JPS60181366A - Production of moisture pervious waterproof 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 that simultaneously has the dual functions of 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 during these dry or wet coating processes in terms of film 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 diameter of 0.00 mm (below the water column) or more, the moisture permeability is 4. QOO~5,000 g/n?・24hrs
(J, IS Z-0208 measurement) is currently available. This moisture permeability level is 7,
If it can be improved to 000g/rrr・24hrs or more, it will have almost the same moisture permeability as a non-coated fabric that is simply made by 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, making it possible to perform even more strenuous exercise or work comfortably, but the water pressure resistance is 1. , 7.0 for items over 500mm
The reality is that even to this day, a fabric with a moisture permeability of 00 g/rd · 24 hrs or more has not yet been obtained. 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 7,000 g/n? - The purpose is to obtain a waterproof fabric with high moisture permeability of 24 hours or more.

In order to achieve this object, the present invention has the following configuration.

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

After applying a resin solution consisting of a hydrophilic polymer and a polar organic solvent to one or both sides of a fiber base material, the fiber base material is heated to
Soaked in 30°C water 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 water repellent after drying.

Hereinafter, one aspect of the present invention will be explained 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 photosynthetic 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 hydrophilic polymer and a polar organic solvent is applied.

The polyamino acid urethane resin used here has optical activity γ
-Alkyl-glutamate-N-carboxylic anhydride (hereinafter, N-carboxylic anhydride is abbreviated as NC^) and a urethane prepolymer having an isocyanate group at the end are mixed, and then amines are added. It is made of a reacted polyamino acid urethane copolymer resin (hereinafter abbreviated as PAtl resin), and the solvent during the 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 PAU resin to the fiber base material. Optical activity γ-
As an alkyl-glutamate-'NCA.

It may be D-glutamate or D-glutamate.

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

γ-Alkyl-glutamate NCA such as γ-ethyl-L-glutamate-NCA, T-methyl-D-glutamate-NC8, γ-ethyl-〇-? γ-alkylroot-NCAs such as 'rutamate NG can be used alone or as mixtures thereof. Also, γ-alkyl glutame)-
It is also possible to use α-amino acid-NC^ mainly composed of NC8 as the amino acid component of IIAU resin, and furthermore, optically active T-alkyl glutamate-NCA and other amino acids NCΔ, such as glycine NCA, L-asparagine. Acid-β-methyl ester NCA, L-alani. 7
NCA, D-'? A mixture with Rani 7 NCA etc. can also be used. However, considering the physical properties and price, γ
-Methyl-L-glutamate-NC^ or γ-methyl-D-glutamic acid 1=NcA is often industrially more advantageous to use alone.

The urethane prepolymer having an isocyanate group at the terminal has an equivalent ratio of isocyanate and polyol of Nco101.
It is obtained by reacting under the conditions of 1>1. As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. may be used alone or as a mixture thereof. Also, as a polyol component. Polyether glycol, polyester glycol, etc. used in ordinary urethane products can be used alone or in 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 pure amount of PAU resin that adheres to the textile fabric is 5 g.
/rd or more is desirable. Adhesion amount is 5g/d
If it is less than 1,500 mm, 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, PAII resin has the ability to allow water vapor to pass through even if it is a non-porous film. In the case of the conventional moisture-permeable waterproof fabric having a porous bovine tan resin film, the water pressure resistance is 1 to 5.
00mm or more, the moisture permeability is at most 5,000g/
Whereas you can only get about nr/24hrs, 9
In the present invention, by using PAD resin, the water pressure resistance is 1.500 mm or more and the moisture permeability is 7.000 g.
/rd・24hrs or more moisture permeable waterproof fabric can be obtained.

Next, hydrophilic polymers in the present invention are those that are soluble in polar solvents and water and can be extracted from water, and specifically include polyvinylpyrrolidone, amine salts of carboxyl vinyl polymers, and highly polymerized polyethylene glycols , polyvinyl alcohol.

Examples include hydroxyalkyl cellulose, carboxymethyl cellulose and derivatives thereof. The amount of hydrophilic polymer to be used is 0.000000000000000000 yen per PAU resin.
It is desirable to use it in a proportion of 1 to 5%. Usage is 0
．． If it is less than 1%, the moisture permeability will be poor, and if it is more than 5%, the waterproofness will be 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 pores large enough to prevent water from passing through the PAU resin film, which has better moisture permeability than polyurethane resin. This is due to the fact that there are an infinite number of them.

When PAD resin and hydrophilic polymer are immersed in water at the same time, a desolvation effect occurs due to the coagulation process, and the PAD resin coagulates and the hydrophilic polymer is also removed.
Coagulation of the resin is carried out before the removal of the hydrophilic polymer and is carried out in the presence of the hydrophilic polymer, so rapid coagulation does not occur and a PAU skin modification with a uniform and fine porous structure is formed. be done. This PAU film is retained without disappearing even during the drying process, ensuring moisture permeability. If the amount of hydrophilic polymer is too small, the number of fine porous parts will decrease, resulting in poor moisture permeability. Moreover, if there is too much hydrophilic polymer, the pores will become large and the water pressure resistance will be poor.

In the present invention, the above-mentioned PAD resin, hydrophilic polymer, and polar organic solvent are mixed and used. Polar organic solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylenephosbonamide, and the like.

These substances are highly soluble in water, and 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 also eluted into water, making it possible to obtain a resin having countless pores.

A resin solution consisting of a PAD resin, a hydrophilic polymer, 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 an I) AU resin film having countless pores, and the action of the hydrophilic polymer creates pores of appropriate size that provide good moisture permeability and water pressure resistance. can be obtained.

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.
Atl resin film cannot be obtained.

After coagulating the PAO resin in water, the fabric is washed with hot water to remove the remaining solvent and hydrophilic polymer. Conditions for hot water washing vary depending on the amounts of Pall resin and hydrophilic polymer 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. 18
By applying a water agent (a), the surface of the fabric can be made water repellent, 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 heat treatment is performed after applying the water repellent and drying. Also, in order to improve 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 comprising the PAD resin, hydrophilic polymer, and 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 having a water pressure resistance of 1.500 mm or more and a moisture permeability of 7.000 g/rrf·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 (00 value 56.9) 19
70 g and 1-6-hexamethylene diisocyanate) 5
40g was reacted at 90°C for 5 hours to obtain a urethane prepolymer having an isocyanate group at the end (NGO equivalent weight 234
0) was obtained. 85 g of this urethane prepolymer and 85 g of T-methyl-glutamate-NCA were mixed in a mixed solvent of dimethylformamide/dioxane (weight ratio) -7/3.
66g, add 50g of 2% triethylamine solution with stirring, and react at 30°C for 5 hours to obtain a yellowish brown emulsion-like polyamino acid urethane resin solution with good fluidity and a viscosity of 32.000 cps (at 25°C). I got it. This polyamino acid urethane resin is used in formulation f described below. Here, the warp is nylon 70 denier/24 filament.

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

Banding (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 performed using a calendering machine with mirror-finished rolls at a temperature of 170°C, a pressure of 30kg/cm, and a speed of 20m/min, and then a coating liquid with a resin solid content concentration of 20% as shown in the following recipe 1 was applied. After coating using a knife-over-roll coater at a coating rate of 185 g/rr, the resin was immersed in a 20°C water bath for 1 minute to solidify the resin.

Formulation 1 Polyamino acid urethane resin 100 parts Polyvinyl pyridone 3 parts Dimethylformamide 12 parts Washed in warm water at 60°C for 1 minute, then dried, and then applied Azahi Guard 7, a fluorine-based water repellent emulsion.
10 (Asahi Glass Co., Ltd. product) was padded with a 5% aqueous solution (squeezing ratio: 30%) and heat treated 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 later, and their performance was compared with nine 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.

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 low water pressure method and moisture permeability of No. 1 were determined in accordance with JIS-Z-0208.

It is clear from Table 1 (1) that the moisture permeable waterproof fabric according to the present invention has an outstanding water permeability, recording a moisture permeability of 9,000 g/rd-hrs despite having a water pressure resistance of 2,000 mm or more. It can be seen that it has both moisture and waterproof performance.

Table 1 Comparative Examples A nylon tack fabric of the same standard as Example 1 was prepared, and after scouring and calendering was performed in the same manner as in Example 1, the coating solution shown in the following formulation 2 was applied on a knife-over roll. Coating was performed using a coater at a coating ilt of 85 g/nf. The polyamino acid urethane resin in Formulation 2 was the same as that used in Example 1.

Formulation 2 After applying 100 parts of polyamino acid urethane resin and 20 parts of dimethylbormamide, coagulation, washing, drying, and water repellent treatment using a fluorine water repellent were performed in the same manner as in Example 1.

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

Patent Applicant Unitika Co., Ltd. Procedure Neer iIr jkfE Near 1i” (Spontaneous) 1. Indication of the case Japanese Patent Application No. 59-30780 2. Name of the invention Method for manufacturing a moisture-permeable waterproof fabric 3. Relationship with the summons for amendment 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 Telephone 06-281-5258 (Dial-in) 4, Subject of amendment Column 5 of “a■ of the invention: Detailed explanation” of the specification, content of amendment (11 “Used here -” on page 4, line 7 of the specification to [・-” on page 6, line 14 of the specification) is used.'' and insert the first sentence.

“Polyamino acid urethane resin (hereinafter referred to as PA) used in the present invention
It is called U resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine,
Examples include L-aspartic acid, L-cystine, L-glutamic acid, chrysine, L-lysine, L-methionine, L-leucine and their derivatives, and when synthesizing poly'r-mino acids, amino acids N obtained from amino acids and phosgene are used. -Carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride
That's what it means.

) is commonly used. Polyurethane uses aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates alone or in mixtures thereof as isocyanate components.For example, toluene 2,4-diisocyanate-1, 4,4'-diphenylmethane diisocyanate, 1,6- Examples include hexane diisocyanate and 1,4-cyclohexane diisocyanate. Also,
As the polyol component, ζ is a polyether polyol or a polyester polyol. 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 sepa-J'nic acid, and ring-opening polymers such as caprolactone. The amine used in the copolymerization of amino acids and polyurethane includes 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-NG8 is preferably used as the amino acid component constituting the PAU resin from the viewpoint of film performance, and among the optically active γ-alkyl glutamates, γ-methyl-L is preferred from the viewpoint of price and film properties. -Glutamate NC^ 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 to use a uniform resin composition made of a water-soluble solvent system in terms 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-NG8 and a urethane prepolymer is particularly preferably used. In a mixed solvent system with dioxane, the weight ratio of amino acid and urethane can be adjusted freely while considering the required physical properties of the film in order to obtain a uniform resin solution over a wide range of 90:10 to 10:90. This is because you can choose. (2) From "-" on page 6, line 19 of the specification, "-" to "-" on page 7, line 9 of the specification.

” and insert the first sentence.

[On the other hand, in the case of a conventional moisture-permeable waterproof fabric having a porous urethane resin film, when the water pressure resistance is 1500 mm or more, the moisture permeability is at most 5000 g/m '・24
hrs, whereas when wet coating PAU resin, the water pressure resistance is 1500 hrs.
mm or more and moisture permeability of 7000 g/m”・
It is possible to obtain the surprising result of exhibiting 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 molding of PAU resin is not obvious, but when observing the cross section of the film of the obtained moisture permeable waterproof fabric, it is clear that the polyurethane film is In comparison, in the case of a PAD 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.

Furthermore, the high affinity of PAD resin itself for water vapor is one of the driving forces behind its high moisture permeability.
- of the resin film becomes defective. '' has been corrected to ``Dimethylpolamide diffuses into water faster and the pores of the resin film become larger, resulting in poor water pressure resistance.''

(4) Ming! ItFJ page 12ff! Lines 15-18 “
Fluorine-based treatment was performed. ” to be deleted.

Claims (1)

[Claims] (1) After applying a resin solution consisting of 1 wt of polyamino acid diurethane resin 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 for secondary treatment. A method for producing a moisture-permeable waterproof fabric, which comprises washing with hot water and applying a water repellent after drying.