvent. Particularly preferred among these solvent systems are:
Examples of solvents for dissolving or uniformly dispersing the resulting polymer composition include dimethylformamide alone, a mixed solvent of dimethylformamide and dioxane, or a mixed solvent of methyl ethyl ketone and dimethylformamide. These solvents are also excellent as solvents in terms of stability and coatability of the resin solution during the production of polyurethane resin films or PAU resin films by coating.

The method for forming the moisture-permeable film of the second resin layer includes a conventional coating method (for example, a coating method using a knife coater, comma coater, reverse coater, etc.) with the above-mentioned polyurethane resin solution or PAU resin solution on the first resin layer. After coating, a wet coagulation method or a resin solution obtained by modifying polyurethane resin or PAU resin into a system that is easy to mechanically foam or a W/○ type emulsion system is applied on the first resin layer and dried. Examples include methods.

In the method of the present invention, the water-soluble polymer compound in the first resin layer is eluted and removed from the two-layer coating fabric obtained as described above, and micropores are formed in the first coating resin layer in contact with the fiber fabric. Form a large number of.

Methods for eluting and removing water-soluble polymer compounds include decomposition and elution using enzymes, elution using aqueous solutions of organic acids, inorganic acids, surfactants, etc., and washing using water or hot water. - Method of elution = 13 methods, etc. are listed, and may be appropriately selected depending on the water-soluble polymer compound used, the intended use of the fabric, etc. For example, the water-soluble polymer compound used is starch,
When eluting this starch with an amylase aqueous solution, it is desirable to immerse the coated fabric containing the starch in an amylase aqueous solution of 0.1 wt % or more at 50° C. for 1 minute or more.

The present invention consists of one or more configurations. According to the present invention, a moisture permeable waterproof fabric can be obtained which has a soft feel and has both excellent moisture permeability and waterproof performance.

(Function) Like the moisture-permeable waterproof fabric produced by the method of the present invention, a coating resin layer containing a water-soluble polymer compound is formed as a first resin layer on a fiber fabric serving as a base fabric, and a second resin layer is formed thereon. A moisture-permeable and waterproof polyurethane resin layer or PAU resin (polyamino acid urethane resin) layer is formed as a first resin layer, and the water-soluble polymer compound is eluted and removed from the first resin layer in this state.

The first resin layer has the shape of a continuous foamed film in which countless uniform micropores are formed, and the interface between the first resin layer and the base fabric and the interface between the first resin layer and the second resin layer. Both of them become partially adhered, and as a result, the degree of freedom of the fixed tissue increases and it becomes easier to move, so that the moisture permeable waterproof fabric as a whole of the nine tissues has a soft texture.

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

Evaluation was performed using the following method.

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

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

(3) Strong wear resistance According to JIS I, -1084 (A-1 method).

(4) Water repellency According to JIS L-1096 (spray method).

(5) Texture It was measured by handling, and a three-level evaluation was performed.

0 Soft △ Slightly hard × Hard Example 1 In this example, a moisture permeable waterproof fabric of the present invention was manufactured by the following method using carboxymethyl cellulose (hereinafter referred to as CMC) as a water-soluble polymer compound.

First, a plain woven fabric (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch is prepared using nylon 70 denier/34 filament for both the warp and weft as the base fabric, and is scoured using the usual method. After staining with an acid dye, padding with a 5% aqueous solution of Asahi Guard 710 (manufactured by Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion (squeezing ratio: 35%) L, was heat-treated at 160°C for 1 minute. . Next, using a calendering machine with mirror-finished rolls, the temperature was 160°C and the pressure was 30 kg/cm.

Calendar processing was performed at a speed of 20 m/min, and then a resin solution with a resin solid content concentration of 25% (CMC content 4%) shown in Formulation 1 below was applied in an amount of 100 g/m' using a knife over roll coater. After coating at 120℃
Dry for 2 minutes.

A film of the first resin layer was formed.

[Formulation 1] Next, the following Formulation 2 was applied to the surface of the first resin layer described above using a knife over roll coater, and the amount of coating was adjusted appropriately so that the dry film thickness of the moisture permeable membrane was 10 μm. After coating, drying was performed at 60° C. for 10 minutes.

[Formulation 2] Toluene 20 parts Isopropyl alcohol 20 parts Thereafter, the fabric was immersed for 5 minutes at 50° C. in a 0.1% cellulase aqueous solution (cellulase treatment). 3 A moisture permeable waterproof fabric of the present invention was obtained.

For comparison with the present invention, in this example, the following formulation 3 was used instead of formulation 1, and the cellulase treatment step of immersion in a cellulase aqueous solution was omitted. A moisture permeable waterproof fabric (Comparative Example 1) was obtained.

[Formulation 3] On the same base fabric as above, do not apply the resin solution of Prescription 1, but directly use the resin solution of Prescription 2 at a coating amount of 120g/m2.
' After coating with a reverse coater.

Drying was performed at 60° C. for 10 minutes to obtain a comparative moisture-permeable waterproof fabric (Comparative Example 2).

The performance of the moisture-permeable waterproof fabrics of the present invention and comparison was measured and evaluated, and the results are shown in Table 1.

Table 1 * Moisture Permeability (g/m'・24hr) As is clear from Table 1, the moisture permeable waterproof fabric produced by the method of the present invention has a very flexible wind resistance despite being formed by a dry method. There was a coincidence.

In addition, the fabric had both excellent moisture permeability and waterproof performance.

Example 2 A moisture-permeable waterproof fabric of the present invention was obtained in the same manner as in Example 1, except that the following formulation 4 using PAU resin was used in place of the polyurethane resin formulation of formulation 2 in Example 1. Ta.

[Formulation 4] N-N dimethylformamide 10 parts toluene
10 parts 1 for comparison with the present invention In this example, the above-mentioned formulation 3 was used in place of formulation 1, and the cellulase treatment was omitted. 1 A comparative moisture-permeable waterproof fabric ( Comparative example 3)
I got it.

0 In addition, 1 For comparison with the present invention, 1 The same base fabric as that used in this example was coated with the resin liquid of prescription 4 directly without applying the resin liquid of prescription 4, and then dried. The coating and drying conditions were the same as in Comparative Example 2, except that the coating amount in Comparative Example 2 was changed to 160 g/rn'.
A comparative moisture-permeable waterproof fabric (Comparative Example 4) was obtained.

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

Table 2 As is clear from Table 2, the moisture-permeable waterproof fabric produced by the method of the present invention has a very soft texture even though it is formed by a dry method.

It also had excellent moisture permeability and waterproof performance.

Example 3 In the above-mentioned Example 1, a fabric was prepared in which a film of the first resin layer was formed by a dry method using Formulation 1 as a base fabric, and a PAU resin solution of Formulation 5 below was applied to this fabric to adjust the coating amount. 100g/
After coating using a knife-over roll coater at m', the resin was immersed in water at 15°C for 40 seconds to solidify the resin, and then washed in warm water at 50°C for 10 minutes to coat the second resin layer. A moisture permeable membrane was formed.

[Formulation 5] 2 After this, it was immersed in an aqueous solution of a nonionic surfactant concentration of 19 (liquid temperature 65°C) for 10 minutes to form micropores in the first resin layer to obtain a moisture permeable waterproof fabric of the present invention. Ta.

For comparison with the present invention, in this example, the above-mentioned formulation 3 was used in place of formulation 1 when forming the film of the first resin layer, and the treatment with a nonionic surfactant was omitted. A comparative moisture-permeable waterproof fabric (Comparative Example 5) was obtained in exactly the same manner as above.

In addition, for comparison with the present invention, the resin solution of Formulation 1 was not applied directly to the same base fabric as that used in this example.
Using a reverse coater, apply the resin liquid with recipe 5 in an amount of 1.
After coating at 00g/m'.

Immerse in water at 15°C for 40 seconds to solidify the resin.

Subsequently, a comparative moisture-permeable waterproof fabric (Comparative Example 6) was obtained by washing in warm water at 50° C. for 10 minutes and drying using a wet method.

The performance of the moisture-permeable waterproof fabric of the present invention and the comparative waterproof fabric was measured and evaluated, and the results are shown in Table 3.

Table ※ Moisture Permeability (g/m'・24hr) As is clear from Table 3, the moisture permeable waterproof fabric produced by the method of the present invention has
Even though the resin layer is formed using a dry method,
It has a very flexible texture and has excellent moisture permeability and waterproof performance.

Example 4 In the above-mentioned Example 3, the following formulation 6 was used in place of formulation 5, in which a portion of polyurethane resin was added.Other than that, a moisture-permeable waterproof fabric of the present invention was obtained by the completely same method as in Example 3. .

[Formulation 6] 10 parts of N-N-dimethylformamide 1 for comparison with the present invention In this example, the above-mentioned formulation 3 was used in place of formulation 1 during film formation of the first resin layer, and the nonionic interface A comparative moisture-permeable waterproof fabric (Comparative Example 7) was obtained in exactly the same manner as in this example except that the treatment with an activator was omitted.

In addition, for comparison with the present invention, 9 the same base fabric as that used in this example was directly treated with the resin liquid of the above formulation 6 without applying the resin liquid of the formulation 1. A comparative moisture-permeable waterproof fabric (Comparative Example 8) was obtained by processing under the same conditions as in the wet method of Comparative Example 6, except that the coating amount in Comparative Example 6 was changed to 5 120 g/m'.

The performance of the moisture-permeable waterproof fabric of the present invention and the comparative moisture-permeable waterproof fabric was measured and evaluated, and the results are shown in Table 4.

Table 4 * Moisture permeability (g/m' ・24 hr) As is clear from Table 4, the moisture permeable waterproof fabric produced by the method of the present invention has
Even though the resin layer is formed using a dry method,
It had a very flexible texture6 and also had excellent moisture permeability and waterproof performance.

(Effects of the Invention) According to the method of the present invention, a moisture permeable waterproof fabric having a very soft texture can be produced.

Furthermore, the moisture-permeable waterproof fabric produced by the method of the present invention is a material particularly suitable for sports clothing and outerwear clothing due to its excellent performance.

Claims (1)

[Claims] (1) A coating resin solution containing a water-soluble polymer compound is applied onto a fiber fabric to form a first resin layer, and then,
A second resin layer is formed by applying a coating resin liquid made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin onto the resin layer, and then the water-soluble polymer compound is eluted and removed from the first resin layer. A method for producing a moisture-permeable waterproof fabric having a soft texture.