JPS60173178A - Production of moisture permeable water-proof 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 The present invention relates to a method for manufacturing a fabric that simultaneously has three functions: waterproofness and moisture permeability. Generally, breathability and waterproofness are contradictory functions.

Waterproof fabrics with excellent moisture permeability are obtained by forming continuous fine pores that allow water vapor to escape in the coating resin film during dry or wet coating. Polyurethane elastomers are generally preferably used as coating resins in these dry or wet coating processes in view of their peel strength, rubber elasticity, and flexibility. However, moisture-permeable waterproof fabrics made from polyurethane elastomer are made based on a balance between waterproof performance and moisture-permeable performance.

Waterproof performance is 1.5 according to JIS L-1096 water pressure measurement.
For fabrics with a rating of 00 IIlm (under the water column) or higher, the moisture permeability is 4,000 to 5,000 g/rd/24h.
At present, only those on the order of rs (JIS Z-0208 measurement) have been obtained. The high-density fabric using this filament has almost the same moisture permeability as a non-coated fabric that is simply calendered with 18% water, so it is possible to prevent the inside of clothes from sweating when working in the rain or exercising. Humidity control becomes smoother, making it possible to perform even more strenuous exercise and work in comfort, but with water pressure resistance of 1.50 km or more,
The fabric has a moisture permeability of 00g/rd・24hrs or more.

The reality is that even to this day, this has not yet been achieved. The present invention was developed in view of the current situation, and has a water pressure resistance of 1.500 mm or more and a moisture permeability of 7.5 mm.
The purpose of the present invention is to obtain a waterproof fabric with high moisture permeability of 000 g/n (24 hrs or more).In order to achieve this purpose, the present invention has the following configuration.

That is, the present invention is a polyamino acid urethane resin.

Polyurethane resin, nonionic surfactant and polarity 4!
! After applying a resin solution made of a solvent to the fiber base material, the fiber convex material is immersed in water at 0°C to 30°C, and then washed with hot water,
The gist of this invention is a method for producing a moisture-permeable waterproof fabric, which is characterized by applying a Ja solution after drying.

Hereinafter, nine aspects of the present invention will be described in detail.

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, such fibers such as woven or knitted fabrics are
l A resin solution consisting of a polyamino acid urethane resin, a polyurethane resin, a nonionic surfactant, and a polar organic solvent is applied to one or both sides of the bracket +4.

The polyamino acid urethane resin used here has optical activity γ
-Alkyl-glutamate-N-carboxylic anhydride (hereinafter N-carboxylic anhydride is abbreviated as NCA) and a urethane prepolymer having an isocyanate group at the end are mixed, and then amines are added and reacted. It is made of polyamino acid urethane copolymer resin (hereinafter abbreviated as PAII resin), and the solvent used in the double polymerization is a mixed solvent of dimethylformamide and dioxane (weight ratio 95:
5-30:70) was used. Since this solvent is water-soluble, wet processing can be easily performed when applying the IIAU resin to the fiber base material. Optical activity γ
-Alkyl-glutamate-11G8.

It may be L-glutamate or D-glutamate.5 Specifically, γ-methyl-L-glutamate-NCA.

γ-alkyl groups such as T-ethyl-glutamic acid 1--NC8) - glutamate-NC, γ-alkyl-D-glutamic acid 1--NCAs such as γ-ethyl-D-glutamate-NCA alone or in mixtures thereof It can be used as It is also possible to use α-amino acid-NCA mainly consisting of γ-alkyl-glutamate-CA as the amino acid component of PAU resin, and optically active T-alkyl-glutamic acid-INcA and other amino acids NC For example, glycine NCA, L-aspartic acid-β-methyl ester NC^, L-alanine NCA,
A mixture with D-alanine NCA etc. can also be used. However, in consideration of physical properties and cost, it is often industrially more advantageous to use γ-methyl-L-glucumate-NC^ or γ-methyl-D-glutamate-NC^ alone.

The urethane prepolymer having isocyanate groups at the terminals has an equivalent ratio of isocyanate and polyol of NCO10i.
It is obtained by reacting under the conditions of l>1. As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. may be used alone or as a mixture thereof. In addition, as the polyol component, polyether glycol, polyester glycol, etc. used in ordinary urethane products can be used alone or in the form of a mixture. 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 less than 5 g/d, and it is difficult to obtain a water pressure resistance of 1,500 mm or more.

The reason for using PAU resin in the present invention is as follows. That is, unlike ordinary polyurethane resins, PAD resin has the ability to allow water and air to pass through even if it is a non-porous film. Conventional moisture-permeable waterproof fabrics with a porous urethane resin film have a water pressure resistance of 1.500 m.
m or more, the moisture permeability is at most 5,000 g/m・2
In contrast, in the present invention, by using PAU resin, the water pressure resistance is 1 hrs.
, 500mm or more and moisture permeability 7,000g/n (・2
A moisture permeable waterproof fabric with a durability of 4 hours or more can be obtained.

The polyurethane resin in the present invention is a polymer obtained by reacting polyisocyanate and polyol,
As the polyisocyanate, known aliphatic and aromatic polyisocyanates can be used, such as hexamethylene diisocyanate.

toluene diisocyanate xylene diisocyanate,
and reaction products of excess thereof and polyhydric alcohols. As a polyol.

Known materials such as polyether or polyester used in the production of ordinary polyurethane resins can be used. Examples of polyester include ethylene glycol,
Examples include reaction products of polyhydric alcohols such as diethylene glycol or 1,4-butanediol and polybasic carboxylic acids such as adipic acid, oxalic acid, or sebacic acid. Examples of polyether include polyhydric alcohols such as ethylene glycol and propylene glycol to which one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added.

The amount of polyurethane resin to be used is preferably 1% to 200% based on the PAD resin. If the amount used is less than 1%, moisture permeability will be poor.

If it exceeds 200%, the waterproofness becomes poor.

The method of the present invention is to obtain a fabric with excellent water pressure resistance and moisture permeability, and its principle is to create numerous pores large enough to prevent water from passing through in the PAD resin film, which has relatively good moisture permeability. This is due to

When polyurethane resin and PAII resin are immersed in water at the same time, PAU resin solidifies faster than polyurethane resin, so a space is created at the boundary between PAtl resin and polyurethane resin, and this space determines the size of the pores in the resin film. do. If the amount of polyurethane resin is small, the pores will be small and the moisture permeability will be poor.

Moreover, if the amount of polyurethane resin is large, the pores will become hard and the water pressure resistance will be poor.

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 0.1 to IO parts by weight.

If the amount used is less than 0.1 parts by weight, the pores in the coagulated film of the PAU resin will become too small, 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 500 mm or more cannot be obtained.

In the present invention, the above-mentioned PAD resin, polyurethane resin, nonionic surfactant, and polar organic agent are mixed and used.

Polar organic solvents include dimethylformamide, 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, it becomes polar! Only the solvent dissolves in 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.

The resin solution consisting of PAU resin, polyurethane resin, nonionic surfactant, and polar organic solvent may be applied to the fiber base fabric by a conventional coating method. Generally, resin coating II is 10~300 μm due to machine performance.
It is.

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 PAII resin film with an infinite number of pores, and through the action of the polyurethane resin and nonionic surfactant, it is possible to obtain pores that form a connected microcell structure. .

When immersing the fabric in water, the water temperature should be in the range of 0 to 30℃, and if the water temperature exceeds 30℃, the pores of the resin film will be reduced.
If it becomes larger than μm, the water pressure resistance becomes poor. Further, the dipping time is required to be at least 30 seconds; if it is less than 30 seconds, the resin will not solidify sufficiently and a satisfactory PAU resin film will not be obtained.

After coagulating the PAtl resin in water, the fabric was washed with hot water,
Remove remaining solvent and surfactant.

Conditions for hot water washing vary depending on the amounts of PAυ resin, polyurethane resin and surfactant used, but at a temperature of 30 to 80°C.
It may be carried out for at least 10 minutes, preferably for at least 10 minutes.

After washing with hot water, drying and applying a water repellent to the fabric. By adding a hydrophobic agent, the fabric surface becomes water repellent,
It is possible to obtain a moisture permeable waterproof fabric with a water pressure resistance of 1 and 500 m5 or more. There are various types of water repellents, including 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 TA solution may be applied to the fiber base material before applying the resin solution comprising the PAD resin, nonionic surfactant, and polar organic solvent to the fiber base material.

The present invention has the above structure, and according to the present invention, it is possible to obtain a highly moisture permeable waterproof fabric having a water pressure resistance of 1,500 mm or more and a moisture permeability of 7,000 g/I.24 hrs or more. 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, the polyamino acid urethane resin used in the two examples was manufactured by the following method.

Polytetramethylene glycol (01111i56.9
) and 540 g of 1-6-hexamethylene diisocyanate were reacted at 90°C for 5 hours to obtain a urethane prepolymer having an isocyanate group at the end (NGO
12340) was obtained. This urethane prepolymer 858
and T-methyl-L-glutamic acid)-NC8 were dissolved in 666 g of a mixed solvent of dimethylborumamide/dioxane (weight ratio) = 7/3, and while stirring, 50 g of 2% triethylamine solution was added, and the mixture was heated at 30°C. When the reaction was carried out for 5 hours, a polyamino acid urethane resin solution having a viscosity of 32,000 cps (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 nylon 70 denier/24 filament.

A plain woven fabric (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch using nylon 70 denier/34 filament as the weft was prepared, and after scouring and dyeing with acid dye using the usual method. .

Fluorine-based ID water emulsion Asahi Guard 730 (
Asahi Glass Co., Ltd. product) Puffing was performed with a 1% aqueous solution (squeezing ratio: 35%), and heat treatment was performed at 160° C. for 1 minute. Next, calendering was performed using a calendering machine with a mirror-finished roll at a temperature of 170°C, a pressure of 30kg/ca+, and a speed of 20m/min.
A coating solution having a resin solid content concentration of 18% as shown in the figure was applied at a coating amount of 80 g/td using a knife-over-roll coater, and then immersed in a 20°C water bath for 5 minutes to solidify the resin.

Formulation 1: Polyamino acid urethane resin 100 parts Dimethylformamide 23 parts Here, immerse in warm water at 60°C for 30 minutes, rvE and dry, then add Asahi Guard 710 (Asahi Glass Co., Ltd. product) 5% aqueous solution of fan type 1a water-based emulsion. Banding (squeezing ratio: 30%) was performed, and heat treatment was performed at 16[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.

The fabric structure, which is the processed fabric, was photographed using a scanning electron microscope, and the diameter of the micropores and the structure of the microcells in the cross-sectional direction were determined using the photograph. Water pressure resistance is JIS-L-104
The friction water leakage test using the low water pressure method in No. 1 was conducted using a hand-held friction fastness tester, and the presence or absence of water leakage was determined by rubbing 100 times under a load of 200 g/cd while keeping the fabric surface in a wet state. Moisture permeability was determined according to JIS-Z-0208.

As is clear from Table 1, the moisture permeable waterproof fabric according to the present invention has an outstanding water permeability of 9.000 g/rd-hrs despite having a water pressure resistance of 2.000 W* or more. It can be seen that it has both moisture 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. J7 using a roll coater? and applied 180 g/
The resin was coated at m+ and immersed in a 30°C water bath for 5 minutes at Vt 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 Dimethylformamide 23 parts Here, the sample was immersed in warm water at 60°C for 30 minutes, then dried, and then subjected to water repellent treatment in the same manner as in Example 1.

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 in the same manner as in Example 1, a coating solution shown in the following formulation 3 was coated with knife-over-roll coke. Coating was carried out at a coating rate of 1180 g/rrr. 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 fabric obtained 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 but poor moisture permeability.

Patent Applicant Unitika Co., Ltd. Procedural Notes (Voluntary) 1. Indication of the Case Japanese Patent Application No. 59-29233 2. Name of the Invention Method for Manufacturing a Moisture-Permeable Waterproof Fabric 3. Name of the Person Making the Amendment I. L1 Related Patent Applicant A] Address 1-50 Higashihonmachi, Amagasaki-shi, Hyogo 541 Address 4-68-4 Kitakyutabe-cho, Higashi-ku, Osaka 01. Column 5 of “Detailed explanation”? +If Correct Contents (1) Delete the lines from "- is used here" on the 9th line of page 4 to "- is used" on the 16th line of page 6 and insert the following sentence: .

[Polyamino acid urethane resin used in the present invention (hereinafter referred to as P
It is called AU 4Jl fat. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-
Alanine, L-asparagine M, L-cystine, L-glutamic acid, glycine, L-lysine, L-methionine,
Examples include L-leucine and its derivatives, and the amino acid N-carboxylic anhydride (hereinafter N-carboxylic anhydride is referred to as NCA) is obtained by +4i from an amino acid and phosgene when polyamino acids are synthesized.

) is commonly used. The isocyanate component of the polyurethane is aromatic diisocyanate, aliphatic diisocyanate-1, and alicyclic diisocyanate, singly or in combination.・6-hexane diisocyanate, ■・4-
Examples include cyclohexane diisocyanate. Moreover, polyether polyol and polyester polyol are used as the polyol component. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols include ethylene glycol.

Examples include reaction products of diols such as pyrene glycol and dibasic acids such as adipic acid and sepatic acid, and ring-opening polymers such as caprolactone. As the amines used in the copolymerization of amino acids and polyurethane, ethylenediamine, diethylamine, triethylamine, ethanolamine, etc. are used. As described above, PAU resins are obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymers having isocyanate groups at the terminals. As the amino acid component constituting the PAD resin, optically active γ-alkyl glutamate-1-NCA is preferably used from the viewpoint of film performance, and among the optically active γ-alkyl glutamates, γ -Methyl-I, -glutamate NC or γ-methyl-D-glutamate are often advantageously selected as the amino acid component of the PAD resin.

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. Such resin compositions include:
P A 04i (among fats, a reaction product of optically active γ-alkyl-glutamate-NC8 and a urethane prepolymer is preferably used, but this is because the above reaction product is a solvent system mainly composed of a polar organic solvent, such as dimethylformamide). and dioxane in a mixed solvent system with a weight ratio of amino acid and urethane of 90:10 to 10290
This is because the above-mentioned weight f3 ratio can be freely selected while taking into consideration the physical properties of the film required to obtain a uniform resin solution over a wide range of areas. (2) Delete "The present invention..." from lines 1 to 11 on page 7 of the specification and insert the following sentence.

"On the other hand, with conventional moisture-permeable waterproof fabrics having a porous urethane resin film, when the water pressure resistance is 1500 m+n or more, the moisture permeability is at most 5000 g/m2 for 24 hours.
On the other hand, when wet-coating PA[I resin, the water pressure resistance is 1500 m.
m or more and moisture permeability of 7000 g/m2.24
It is possible to obtain the surprising result of exhibiting moisture permeable and waterproof performance exceeding hrs. The reason why high water pressure resistance and high moisture permeability can be obtained through wet coating processing of PAU resin is not obvious, but when observing the cross section of the membrane of the obtained moisture-permeable waterproof fabric, it is found that compared to polyurethane membrane, PA
In the case of the D resin film, the microcells are small, there are many of them, and they are uniformly distributed, which is thought to be a factor in providing high moisture permeability and high water pressure resistance. Further P
The high affinity of AU resin itself for water vapor may also be the driving force behind its high moisture permeability. (3) On page 11, lines 12 to 14 of the specification, the phrase ``- of the resin film becomes defective.'' was replaced with ``dimethylformamide diffuses into water quickly and the nonionic surfactant In order to promote the diffusion of dimethylformamide into water, the pores in the resin film become larger than 5 μm due to the interaction between the two, resulting in poor water pressure resistance."

(4) Delete ``Fluorine-based treatment'' from lines 7 to 10 on page 14 of the specification.

Claims (1)

[Claims] (11 polyamino acid urethane resin, polyurethane resin,
After applying a resin solution consisting of a nonionic surfactant and a polar organic solvent to the fiber base material. A method for producing a moisture-permeable waterproof fabric, which comprises immersing the fiber base material in water at 0° C. to 30° C., then washing with hot water, and applying a water repellent after drying.