JPS62156363A - Production of moisture permeable waterproof 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 (Industrial Application Field) The present invention relates to a method for producing a highly durable, water pressure resistant, highly moisture permeable waterproof fabric.

(Conventional technology) Generally, moisture permeability and waterproofness are mutually contradictory functions, but
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.

In general, polyurethane elastomer is preferably used as a coating resin during these dry or wet coating processes in terms of film strength, rubber elasticity, and flexibility. Because it is made based on the balance of both, the waterproof performance is JIS L-109.
Water vapor permeability is 4000 to 5000 g/m for fabrics with a depth of 1.500 mm (below the water column) or more when measured with water pressure resistance in step 6.
-Currently, only about 24hrs (JIS Z-0208 measurement) can be obtained.

The inventors of the present invention have greatly improved the level of moisture permeability of conventional polyurethane elastomer-based moisture-permeable waterproof fabrics, making it possible to smoothly control the humidity inside the clothes due to sweating when working in the rain or exercising. A method for manufacturing a moisture-permeable waterproof fabric was previously proposed in Japanese Patent Application No. 10853/1983. That is, this method uses a polyamino acid urethane resin and a special micropore-forming agent to control the microcells and pore diameter of a porous membrane to produce a waterproof fabric with high moisture permeability using a wet coating method.

However, although the polyamino acid urethane resin produced by this method is suitable for obtaining highly moisture permeable waterproof fabrics, detergents used during home washing or dry cleaning may remain, and contaminants may adhere when worn. It had the disadvantage of reduced water pressure resistance.

(Problem that the invention attempts to solve) The present invention was made in view of the above-mentioned current situation.

The object of the present invention is to obtain a highly moisture-permeable waterproof fabric that has excellent durability and water pressure resistance.

(Means and operations for solving the problems) The present invention achieves the above-mentioned objects and has a secondary structure.

That is, the present invention provides a first step of applying a resin solution consisting of a polyamino acid resin, a polyurethane resin, an isocyanate compound, and a polar organic solvent to a fiber fabric, and then immersing it in water, washing it in hot water, and drying it, and the above-mentioned coated surface. Moisture permeability characterized by comprising a second step of applying a resin solution consisting of a polyamino acid urethane resin, an isocyanate compound, a micropore-forming agent 2, and a polar organic solvent to the substrate, followed by immersion in water, washing with hot water, and drying. The gist of this paper is ``Method for manufacturing waterproof fabric.'' Three aspects of the present invention will be described in detail below.

In the present invention, first, a first step is performed in which a resin solution consisting of a polyamino acid resin, a polyurethane resin, an isocyanate compound, and a polar organic solvent is applied to a fiber fabric, and then the fabric is immersed in water, washed with hot water, and dried. The polyamino acid resin used in the present invention is mainly composed of synthetic polyamino acids,
Amino acids include DL-alanine, L-aspartic acid, L-cystine, L-glutamic acid, glycine, LU
Examples include gin, L-methionine, L-leucine and derivatives thereof. When synthesizing polyamino acids, amino acid N-carboxylic anhydrides (hereinafter N-carboxylic anhydrides are referred to as NCA) obtained from amino acids and phosgene are generally used.

The polyurethane resin used in the present invention has aromatic diisocyanate as its isocyanate component,
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, 1,4-cyclohexane diisocyanate, and the like. The polyol component is polyether polyol.

Polyester polyols are used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols are produced by the reaction of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sepatic acid. and ring-opening polymers such as caprolactone and caprolactone. In the method of the present invention, polyester polyurethane is preferably used as the polyurethane having good mixing stability with polyamino acids.

The amino acid component constituting the above-mentioned polyamino acid resin is optically active T-alkyl glutamic acid (T-alkyl glutamic acid) from the viewpoint of film performance.
-NCA is preferably used, and especially T-methyl-L-glutamate NCA or γ
-Methyl-D-glutamate is often advantageously selected.

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.

When blending polyamino acids and polyurethane, a solution is prepared in advance with a solvent that can dissolve both.
This can be achieved by stirring, optionally with heating. Solvents that can dissolve both include dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, and these solvents, as well as chlorinated hydrocarbon compounds such as dichloroethane, chloroform, methylene chloride, and dichloroacetic acid, and chlorinated strong oxides. Among them, a mixed solvent mainly composed of a polar effective solvent, such as a mixed solvent mainly composed of dimethylacetamide, is preferably used. The concentration of the polymer suitable for blending is 5 to 50% by weight (hereinafter % represents weight %), and a range of 10 to 30% is usually used.

The weight ratio of polyamino acid and polyurethane used in the present invention can be varied over a wide range from 90:10 to 10:90, and may be appropriately selected depending on the required performance of the resin film. Those in which the weight ratio is in the range of 50=50 to 20:80 are particularly preferred from the viewpoint of film performance. Hereinafter, a resin obtained by mechanically mixing a polyamino acid and a polyurethane will be referred to as a blend resin.

In the present invention, a compound having high affinity with the fiber base fabric is used in combination for the purpose of improving the peeling resistance between the above-mentioned blend resin film and the fabric. In the present invention, an isocyanate compound is also used as the compound. Examples of the isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, or addition of 3 moles of these diisocyanates and 1 mole of a compound containing active hydrogen (e.g., trimethylolpropane, glycerin, etc.) The triisocyanate i obtained by the reaction is used. The above-mentioned isocyanates may be in the form of free isocyanate groups, or may be stabilized by adding phenol, methyl ethyl ketoxime, etc., and the blocks may be dissociated by subsequent heat treatment. 2 types can be used depending on workability, purpose, etc. The amount of the isocyanate compound to be used is preferably 0.1 to 10%, preferably 0.5 to 5%, based on the blend resin. If the amount used is less than 0.1%, the adhesive strength of the resin to the fabric will be poor, and if it exceeds 10%, the texture will be hardened, which is not preferable.

In the present invention, the above-mentioned blend resin, isocyanate compound, and polar organic solvent are used in combination. Examples of the polar organic solvent used here include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylenephosphonamide. .

These substances are highly soluble in water, and when a polar organic solvent solution of a water-insoluble resin is immersed in water, only the polar organic solvent dissolves in water and the resin coagulates in water. The resin coagulation method is generally called the wet coagulation method. When the resin is coagulated by the wet coagulation method, a trace amount of the polar organic solvent present in the resin is dissolved in water, so that a resin film having countless micropores can be obtained.

Furthermore, when observing the film surface of the blended resin of the coating fabric obtained in the first step of the method of the present invention, it was found that it had countless micropores with a diameter of 1 μm or less, and that the film surface was smoother than that of the polyamino acid urethane resin. It is believed that this contributes to good initial water pressure resistance, improved stain resistance, and reduced detergent residue, that is, to maintenance of water pressure resistance with excellent durability.

A resin solution consisting of a polyamino acid resin, a polyurethane resin, an isocyanate compound, and a polar organic solvent can be applied to a fiber fabric by a conventional coating method. Generally, the coating thickness of resin is 10 to 30 mm due to machine performance.
It is 0 μm.

The fiber fabrics mentioned here include nylon 6 and nylon 6.
Polyamide-based synthetic fiber represented by 6.

A single knitted fabric composed 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 non-woven fabrics.

After applying the above-mentioned resin solution to the fiber fabric, the fabric is immersed in water, and the water temperature at this time is preferably in the range of 0 to 30°C. diffusion becomes faster and the micropores of the resin film become larger.

As a result, the water pressure resistance may become poor. Also.

The dipping time must be at least 20 seconds; if it is less than 20 seconds, the resin will not solidify sufficiently and a satisfactory blended resin film will not be obtained.

After coagulating the blended resin in water, wash the fabric with hot water,
Remove remaining solvent. The hot water washing conditions vary depending on the mixing ratio of polyamino acid resin and polyurethane resin.
Usually, it is sufficient to perform the heating at a temperature of 30 to 80°C for 5 minutes or more.

After washing with hot water, dry.

The above is the first step in the method of the present invention.

Next, in the present invention, as a second step, a resin solution consisting of a polyamino acid urethane resin, an isocyanate compound, a micropore forming agent, and a polar organic solvent is applied to the surface coated in the first step, and then immersed in water, Wash with hot water and dry.

The polyamino acid urethane resin (hereinafter referred to as PAU resin) used here is a copolymer consisting of polyamino acids and polyurethane, and the amino acids include DL-alanine, L-
Aspartic acid, L-cystine, L-glutamic acid, glycidi, L-lysine.

Examples include L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, amino acid N-carboxylic anhydride (hereinafter referred to as
N-carboxylic acid anhydride is called NCA. ) is commonly used. As the isocyanate component of polyurethane, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in mixtures thereof.9 For example, tolylene 2,4-diisocyanate.

4,4'-diphenylmethane diisocyanate.

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

The polyol component is polyether polyol.

Polyether polyols are used. Polyethylene glycol is a polyether polyol.

Examples of polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and cehatic acid, and ring-opening polymers such as caprolactone. can be mentioned.

Examples of amines used in the copolymerization of amino acids and polyurethane include ethylenediamine, diethylamine, triethylamine, and ethanolamine. As described above, PAU resins are obtained by adding amines to the reaction between various amino acids NCA and urethane prepolymers having isocyanate groups at the ends.

The amino acid component constituting the above-mentioned PAU resin is optically active T-alkyl glutamate NCA from the viewpoint of film performance.
are preferably used, especially γ-methyl-L-gluta from the viewpoint of price and film properties.

The mate NCA or T-methyl-0-glutamate is often advantageously selected.

Examples of the /a pore-forming agent used in the present invention include anionic surfactants, nonionic surfactants, and hydrophilic polymers. The amount used is 0.1 to 10% in the case of anionic surfactants and nonionic surfactants, and 0 in the case of hydrophilic polymers based on the solid content of the PAU resin used together.
．． It is desirable that the content be in the range of 0.05 to 5%. If the amount of these micropore-forming agents used is less than the above range, P
The pores of the AU resin film become too small, making it difficult to obtain interconnected microcells and resulting in poor moisture permeability.

Furthermore, if the amount exceeds the above range, the pores become too large and a water pressure resistance of 1500 mm or more cannot be obtained. The anionic surfactant used as the above-mentioned micropore forming agent is
Conventionally known alkyl sulfate ester salt.

These include alkylbenzene sulfonates, α-olefin sulfonates, argylsulfonates, fatty acid amide sulfonates, dialkyl sulfosuccinates, etc., or any mixture thereof.

Nonionic surfactants are polyoxyethylene alkyl ether, polyethylene alkylphenyl ether, polyoxyethylene aliphatic ester, polyoxyethylene aliphatic amide ether 1 polyhydric alcohol aliphatic ester, polyoxyethylene polyhydric alcohol fatty acid ester , Jm fatty acid sucrose ester 2-alkylodamide, etc., or any mixture thereof.

Hydrophilic polymers include polyvinylpyrrolidone, polyacrylic acid, polyacrylic ester, carboxyvinyl polymer organic amine, polyethyleneimine, etc., and are substances that can be dissolved, dispersed, or emulsified in polar organic solvents and soluble in water. It refers to a polymer that has a

Moreover, the same isocyanate compound and polar organic solvent used in the second step as those used in the first step can be used.

In the second step of the present invention, the above-mentioned micropore forming agent and P
After applying a resin solution consisting of AU resin, an isocyanate compound, and a polar organic solvent, the fabric is immersed in water, but the water temperature at this time is preferably in the range of 0 to 30°C, and if the water temperature exceeds 30°C, dimethyl This is because the formamide diffuses into the water faster and the fine pores in the resin film become larger.

As a result, the water pressure resistance may become poor. Also.

The dipping time must be at least 10 seconds; if it is less than 10 seconds, the resin will not coagulate sufficiently and a satisfactory PAU 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 micropore forming agent used, but the temperature is 30 to 80°C.
It is sufficient to carry out the process at a temperature of 3 minutes or more. After washing with hot water, dry.

The fiber fabric used in the present invention may be a fabric that has been treated with T8 water, but this fiber fabric does not necessarily need to be treated with water repellency in advance, and the fabric obtained after coating may be treated with water repellency. Good too.

Regarding the water repellent agent and water repellent treatment method used here, the padding method is used as appropriate in accordance with the method used when the fiber fabric is previously treated with water repellency as described above.

(Ω water treatment may be performed by a spraying method, coating method, etc.) In addition, in order to improve the durability of water repellency, tΩ water treatment can also be performed by using a resin such as a melamine resin in combination.

In the method of the present invention, it is also possible to perform water repellent treatment both before and after coating, and in this case, a product with even better water pressure resistance can be obtained. Further, in order to improve the smoothness and flexibility of the fabric, a polysiloxane resin may be further applied to the fabric. As the polysiloxane to be applied, dimethylpolysiloxane, phenyl group-containing polysiloxane, modified silicone oil such as amino-modified or olefin-modified silicone oil, methylhydrogen polysiloxane, or a mixture of dimethylpolysiloxane and methylhydrogen polysiloxane can be used. Although it may be selected as appropriate, dimethylpolysiloxane having a molecular weight of about 5,000 to 30,000 is preferably used in the present invention. This polysiloxane treatment first of all imparts smoothness to the fabric and can reduce frictional damage to the film 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. This polysiloxane treatment may be applied in the form of an aqueous dispersion, an emulsion, etc., but in order to prevent treatment spots from occurring, 1.1.1. It may also be applied as a solution in a solvent such as hexane or mineral turpentine. The polysiloxane resin may be applied by a commonly used padding method, coating method, spraying method, or the like. The amount of polysiloxane deposited is preferably 0.1% or more in terms of solid content based on the weight of the fiber.

The present invention has the above configuration, but the reason why the moisture permeable waterproof fabric of the present invention has high water pressure resistance and high moisture permeability is not clear, but the obtained moisture permeable waterproof fabric When observing the cross section of the film formed in the first step, the cross section of the film formed in the first step has countless microcells with a diameter of 1 μm or less, and the cross section of the film formed in the second step has many microcells with a diameter of 1 to 5 μm. This is thought to be a factor in providing high moisture permeability and high water pressure resistance. Furthermore, the high affinity of polyamino acid resins and PAU resins themselves for water vapor may be one of the driving forces behind their high moisture permeability.

Considering the molecular structure of the blend resin and PAU resin used in the present invention, the amino acid component forms an α-helical structure, while the urethane component forms a random coil structure. This was confirmed by the assignment of an amide hand in the infrared absorption spectrum (amide V 615 cm-', a key hand of the α-helinox conformation of polyγ-alkyl-monoglutamate) in the porous membrane produced by the wet coagulation method of the present invention. ing. In general, in the case of amino acid resins, high S? The driving force behind the WL property is its high diffusion coefficient, and this is thought to be due to the α-helical structure of the amino acid resin, which has a large side chain.

(Example) Next, the present invention will be further explained with reference to Examples.

The performance of the fabric in this example was measured and evaluated by the following method.

(1) Water pressure resistance According to JIS L-1096 (low water pressure method), the water pressure resistance of the sample was measured before and after the washing weather resistance test in item (5) below.

(2) ↑θ Water content JIS L-1096 (spray method) (3) Moisture permeability JIS Z-0208 (4
) Washing durability test Washing according to JIS L-0842 (A-2 method) was repeated 10 times.

Example 1 Blend resin A and blend resin B of polyamino acid and polyurethane used in this Example 1 and Examples 2 to 3 described later, and PAU resin were manufactured by the following method.

[Production of Blend Resin A] Polytetramethylene adipate (molecular weight approximately 1000) having a terminal hydroxyl group and methylene bis-4-phenylisocyanate are reacted at 100'C for 5 hours to form a urethane bleed poly-? -Polyurethane 180 obtained by binding and chain-extending it with butanediol
1 part is dissolved in 420 parts of dimethylformamide. on the other hand,
400 parts of an ethylene dichloride solution of polyglutamic acid-γ-methyl ester (solid content 20%, 2 molecules, approximately 250,000) is diluted with 400 parts of dimethylformamide. Next, 180 parts of the polyamino acid solution and 140 parts of the polyurethane solution are mixed under strong stirring. continuation.

Ethylene chloride was distilled off under reduced pressure, and a dimethylformamide solution of a blend resin with a weight ratio of polyamino acid and polyurethane of 30:10 (solution viscosity at 25°C: 2
248 parts of 5000 CPS were obtained. This will be referred to as blend resin A. This blend resin A is used in formulation 1 described below.

(Production of Blend Resin B) In the production of Blend Resin A, the weight ratio of polyamino acid and polyurethane was carried out in exactly the same manner as in the production of Blend Resin A, except that 300 parts of the polyamino acid solution and 150 parts of the polyurethane solution were used. 300 parts of a dimethylformamide solution (solution viscosity at 25°C: 23,000 CPS) of a blend resin with a ratio of 40:60 was obtained. This is referred to as blend resin B. This blend resin B will be used in Example 3 below. .

(PAU resin manufacturing) Polytetramethylene glycol C00 value 56.9) 19
70g and 1-6-hexamethylene diisocyanate) 5
04g was reacted at 90°C for 5 hours to form a urethane prepolymer having isocyanate groups at the terminals (NGO equivalent weight: 234g).
0) was obtained. 85 g of this urethane prepolymer and 85 g of T-methyl-L-glutamate-NCA were mixed in a mixed solvent of dimethylformamide/dioxane (weight ratio = 7/3).
Dissolve in 66g.

Add 50 g of 2% triethylamine solution while stirring and react at 30°C for 5 hours, resulting in a viscosity of 32.000.
A PAU resin solution of CPS (25° C.) in the form of a yellowish brown emulsion with good fluidity and a resin solid content concentration of 20% was obtained. P this
Made of AU resin. This PAU resin is used in formulation 2 of the resin description.

A moisture-permeable waterproof fabric of the present invention was produced using blended resin A and PAU resin in the following manner.

First, a plain woven fabric (taffeta) with a warp density of 120 wood/inch and a weft density of 90 wood/inch using nylon 70 denier/48 filament for both the warp and weft is prepared as a base fabric, and this is scoured using the usual method. After dyeing with acid dye, pat with 5% aqueous solution of Asahi Guard 710 (product of Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion (squeezing ratio: 35%), and heat treatment at 160°C for 1 minute after drying. I did it. Next, calendering was performed using a calendering machine with mirror-finished rolls at a temperature of 170° C., a pressure of 30 kg/cm, and a speed of 20 m/7 min.

Coat a resin solution with a resin solid content concentration of 21% as shown in Formulation 1 below using a knife over roll coater ff110
After coating at g/m, the resin was immersed in a 15°C water bath for 40 seconds to solidify the resin. Then, in warm water at 50°C for 10
Washed for minutes and dried.

Prescription 1 Blend resin A100 parts Crisbon BL-50 (isocyanate compound.

Dainippon Ink & Chemicals Co., Ltd. product) 1 part dimethylformamide 14 parts Next, apply a resin solution with a resin solid content concentration of 18% shown in the following recipe 2 to the resin-coated surface of the fabric using a knife-over-roll coater. ff150 g/n? After coating, the fabric was immersed in a water bath at 15°C for 0 minutes to solidify the resin, followed by washing in warm water at 50°C for 5 minutes and drying to obtain a moisture-permeable waterproof fabric of the present invention. .

Formulation 2 PAU resin
．． 5 parts Holivinylpyrrolidone (hydrophilic polymer with a molecular weight of 400,000 and a micropore forming agent)
5 parts dimethylformamide 14 parts 1 for comparison with the present invention A moisture-permeable waterproof fabric for comparison was prepared in exactly the same manner as in this example except that PAU resin was used in place of blend resin A in formulation 1 of this example. Obtained.

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

As is clear from Table 1, the moisture permeable waterproof fabric according to the present invention has a water pressure resistance of 1500 m, which is the practical limit even after washing.
It showed good durability far exceeding m, and also had high moisture permeability and no problems with other performances.

Example 2 In manufacturing the moisture permeable waterproof fabric of Example 1 above.

Crisbon assister 5 in formulation 2 of the resin liquid used
A moisture permeable waterproof fabric of the present invention was produced in exactly the same manner as in Example 1, except that the amount of D-11 (micropore forming agent) used was 1 part. When the performance of the obtained fabric was measured, the water pressure resistance was 3600 mm before washing and 2100 mm after washing, and even after one wash it far exceeded the practical limit of 1500 mm, showing good durability. 792
High moisture permeability at 0g/m・24hrs, problematic at ↑ΩΩ variation of 100 (excellent performance was shown in both cases).

Example 3 In the production of the moisture-permeable waterproof fabric of Example 1.

Blend resin B was used in place of blend resin A in formulation 1 of the resin liquid used, and the amount of Crisbon Assister 5D-11 (micropore forming agent) used in formulation 2 of the resin liquid used was 1 part.

A moisture permeable waterproof fabric of the present invention was produced in exactly the same manner as in Example 1. When the performance of the obtained fabric was measured,
Water pressure resistance is 3500mm before washing and 2100mm after washing, and even after washing it shows good durability, far exceeding the practical limit of 1500mm, and moisture permeability is 803mm.
High moisture permeability at 0g/m/24hrs.

Furthermore, there was no problem at the water-covering degree of 100, and excellent performance was exhibited in all cases.

(Effects of the Invention) The present invention provides wet coating using a blend resin liquid in which a polyamino acid resin and a polyurethane resin are mechanically mixed in a common solvent, and then a wet coating using a PAD resin liquid to form micropores. It has a structure in which coating is performed, and with this structure, it is possible to obtain a moisture-permeable waterproof fabric that has excellent durability and satisfies water pressure resistance.

The moisture permeable waterproof fabric of the present invention is a material well suited for sports clothing due to its excellent performance.

Claims (1)

[Claims] (1) The first step is to apply a resin solution consisting of a polyamino acid resin, a polyurethane resin, an isocyanate compound, and a polar organic solvent to a fiber fabric, and then immerse it in water, wash it with hot water, and dry it. After applying a resin solution consisting of a urethane resin, an isocyanate compound, a micropore forming agent, and a polar organic solvent, it is immersed in water.
A method for producing a moisture-permeable waterproof fabric, comprising a second step of washing with hot water and drying.