JPS60162872A - Production of moisture permeable water-proof fabric - 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 producing a fabric structure having three functions of waterproofness and moisture permeability at the same time.

Generally, breathability and waterproofness are contradictory functions, but
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 terms of film strength, rubber elasticity, and flexibility. However, in the case of moisture-permeable waterproof fabric made from polyurethane elastomer, it is made based on a balance between waterproof performance and moisture permeability, so its waterproof performance is 1.500a when measured with water pressure resistance according to JIS +, -1096.
For fabrics of +m (below the water column) or more, the moisture permeability is 4.
OOO~5. OOOg / nf ・24hrs (J
At present, only those equivalent to IS Z-0208 measurements) have been obtained. This moisture permeability level is 7,000
g/n (・If it can be improved to 24 hrs or more, the moisture permeability will be almost the same as a non-coated fabric made by simply applying water repellency and calendaring to a high-density fabric using ultra-fine filaments for warp and warp yarns. This makes it easier to control the humidity inside the clothes due to sweating when working in the rain or exercising, and this makes it possible to perform even more strenuous exercise or work comfortably, but the water resistance is low. 1.7,000 for items over 500mm
The reality is that a fabric with a moisture permeability of g/nr/24 hrs or more has not yet been obtained to date. 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+ nm or more and a moisture permeability of 7,000 g/rd/24 hrs or more. That is. In order to achieve this object, the present invention has the following configuration.

That is, the present invention is directed to "after applying a resin solution consisting of a polyamino acid urethane resin, a polyurethane resin, and a polar organic solvent to one or both sides of a 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, first washing it in hot water, and then applying a water repellent 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, polyamino acid urethane resin,
A resin solution consisting of polyurethane resin and a polar organic solvent is applied.

The polyamino acid urethane resin used here is optically active T
-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. Polyamino acid urethane copolymer resin (hereinafter abbreviated as PAU resin).

), and the solvent for monopolymerization 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 PAU resin to the fiber base material. As optically active γ-alkyl glutamate-NCA.

It may be L-glutamate or D-glutamate.

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

To T-alkyl-glutamate NC such as γ-ethyl-glutamate-NG, γ-methyl-D-glutamate-NCA, T-ethyl-D-glutamate-N
T-alkyl-D-glutamate-NCAs such as CA can be used alone or in mixtures thereof.

In addition, it is also possible to use α-amino acid-NCA mainly composed of γ-alkyl-glucumate-NC^ as the amino acid component of PAD resin, and optically active γ-alkyl-glutamate-NeA and other amino acids NC^ For example, a mixture with glycine NCA, L-aspartic acid-β-methyl ester NCA, L-alanine NCA, 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-glutamate-NC or T-methyl-D-glutamate-NCA alone.

The urethane prepolymer having an isocyanate group at the terminal has an equivalent ratio of isocyanate and polyol of NGO10H.
It is obtained by reacting under the conditions of >1. As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. may be used alone or as a mixture thereof. In addition, as a polyol component, polyether glycol, polyester glycol, 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 300 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 PAIJ resin attached to the fiber base fabric is 5g in pure form.
It is desirable that the coating weight is at least /nf, and if the amount of adhesion is less than 5 g/d, it is difficult to obtain a water pressure resistance of 1,500 mm or more.

The reason for using PA[I resin in the present invention is as follows. That is, unlike ordinary polyurethane resins, PAU resin has the ability to allow water vapor 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
If it is mn+ or more, the moisture permeability is at most 5,000g/n.
Whereas only about f・24hrs can be obtained, in the present invention, by using PAU resin, the water pressure resistance is 1.500+nl11 or more and the moisture permeability is 7.000.
A moisture permeable waterproof fabric having a g/rd ・24 hrs or more can be obtained.

Next, the polyurethane resin in the present invention is a polymer obtained by reacting a polyisocyanate and a polyol. As the polyisocyanate, known aliphatic and aromatic polyisocyanates can be used.9 For example, hexamethylene diisocyanate, toluene diisocyanate, xylene Mention may be made of diisocyanates and the reaction products of their excess with polyhydric alcohols. As the polyol, known polyethers, polyesters, and other polyols used in the production of ordinary polyurethane resins can be used. Examples of polyesters include reaction products of polyhydric alcohols such as ethylene glycol, diethylene glycol or 1,4-butane diol and polybasic carboxylic acids such as adipic acid, citric acid or sebacic acid. Examples of the 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 used is preferably 1% to 200% based on the PAυ 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 of a size that cannot allow water to pass through in the PAυ resin film, which has relatively good moisture permeability. This is due to

When polyurethane resin and PAU resin are immersed in water at the same time, PAD resin solidifies faster than polyurethane resin, so a space is created at the boundary between PAD 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 become smaller,
Moisture permeability becomes poor.

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

In the present invention, the above-mentioned PAtl resin and polyurethane resin are used in combination with a polar organic agent. 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, only the polar organic solvent dissolves in the water, and the resin coagulates 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 eluted into water, so a resin having countless dark blue pores can be obtained.

The resin solution consisting of PAU resin, polyurethane resin, and 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 PAU resin film with countless pores, and the action of the polyurethane resin makes it possible to obtain pores of an appropriate size that provide good moisture permeability and water pressure resistance. can.

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 large and the water pressure resistance will be poor. In addition, the immersion time must be at least 30 seconds; if it is less than 30 seconds, the resin will not solidify sufficiently, resulting in a satisfactory P.
AU resin film cannot be obtained.

After coagulating the PA[l resin in water, the fabric was washed with hot water,
Remove remaining solvent. The hot water washing conditions vary depending on the amount of PAU resin and polyurethane resin used, but 30
It may be carried out at a temperature of ~80°C for 3 minutes or more.

After washing with hot water, drying and applying a water repellent to the fabric. By applying a water repellent, the surface of the fabric can be given IB water resistance, and 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 a TA water agent is applied and a heat treatment is performed after 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 the resin solution consisting of the PAIJ resin, polyurethane resin, and polar organic solvent is applied 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 having a water pressure resistance of 1.500 II 1 m 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, a polyamino acid urethane resin used in this example was manufactured in the following manner.

Polytetramethylene glycol (01 value 56.9) 19
70g and 50g of 1-6-hexamethylene diisocyanate
4g was reacted at 90°C for 5 hours to obtain a urethane prepolymer having an isocyanate group at the end (NGO equivalent weight: 2340
) was obtained. This urethane prepolymer 85g1l! :T
-Methyl-L-glutamate-NCA 85g was dissolved in 666g of a mixed solvent of dimethylformamide/dioxacyl (weight ratio) = 7/3, 50g of 2% triethylamine solution was added while stirring, and the reaction was carried out at 30°C 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. .

Pa-noding (squeezing ratio: 35%) was performed with a 1% aqueous solution of Asahi Guard 730 (product of Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion, and heat treatment was performed at 160° C. for 1 minute. Next, calendering was carried out using a calendering machine with mirror-finish rolls at a temperature of 170°C, a pressure of 30kg/c+++, and a speed of 20m/min, followed by the following formulation 1.
Coating i with a resin solid content concentration of 20% shown in Figure 1 was applied using a knife over roll coater at a coating amount of 90 g/rd, and then immersed in a 20°C water bath for 1 minute to solidify the resin.

Formulation 1 Polyamino acid urethane resin 100 parts Dimethylformamide 20 parts Washed in warm water at 60°C for 10 minutes, then dried, and then added 5% Asahi Guard 710 (product of Asahi Glass Co., Ltd.), a fluorine-based water repellent emulsion. Banding was performed with an 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, a comparative sample was prepared according to the comparative example described below, and the performance was compared with the two products 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.

Water pressure resistance is JTS-L-1041 low water pressure method, moisture permeability is J
Based on IS-Z-0208.

As is clear from Table 1, although the moisture permeable waterproof fabric according to the present invention has a water pressure resistance of 2.000 mm or more, its moisture permeability is 10.500 g/rrf・hrs.
It can be seen that it has both outstanding moisture permeability and waterproof performance.

Table 1 Comparative Examples A nylon tack fabric of the same specifications as Example 1 was prepared, and after scouring and sorendering it in the same manner as in Example 1, a coating liquid shown in the following recipe 2 was applied with a knife. Coating amount 90 g/nf using over roll coater
It was applied at. The polyamino acid urethane resin used in Formulation 2 was the same as that used in Example 1.

Prescription 2 Polyamino acid urethane resin 100 parts Dimethylformamide 20 parts After application, solidification was performed in the same manner as in Example 1.

Washing, drying, and water repellent treatment using a fluorine-based indium solution were performed.

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

Patent Applicant Uni-Tei Riki Co., Ltd. 1 17th Supplement "E" 1-11, Indication of the Case Japanese Patent Application No. 13081/1981 2, Name of the Invention Method for Manufacturing a Moisture-permeable Waterproof Fabric 3, Person Making the Amendment Related Patent Applicant Address: 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture 541 Address: 4-68 Kitakyutabe-cho, Higashi-ku, Osaka Name: Unitika Co., Ltd. Patent Department 4, ``Detailed Description of the Invention'' in the specification subject to amendment '' column (hereinafter referred to as PAll resin) lists amino acids and polysine, L-lysine, L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, amino acids N-carboxylic acid obtained from amino acids and phosgene are listed. Acid anhydride (hereinafter, N-carboxylic acid anhydride is referred to as NCA).

) is commonly used. Polyurethane uses aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates alone or in mixtures thereof as isocyanate components. Examples include toluene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, Examples include 1.4-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 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, PAtl resins are obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymers having isocyanate groups at the ends. Optically active T-alkyl glutamate-NC is preferably used as the amino acid component constituting the PAD resin from the viewpoint of film performance, and among the optically active T-alkyl glutamates, γ-methyl-L is preferred from the viewpoint of price and film properties. -Glutamate NCA or γ-
Methyl-D-glutamate is often advantageously selected as the amino acid component of the PAU 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:
Among PAD resins, a reaction product of optically active γ-alkyl-glutamate-NCA and a urethane prepolymer is particularly preferably used. In order to obtain a uniform resin solution over a wide range of 90:10 to 10:90 in the weight ratio of amino acids and urethane in a mixed solvent system, the above weight ratio can be freely selected while considering the required physical properties of the film. This is because it can be done. ” (2) From “-” on page 6, line 20 of the specification “-” to “-” on page 7, line 10 of the specification.

” and insert the first 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 1500ms+ or more, the moisture permeability is at most 5000g/m"・24hr
In contrast, when wet-coating PAD resin, the water pressure resistance is 1500 mm.
or more and moisture permeability is 7000 g/m”・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 by wet coating processing of PAD resin is not obvious, but when observing the cross section of the film of the obtained moisture-permeable waterproof fabric, it is found that compared to polyurethane film, PA
In the case of the mouth resin film, the microcells are small and
There are a large number (uniformly distributed), which is thought to be a factor in providing high moisture permeability and high water pressure resistance.
The high affinity of AD resin itself for water vapor may also be a driving force behind its high moisture permeability. ” (3) On page 10, lines 11 to 13 of the specification, “
-・ of the resin film becomes defective. "Dimethylformamide diffuses into water faster.

The pores in the resin film become larger, resulting in poor water pressure resistance. ” he corrected.

(4) “Fluorium-based...
・I did. ” to be deleted.

Claims (1)

[Claims] +11 polyamino acid urethane resin, polyurethane resin,
After applying a resin solution consisting of a polar organic solvent and a polar organic solvent to one or both sides of a fiber base material, the fiber base material is immersed in water at 0°C to 30°C, first washed with hot water, and then dried, and then provided with a water-repellent coating. A method for producing a moisture-permeable waterproof fabric.