JPS60154054A - Moisture-permeable waterproof cloth and manufacture thereof - 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 The present invention relates to a fabric structure having three functions of waterproofness and moisture permeability at the same time, and a method for manufacturing the same. Generally, moisture permeability and waterproofness are contradictory functions, but waterproof fabrics with excellent moisture permeability form continuous micropores that allow water vapor to escape in the coating resin film during dry or wet coating processing. It is obtained by letting

Polyurethane elastomers are generally preferably used as coating resins during these dry or wet coating processes in terms of film strength, rubber elasticity, and flexibility. However, in the case of breathable waterproof fabric made from polyurethane elastomer, it is made based on a balance between waterproof performance and moisture permeability, so its waterproof performance is JIS L-.
For fabrics with a water pressure resistance measurement of 1,500mm (under the water column) or more of 1096.

Moisture permeability is 4,000-5,000 g/rrr・
At present, it is not possible to obtain a speed of about 24 hrs (JIS Z-0208 measurement). If this moisture permeability level can be improved to 7,000g/rd・24hrs or more, it will be almost the same as a non-coated fabric that is simply a high-density fabric using ultra-fine filaments in the warp that is water-repellent and calendered. Since they have the same level of moisture permeability, it is easier to control the humidity inside the clothes due to sweating when working in the rain or exercising.

This has made it possible to perform even more strenuous exercise and work in comfort, but even today, fabrics with a water pressure resistance of L500 mm or more and a moisture permeability of 7,000 g / % / 24 hrs or more are still available. The reality is that this is not the case. The present invention was made in view of the current situation, and the purpose is to obtain a highly moisture permeable waterproof fabric that has a water pressure resistance of 1,500 mm or more and a moisture permeability of 7,000 g/rd・24 hrs or more. It is something to do.

The present invention that achieves this object has the following configuration.

That is, the present invention provides an r(11) film having microcells interconnected by pores in the thickness direction, and having countless micropores with a surface diameter of 5 μm or less communicating with the microcells on the surface of the film. A porous film made of a synthetic polymer mainly composed of urethane resin is provided on one or both sides of the uh fiber base material, and has a moisture permeability of 7,000 g/rd・2.
A moisture-permeable waterproof fabric with a water resistance of 4 hrs or more and a water pressure resistance of 1,500 mm or more" and "(2) After applying a resin solution consisting of a polyamino acid urethane resin, a nonionic surfactant, and a polar organic solvent to one or both sides of the fiber base material. , the fiber base material is heated to 0°C
It was immersed in ~30°C water, then washed with hot water, dried, and then ta
The gist of this paper is ``a method for producing a moisture-permeable waterproof fabric characterized by applying a liquid agent.''

Two aspects of the present invention will be described in detail below.

The fiber base materials 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 polyvinyl alcohol synthetic fibers. Examples include woven and knitted fabrics made of semi-synthetic fibers such as triacetate and blended fibers such as nylon 6/cotton and polyethylene terephthalate/cotton.

In the method of the present invention, first of all, polyamino acid urethane resin,
A resin solution consisting of a nonionic surfactant and a polar organic solvent is applied.

The polyamino acid urethane resin used here is optically active T
After mixing N-carboxylic acid anhydride (hereinafter N-carboxylic acid anhydride is abbreviated as NCA) and a urethane prepolymer having an isocyanate group at the end, amines are mixed. It is made of a polyamino acid urethane copolymer resin (hereinafter abbreviated as PAυ resin) that is added and reacted, and the solvent for monopolymerization is a mixed solvent of dimethylformamide and dioxane (weight ratio: 95;
5 to 30 near 0) was used. Since this solvent is water-soluble, wet processing can be easily performed when applying the PAU resin to the fiber base material. As optically active γ-alkyl glutamate-NCA.

L-glutamate-1. or D-glutamate may be used.

Specifically, γ-methyl-L-glutamate-NCA.

γ-alkyl-D-glutamic acid)-NCA such as T-ethyl-L-glutamate-NCA, or γ-alkyl-D-glutamic acid-NCA such as γ-ethyl-D-glutamate-NCA alone. or as a mixture thereof. It is also possible to use α-amino acid-NCA mainly composed of γ-alkyl-glucumate-NCA as the amino acid component of PAD resin, and optically active γ-alkyl-glutamate-NCA and other amino acids can also be used as the amino acid component of PAD resin. Mixtures with NCAs such as glycine NCA, L-aspartic acid-β-methyl ester NCA, L-alanine NCA, D-alanine NCA, etc. can also be used. however,
Considering physical properties and price, γ-methyl-mono-glucumate-N (:A or T-methyl-D-glutamate-N
It is often industrially advantageous to use CA alone.

The urethane prepolymer having an isocyanate group at the terminal has an equivalent ratio of isocyanate and polyol of NGO10i.
It is obtained by reacting under the conditions of 1>1. As the isocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc. may be used alone or as a mixture thereof. In addition, as polyol components, polyether glycols, polyester glycols, etc. used in ordinary urethane products can be used alone or in the form of a mixture, and the average molecular weight of these polyethers and polyesters is 200 to 30.
A value of 0 or more is preferably used. The amines used in the copolymerization include primary alkylamines such as ethylenediamine, alcoholamines such as ethanolamine, tertiary alkylamines such as triethylamine, and secondary amines such as diethylamine.

The amount of PAD resin attached to the fiber base fabric is 5g/
It is desirable that the amount is more than +rr, and the adhesion amount is 5g/r+?
If it is less than 1,500 mm, it is difficult to obtain water pressure resistance of 1,500 mm or more.

The reason for using PAD resin in the present invention is as follows. That is, PAU resin, unlike ordinary polyurekne resin, has the ability to allow water vapor to pass through even if it is a non-porous film. Conventional moisture-permeable waterproof fabric with a porous urethane resin film has a water pressure resistance of 1.500 mm.
Above that, the moisture permeability is at most 5,000g/rd.
・In contrast to the 24hrs resistance, the present invention uses PALI resin, which has a water pressure resistance of 1.500mm or more and a moisture permeability of 7.000g/
A waterproof fabric with moisture permeability of rd/24hrs or more can be obtained.

Next, the nonionic surfactant in the present invention is polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol-
It refers to fatty acid esters, fatty acid sucrose esters, alkylo-doamides, etc., or any mixture thereof, and has the effect of appropriately controlling the pores in the resin film when coagulating PAD resin in water. .

Due to this effect, excellent waterproofness and moisture permeability can be obtained.

The amount of nonionic activator used is based on the amount of PAU resin used.
It is desirable that the amount is in the range of 1 to 10 parts by weight.

If the amount used is less than 1 part by weight, the pores in the coagulated film of the PAU resin become too small and connected microcells cannot be obtained, resulting in poor moisture permeability. If 10 parts by weight or more is used, the pores become too large and a water pressure resistance of 1.500 mm or more cannot be obtained.

In the present invention, the above-mentioned PAD resin, nonionic surfactant, and polar organic agent are mixed and used. Polar organic solvents include dimethylformamide, 3-dimethylacetamide, N-methylpyrrolidone, and hexamethylenephosphonamide. These substances are highly soluble in water,
When a polar organic agent solution of a water-insoluble resin is immersed in water, only the polar organic solvent dissolves in the water, and the resin solidifies in the water.

A resin coagulation method using such a method is generally called a wet coagulation method. When a resin is coagulated by a wet coagulation method, a trace amount of the polar organic solvent present in the resin is also eluted into water, making it possible to obtain a resin having countless pores.

A resin solution consisting of a PAD resin, a nonionic surfactant, and a polar organic solvent may be applied to the fiber base fabric by a conventional coating method. Generally, the coating thickness of the resin is 10 to 300 μm due to machine performance.

After applying the resin solution to the fiber substrate, the fabric is immersed in water. As mentioned above, this process makes it possible to form a PAD resin film having an infinite number of pores, and also to obtain pores that form a connected microcell structure due to the action of the nonionic surfactant.

When the fabric is immersed in water, the water temperature should be in the range of 0 to 30°C; if the water temperature exceeds 30°C, the pores of the resin film will become larger than 5 μm, resulting in poor water pressure resistance. Further, the dipping time must be at least 30 seconds; if it is less than 30 seconds, the resin will not coagulate sufficiently and a satisfactory PAD resin film will not be obtained.

After coagulating the PAD resin in water, the fabric is washed with hot water to remove residual solvent and surfactant.

Conditions for hot water washing vary depending on the amounts of PAD resin and surfactant used, but it may be carried out at a temperature of 30 to 80° C. for 3 minutes or more.

After washing with hot water, drying and applying a water repellent to the fabric. By adding a water repellent agent, the fabric surface becomes water repellent,
A moisture-permeable waterproof fabric with a water pressure resistance of 1 and 500 mm or more can be obtained. There are various types of water repellents such as paraffin-based, silicon-based, and fluorine-based water repellents, and in the present invention, they may be selected as appropriate depending on the application.

When particularly good water repellency is required, a fluorine-based water repellent is used, and heat treatment is performed after applying the water repellent and drying.

Further, in order to increase the durability of water repellency, a resin such as melamine resin may be used in combination. The water repellent may be applied by a commonly used banding method, coating method, spraying method, or the like.

In order to improve water repellency, a water repellent may be applied to the fiber base material before applying the resin solution consisting of the PAU resin, the nonionic surfactant, and the polar organic solvent to the fiber base material.

The present invention has the above configuration, and according to the present invention, it is possible to obtain a highly moisture permeable waterproof fabric that has a water pressure resistance of 1,500 mm or more and a moisture permeability of 7,000 g/m・24 hrs or more. can. The moisture-permeable waterproof fabric of the present invention is a material suitable for sports clothing and the like.

The present invention will be further explained below with reference to Examples.

The present invention is not limited to these.

Example 1 First, a polyamino acid urethane resin used in this example was manufactured by the following method.

Polytetramethylene glycol (011+il[i56
．． 9 > 1970 g and 540 g of 1-6-hexamethylene diisocyanate) were reacted at 90°C for 5 hours to form a urethane prepolymer with terminal isocyanate groups (NG
O equivalent weight 2340) was obtained. This urethane prepolymer 8
5g and T-methyl-L-glutame) -NCA 85
g to dimethylformamide/dioxane (weight ratio) -7
Dissolve in 666g of mixed solvent of /3 and add 2% while stirring.
When 50 g of triethylamine solution was added and the reaction was carried out at 30°C for 5 hours, a polyamino acid urethane resin solution having a viscosity of 32.0OOcps (25°C) and a yellowish brown emulsion with good fluidity was obtained. This polyamino acid urethane resin is used in Formulation 1 described below. Here, the warp is made of nylon 7
0 denier/24 filament ゛Nylon 70 weft
Plain woven fabric (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch using denier/34 filaments.
After preparing and scouring it in the usual way and dyeing it with acid dye.

Asahi Guard 730, a fluorine-based TA water emulsion (
Banding was performed with a 1% aqueous solution (product of Asahi Glass Co., Ltd.) (squeezing ratio: 35%), and heat treatment was performed at 160°C for 1 minute. Next, using a calendering machine with mirror-finished rolls, the temperature was 170°C, the pressure was 30kg/cm, and the speed was 20m/cm.
After calendering under the conditions of 10 minutes, a coating solution with a resin solid content concentration of 18% as shown in the following formulation 1 was applied at a coating amount of 80 g/% using a knife-over roll coater, and then placed in a water bath at 20°C. for 5 minutes to solidify the 411 fat.

Formulation 1 Polyamino acid urethane resin 100 parts Dimethylformamide 23 parts Here, immersion in warm water at 60°C for 30 minutes, followed by drying, followed by fluorine-based water repellent emulsion Asahi Guard 710 (Asahi Glass Co., Ltd. product) 5 % aqueous solution (squeezing ratio: 30%), and heat treatment was performed at 160° C. for 1 minute to obtain a moisture permeable waterproof fabric of the present invention.

For comparison with the method of the present invention, comparative samples were prepared according to Comparative Examples 1 and 2 described below, and the performance was compared with one product of the present invention. The results are shown in Table 1 together with the performance of the product of the present invention.

The performance was measured and evaluated using the following method.

A photograph of the fabric structure, which is the processed cloth, is taken using a scanning electron microscope, and the diameter of the micropores and the structure of the microcells in the cross-sectional direction are investigated using the photograph. Water pressure resistance is JIS-L-104
The friction water leakage test using the low water pressure method (1) was conducted using a Gakushin friction fastness tester, and the presence or absence of water leakage was determined by applying a load of 200 g/cJ, keeping the surface of the fabric moist and streaky, and rubbing the fabric 100 times. Moisture permeability was determined according to JIS-Z-028.

As is clear from Table 1, the moisture permeable waterproof fabric according to the present invention has a moisture permeability of 8,500 g/n, despite having a water pressure resistance of 2.000 mm or more.・HRS is recorded, and it can be seen that it has both outstanding moisture permeability and waterproof performance.

Table 1 Comparative Example 1 A nylon tack fabric of the same standard as in Example 1 was prepared, and after scouring and calendering in the same manner as in Example 1, a coating solution shown in the following formulation 2 was applied over a knife. The resin was coated using a roll coater at a coating amount of 80 g/rr, and then immersed in a 30°C water bath for 5 minutes to solidify the resin. In addition.

The polyamino acid urethane resin in Formulation 2 was the same as that used in Example 1.

Formulation 2 Polyamino acid urethane resin 100 parts Calcium carbonate (particle size 400 mS) 15 parts Dimethylformamide 20 parts Here, immersion in warm water at 60°C for 30 minutes, followed by drying, and then the same method as in Example 1 was carried out. Water repellent treatment was carried out using the following method.

The obtained fabric structure had good moisture permeability as shown in Table 1, but poor waterproof performance.

Comparative Example 2 A nylon taffeta fabric of the same standard as in Example 1 was prepared, and after scouring and calendering was performed on it in the same manner as in Example 1, a coating solution shown in the following formulation 3 was applied using a knife over roll coater. It was applied at a coating amount of 80 g/rd. The polyamino acid urethane resin in Formulation 3 was the same as that used in Example 1.

Formulation 3 Polyamino acid urethane resin 100 parts Dimethylformamide 28 parts Dioxane 12 parts After coating, dry at 80°C for 5 minutes, then put into water at 20°C to remove the solvent remaining in the film. It was left for 30 minutes. It was then dried. The surface film of the obtained fabric was a translucent film, unlike the films of Example 1 and Comparative Example 1. Thereafter, water repellent treatment was performed in the same manner as in Example 1. As shown in Table 1, the fabric structure thus obtained had good waterproof performance C, but poor moisture permeability.

Patent Applicant Uni Jinriki Co., Ltd. Procedural Amendment (Voluntary) May 4, 1980 Commissioner of the Japan Patent Office Patent Application No. 10853/1985 2 Title of Invention I3 Moisture Waterproof Fabric and Manufacturing Method Thereof 3 Amended Relationship with the Patent Case Patent Applicant Residence 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture 541 Address 4-68 Kitakyutabe-cho, Higashi-ku, Osaka Name Yu-Tei Riki Co., Ltd. Patent Department Telephone 06-281-5258 (Dial-in) 4. Column 5 of "Detailed Description of the Invention" of the specification to be amended? #Positive content tll [-1 used here on page 5, line 4 of the specification] to [- on page 7, line 11 are used. Delete up to j and insert the first sentence.

“Polyamino acid urethane resin (hereinafter referred to as PA) used in the present invention
It is called II resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include OL-alanine, L-aspartic acid, L-cystine, L-glutamic acid, chrysine, L-lysine, L-methionine, L-leucine and their like. When synthesizing polyamino acids, amino acid N-carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride) obtained from amino acid and phosgene is
That's what it means.

) is commonly used. In polyurethane, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates are used singly or as a mixture thereof as incyanate components.2For example, toluene, 2,4-diisocyanate, 1,54,4'-diphenylmethane diisocyanate, 1,6-hexane, etc. Examples include diisocyanate, 1,4-cyclohexane diisocyanate, and the like. Also,
As the polyol component, polyether polyols and polyester polyols are used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.
Ethylene glycol is also used as a polyester polyol.

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 ethylenediamine, diethylamine, triethylamine, ethanolamine, and the like. 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. Optically active γ-alkyl glutamate-NCA is preferably used as the amino acid component constituting the PAυ resin from the viewpoint of film performance, and among the optically active γ-alkyl glutamates, γ-methyl-L- Glutamate NCA or γ-methyl-D-glutamate is often advantageously selected as the amino acid component of the PAυ resin.

In order to obtain the porous membrane of the present invention, it is advantageous in terms of both coating properties and wet film forming properties to use a uniform resin composition made of a water-soluble solvent system. Such resin compositions include:
Among PAD resins, a reaction product of optically active γ-alkylglutamic acid (γ-glutamic acid)-NCA and a urethane prepolymer is particularly preferably used. This is because the weight ratio of amino acid to urethane can be selected from a wide range of 90:10 to 10:90 in a mixed solvent system. (2) From page 7, line 16 of the specification, “PAD resin is used in the present invention” to page 8, line 6, “-”.

” and insert the second sentence.

"On the other hand, in the case of conventional moisture-permeable waterproof fabrics having a porous urethane resin film, when the water pressure resistance is 1,500 mm or more, the moisture permeability is at most 5,000 g/m2.24
While only hrs 41 degrees can be obtained, PAD
When wet coating resin, the water pressure resistance is 15
00mm or more and moisture permeability of 7000g/m”
・It is possible to obtain the surprising result of showing moisture permeable and waterproof performance for 24 hours or more. The reason why high water pressure resistance and high moisture permeability can be obtained by wet coating processing of PAU resin is not clear, but when observing the cross section of the membrane of the resulting moisture-permeable waterproof fabric, it is clear that it is compared to a polyurethane membrane. , in the case of PAD resin film, the microcells are small,
Moreover, their number is large and uniformly distributed, which is thought to be a factor in providing high moisture permeability and high water pressure resistance. Furthermore, the high affinity of PAD resin itself for water vapor may be one of the driving forces for providing high moisture permeability. (3) Insert the following sentence between the 5th and 6th lines of page 9 of the specification.

``Also, as far as the moisture-permeable waterproof fabric according to claim 1 of the present invention is concerned, its production is not limited to the use of the above-mentioned nonionic surfactant.'' (4) Specification On page 10, lines 11 to 13, the phrase ``The resin film becomes defective.'' is replaced by ``The dimethylformamide diffuses into the water quickly.''

Since the nonionic surfactant promotes the diffusion of dimethylformamide into water, the interaction between the two causes the pores in the resin film to become larger than 5 μm, resulting in poor water pressure resistance. ” he corrected.

(5) Delete "Fluorine-based treatment" from lines 5 to 8 on page 13 of the specification.

Claims (2)

[Claims] (1) Mainly composed of 5-polyamino acid urethane resin, which has microcells interconnected by pores in the thickness direction of the coating, and countless micropores with a surface diameter of 5 μm or less communicating with the microcells on the coating surface. Moisture permeability 7000, which has a porous film made of a synthetic polymer on one side of a fiber base material.
g/rd ・24hrs or more, water pressure resistance 1500mm
Breathable waterproof fabric. (2) After applying a resin solution consisting of a polyamino acid urethane resin, a nonionic surfactant, and a polar organic solvent to one or both sides of the fiber base material, the fiber base material is immersed in water at 0°C to 30°C. 3. A method for producing a moisture-permeable waterproof fabric, which comprises washing with hot water and applying a water repellent after drying.