JPS60173176A - 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 producing a moisture-permeable waterproof fabric that has the three functions of waterproofness and moisture permeability and has a good feel. Generally, moisture permeability and waterproofness are contradictory functions, but waterproof fabrics with excellent moisture permeability have numerous continuous micropores that allow water vapor to escape in the coating resin film during dry or wet coating processing. It is obtained by forming In these dry or wet coating processes, polyurethane elastomer is generally preferably used as the coating resin in terms of film strength, rubber elasticity, and flexibility. However, polyurethane elastomers have a wet feel, and when they come into direct contact with the skin, they feel cold and cause discomfort. Particularly when the skin is wet due to sweat, etc., discomfort is aggravated, and there are also problems such as difficulty in smoothly putting on and taking off the wearer.

The present invention was made in view of the current situation.

The object of the present invention is to obtain a moisture-permeable waterproof fabric that has excellent moisture permeability and high waterproofness, and has a texture that does not feel wet. In order to achieve this object, the present invention has the following configuration.

That is, the present invention applies a resin solution consisting of at least one compound selected from an anionic surfactant, a nonionic surfactant, and a hydrophilic polymer, a polyurethane resin, and a polar organic solvent to a fiber base material. This is immersed in water and then dried.First, a resin solution consisting of a polyamino acid urethane resin, a nonionic surfactant and a polar organic solvent is applied to the resin-coated surface of the fiber base material, followed by immersion in water and then dried. The gist of the present invention is a method for producing a moisture-permeable waterproof fabric, which is characterized in that a water repellent is then applied thereto.

Hereinafter, five aspects 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 synthetic fibers, polyvinyl alcohol synthetic fibers, and polyvinyl alcohol synthetic fibers. Examples include two-knit woven 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, at least one compound selected from anionic surfactants, nonionic surfactants, and hydrophilic polymers, a polyurethane resin, and a polar A resin solution made of an organic solvent is applied.

The anionic surfactants used here include conventionally known alkyl sulfate salts, alkylbenzene sulfonate salts, and α-olefin sulfonate salts.

These include alkyl sulfonates, fatty acid amide sulfonates, dialkyl sulfosuccinates, etc., or any mixture thereof.

Nonionic surfactants are polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester 2 It refers to fatty acid esters, alkylo-doamides, etc., or any mixture thereof.

Furthermore, the hydrophilic polymer is polyvinylpyrrolidone.

Polyacrylic acid, polyacrylic acid ester, carboxyvinyl polymer organic amine, polyethyleneimine, etc. are polar polymers that can be dissolved, dispersed, or emulsified in a solvent and are soluble in water.

Anionic surfactants, nonionic surfactants, and hydrophilic polymers have the effect of properly articulating the pores existing in the resin film when coagulating polyurethane resin in water, and this action provides excellent permeability. Provides moisture. These can be used alone or in combination.

The amounts of anionic surfactants, nonionic surfactants, and hydrophilic polymers used vary depending on whether they are used alone or in combination, but range from 0.1 to 0.1% of the polyurethane resin. It is desirable to use it within a range of 10%. If the amount used is less than 0.1%, moisture permeability will be poor.
Also, at 10% or more.

Even if the polyamino acid urethane resin described below is applied, the waterproofness will be poor.

The polyurethane resins used in the present invention include polyols such as polyether polyols, polyester polyols, various grafted polyols, halogenated polyols, polyols with diene chains, polycarbonate polyols, acrylic polyols, and epoxy polyols, as well as tolylene diisocyanate and diphenylmethane diisocyanate. isocyanate.

Polymeric diphenylmethane diisocyanate.

It is an addition polymerization reaction product with isocyanate such as hexamethylene diisocyanate, but in some cases, diamine etc. may be used in combination as a crosslinking or chain extender during addition polymerization, and a microporous film can be formed by wet coagulation. Any material having formation ability can be used in the present invention.

In the present invention, at least one compound of the above-mentioned anionic surfactant 3, a nonionic surfactant and a hydrophilic polymer, a polyurethane resin, and a polar organic solvent are mixed and used. Polar organic solvents include dimethylformamide,
Examples include dimethylacetamide, N-methylpyrrolidone, hexamethylenephosbonamide, and the like. These substances are highly soluble in water, and when a polar organic solvent solution of a water-insoluble resin is immersed in water, only the polar organic solvent dissolves in 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.

This polyurethane resin solution can be applied to the fiber base material by a conventional coating method.

The amount of resin deposited varies depending on the type of polyurethane resin, but is preferably in the range of 5 to 100 g/rrf in terms of dry weight. If the amount of adhesion is less than 5 g/rrl, the waterproof property may be poor, and if the amount is more than 100 g/rrl, the moisture permeability may be poor.

After applying the resin solution to the fibrous substrate, the fabric is immersed in water. As described above, this process allows the formation of a polyurethane resin film having countless pores. The water temperature when immersing the fabric in water is desirably 0 to 30°C, and the immersion time is required to be 2 minutes or more. Water temperature is 30
℃ or higher or the immersion time is less than 2 minutes, a good resin film cannot be formed and the waterproof property becomes poor. After applying the resin solution, dry it.

In the method of the present invention, a resin solution consisting of a polyamino acid urethane resin, a nonionic surfactant, and a polar organic solvent is applied next onto the polyurethane resin film formed by the above-described method.

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 a polyamino acid urethane copolymer resin (hereinafter abbreviated as PAtl resin), 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 PAD 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.

γ-alkyl monoglutamate such as T-ethyl-L-glutamate) -NCA, γ-methyl-D-glutamate NC^, T-ethyl-D-glutamate-
γ-Alkylroot-NCAs such as NCA can be used alone or in mixtures thereof. In addition, α-amino acid-NCA mainly converted to γ-alkyl-glutamate-NG is added to PAU.
It can also be used as an amino acid component of resin, and it can also be used as an optically active T-alkylglutamic acid component.
A and other amino@NCAs, such as glycine NCA.
L-aspartic acid-β-methyl ester NCA. L
-Mixtures with alanine NCA, D-alanine NCA, etc. can also be used. However, considering physical properties and cost, it is often industrially more advantageous to use T-methyl-L-glutamate-NCA or T-methyl-D-glutamate-NCA alone.

Urethane prepolymers have isocyanate groups at the ends. Equivalence ratio of isocyanate and polyol is NCO101
It is obtained by reacting under the conditions of 1>1. As the isocyanate component, 5-aromatic diisocyanate, aliphatic diisocyanate-1, alicyclic diisocyanate, 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 the form of a mixture, and the average molecular weight of these polyethers and polyesters is between 200 and 3.
00 or more is preferably used. The amines used in co-merging include primary alkyl amines such as ethylenediamine, alcohol amines such as ethanolamine,
Tertiary alkylamines such as triethylamine and secondary amines such as diethylamine are used.

The amount of PAtl resin attached to the fiber base fabric is 0 in pure content.
It is desirable that the amount is in the range of 5 to 20 g/rrr; if the amount of adhesion is less than 0.5 g/rd, the surface will not feel dry or slippery, and if the amount of adhesion is 20 g/rrr or more, the fabric obtained will be , the texture becomes hard.

Next, the nonionic surfactants in the present invention include polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester,
Polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester.

Polyoxyethylene polyhydric alcohol-fatty acid ester,
It refers to fatty acid sucrose ester, alkylo-doamide, etc., or any mixture thereof, and has the effect of appropriately controlling the pores present in the resin film when coagulating the PAD resin in water.

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

The amount of nonionic surfactant used is preferably in the range of 0.1 to 10 parts by weight based on the amount of PAD resin used.

If the amount used is less than 0.1 part by weight, the pores in the coagulated film of PAII resin will become too small, resulting in poor moisture permeability, and if it is used in excess of 10 parts by weight, the pores will become too large, resulting in poor waterproof performance. Become.

In the present invention, a resin liquid containing the above-mentioned PAυ resin, a nonionic surfactant, and a polar organic agent is applied onto a polyurethane resin film formed on a fiber base material. Dimethylformamide is a polar organic solvent.

Dimethylacetamide, N-methylpyrrolidone.

Examples include hexamethylene phosphonamide. 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 the resin is coagulated by the wet coagulation method, a trace amount of the polar organic solvent present in the resin y' is also eluted into water, so that a resin having countless pores can be obtained.

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.

After applying the resin solution to the fiber substrate, the fabric is immersed in water. As mentioned above, a PAD resin film having countless pores can be formed by this step, and an appropriate number of pores can be obtained by the action of the nonionic surfactant.

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 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 PALI resin and surfactant used, but 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 hydropower agent to the fabric. By adding a water repellent agent, the fabric surface becomes water repellent,
A moisture permeable waterproof fabric with good water pressure resistance can be obtained. 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 a heat treatment is performed after applying an LA water agent 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 padding method, coating method, spraying method, or the like.

The present invention has the above configuration, and according to the present invention, it is possible to obtain a moisture-permeable waterproof fabric that has good waterproofness and moisture permeability, has a dry touch surface, and is easy to put on and take off.

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 value 56.9) 1
970g 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 3123).
40) was obtained. 85g of this urethane prepolymer and T-
When 885 g of methyl-5-glutamate NC8 was dissolved in 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio) -7/3, 50 g 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 2 described below. Here, the warp is made of nylon 70 denier/2
A plain woven fabric (tuck) with a warp density of 120 threads/inch and a weft density of 90 threads/inch using nylon 70 denier/34 filaments for the 4-filament weft was prepared, and this was scoured and dyed with an acid dye in the usual manner. After.

A coating amount of 80 g/r was applied using a knife-over roll coater using a coating solution with a resin solid content concentration of 18% as shown in the following Formulation I.
After coating in step d, the resin was immersed in an aqueous solution at 20° C. for 5 minutes to solidify the resin.

Formulation 1: 10 parts of dimethylformamide The sample was immersed in warm water at 60° C. for 30 minutes, and then dried. Subsequently, the resin solid content concentration 18 shown in the following formulation 2
% coating solution was applied using a knife-over roll coke at a coating amount of 20 g/rK, and then placed in a water bath at 20°C for 50 minutes.
The resin was immersed for a minute to solidify the resin.

Formulation 2 Polyamino acid urethane resin 100 parts Dimethylbormamide 23 parts Here, immersion in warm water at 60°C for 30 minutes, followed by drying, followed by 5% fluorine water repellent emulsion Azahi Guard 710 (Asahi Glass Co., Ltd. product) Padding 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.

Table 1 shows the water pressure resistance, moisture permeability, and texture of the obtained fabric.

The water pressure resistance was determined by the low water pressure method of JIS-L-1041, and the moisture permeability was determined by JIS-Z-0208.

As is clear from Table 1, the moisture permeable waterproof fabric prepared by the method of the present invention had excellent waterproof properties and moisture permeability, and also had a dry feeling with good surface touch.

Table 1 Proceedings device (spontaneous) ■, Indication of the case Japanese Patent Application No. 51-29231 2, Name of the invention Method for manufacturing a moisture-permeable waterproof fabric 3, Person making the amendment Relationship with the case Patent applicant address Hyogo 1-50 Higashihonmachi, Amagasaki City, Prefecture 541 Address 4-68 Kitakyutabe-cho, Higashi-ku, Osaka Name Unitika Co., Ltd. Patent Department 4 Column 5 of "Detailed Description of the Invention" of the specification subject to amendment Contents + 11 Details 7F Page 8 Line 8 “Used here...
" to "- is used." on page 10, line 15, and insert the first sentence.

“Polyamino acid urethane resin (hereinafter referred to as PA) used in the present invention
D resin) is a copolymer consisting of amino acids and polyurethane, and the amino acids include OL-alanine,
Examples include L-aspartic acid, cystine, L-glutamic acid, glycine, L-lysine, L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, the amino acid N-carboxylic acid obtained from amino acids and phosgene. Anhydride (hereinafter, N-carboxylic acid anhydride is referred to as NCA).

) is commonly used. In the polyurethane, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates are used singly or as a mixture thereof as incyanate components. For example, toluene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate. , 1,4-cyclohexane diisocyanate-1, 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 zolopyrene 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 incyanate groups at the terminals. As an amino acid component constituting the PAD resin, optically active γ-゛! Alkyl-glutamate-NCA is preferably used, and among the optically active T-alkyl-glutamates, γ-methyl-monoglutamate NC^ or T
-Methyl-D-glutamate is often advantageously chosen as the amino acid component of the PAD resin.

In order to obtain the porous Iq 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. As such a resin composition, a reaction product of optically active γ-alkyl glutamate-NCA and a urethane prepolymer among I'All resins is preferably used, but this is because the above reaction product is mainly composed of a polar organic solvent. The solvent system is, for example, a mixed solvent system of dimethylformamide and dioxane in which the ratio of amino acid to urethane is 90:10 to 10:
This is because the above-mentioned weight 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 90%. ] (2) In lines 2 to 4 of page 13 of the specification, the phrase ``- of the resin film becomes defective.'' was replaced with ``dimethylformamide 1! diffuses quickly into the water, resulting in a non-ionic interface. Since the activator promotes the diffusion of dimethylpolamide 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.

Claims (1)

[Claims] (11 At least one selected from anionic surfactants, nonionic surfactants, and hydrophilic polymers is added to the fiber base material.)
A resin solution consisting of various compounds, a polyurethane resin, and a polar organic solvent is applied, and this is immersed in water and then dried.
Next, a resin solution consisting of a polyamino acid urethane resin, a nonionic surfactant, and a polar organic solvent is applied to the resin-coated surface of the fiber base material, followed by immersion in water and drying, followed by a water repellent agent. A method for producing a moisture-permeable waterproof fabric characterized by imparting the following properties.