JPS6312768A - Production of moisture permeable waterproof fabric having wrinkles - 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 (Field of Industrial Application) The present invention relates to a method for manufacturing a wrinkled moisture-permeable waterproof fabric.

(Prior art) Wrinkled cloth using woven fabrics has been well known, and wrinkle treatment of nylon material is particularly common, but when this treated cloth is coated, the degree of wrinkles is reduced. Therefore, it is difficult to obtain desirable wrinkles like those of ordinary wrinkled cloth.

Furthermore, when it comes to fabrics made of high Young's modulus fibers such as polyester fibers and vinylon fibers, it is difficult to even obtain uneven fabrics by wrinkle processing.

On the other hand, if the coated fabric is forcibly wrinkled afterwards, there are concerns that the performance of the coated fabric itself will deteriorate, so this method is not currently used. .

(Problem that the invention attempts to solve) The present invention was made in view of the above-mentioned current situation.

The object of the present invention is to produce a moisture-permeable waterproof fabric that has permanent wrinkles without impeding moisture permeability or waterproof performance.

(Means for Solving the Problems) In order to achieve the above-mentioned objects, the present invention has the following configuration. That is, the present invention provides a polyamino acid urethane resin, a first step of fixing a high-density fabric containing thermoplastic synthetic fibers with a hollow cross section of 30% or more in a bent state and imparting wrinkles to the fabric.

Moisture-permeable waterproofing with wrinkles, characterized by comprising a second step of applying a resin solution comprising an isocyanate compound, a micropore-forming agent, and a polar organic solvent to the fabric, immersing it in water, washing with hot water, and drying. The gist is the method of manufacturing textiles.

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

The degree of hollowness in the present invention refers to the ratio of the area of the hollow voids to the area including the hollow voids in the cross section of the fiber, and in the present invention, it is necessary to have a degree of hollowness of 30% or more. It is. If the degree of hollowness is less than 30%, it is difficult to provide wrinkles, especially in the case of high Young's modulus fibers, and when such fibers are coated, the degree of wrinkles decreases, resulting in the wrinkles defined in the terms of the present invention. A moisture-permeable waterproof fabric cannot be obtained.

In the present invention, a thermoplastic synthetic fiber filament yarn with a hollow cross section of 30% or more (hereinafter referred to as hollow cross section fiber) is used.

), but the thermoplastic synthetic fibers referred to in the present invention refer to polyester fibers, polyamide fibers, polyacrylonitrile fibers, polyethylene fibers, polypropylene fibers, acetate fibers, etc. that are easily deformed by applying heat. However, it refers to a fiber that maintains its deformed state even when cooled, and does not specify the type of fiber.

A filament yarn with a hollow cross section is a long fiber yarn that has a hollow void in its fiber cross section, and the hollow shape may be round, square, triangular, or the like. Further, the number of hollow voids may be one or more (it may be one or more, but the overall degree of hollowness must be 30% or more).

The term "high-density fabric" as used in the present invention9 refers to a fabric whose fibers are arranged in such a way that resin leakage does not occur during normal coating processing.2For example, in the case of nylon plain fabric, the total number of warp and weft yarns is equivalent to 70 denier. This applies to textiles having a density of 200 fibers/inch or more. It goes without saying that the total number of warp and weft yarns will vary depending on the type of fiber and the apparent thickness of the threads, but when hollow fibers are used, the apparent thickness of the threads is large, making it difficult to fabricate high-density fabrics. However, a lightweight fabric can be obtained.

Although the m-product of the present invention is woven using hollow cross-section fibers, it is not necessary that all the warps and wefts are hollow cross-section fibers, and depending on the desired wrinkle shape and the number of wrinkles, any non-hollow fiber may be used. Fibers can be used in combination. When wrinkle processing is performed after weaving using hollow cross-section fibers for both the warp and the weft, sufficient wrinkles appear when the degree of hollowness is about 30 to 40%.

In addition, regarding the wrinkle form, the higher the degree of hollowness, the better the unevenness and wrinkles of the fabric. Only yarn consisting of hollow cross-section fibers is used for either the warp or weft.

On the other hand, when weaving is performed using a yarn made of any fiber that does not have a hollow space and wrinkled, only the hollow cross-section fiber portion is heat-set in a bent state, and wrinkles due to the bending of the hollow fibers appear. do.

In this way, depending on the degree of hollowness or in combination with fibers without hollowness, it is possible to provide wrinkles with good reproducibility.

In order to heat-set the fabric in a bent state and create wrinkles, it is sufficient to adopt a normal wrinkle processing method.9 For example, wrinkles can be added to the processed wrinkles using a jet dyeing machine, washer, etc., or packing wrinkles can be created using an overmeyer. It is possible to adopt a method that can thermally or mechanically fix the wrinkles on the fabric, such as rope wrinkles using a wince.

In the present invention, the first step is to wrinkle the fabric as described above, and then the second step is to apply a polyamino acid urethane resin and an isocyanate compound.

A resin solution consisting of a micropore-forming agent and a polar organic solvent is applied to the fabric, which is then immersed in water, washed with hot water,
dry. The polyamino acid urethane resin (hereinafter referred to as PAU resin) used here is.

It is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine, L-aspartic acid, L-cystine, and L-glutamic acid.

Examples include glycine, L-lysine, L-methionine, L-leucine and their derivatives. When synthesizing polyamino acids, the amino acid N-carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride) obtained from an amino acid and phosgene is used. N.C.A.
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 the isocyanate component.
4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate,
Examples include 1,4-cyclohexane diisocyanate. Further, as the polyol component, polyether polyol and polyester polyol are used. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Polyester polyols include reactions between diols such as ethylene glycol and propylene glycol and dibasic acids such as adipic acid and cepatic acid. Examples include products 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 amines g N CA and urethane prepolymers having incyanate groups at the ends. P
As the amino acid component constituting the AU resin, optically active γ-alkylglutamate-NCA is preferably used from the viewpoint of film performance.

Furthermore, among the optically active T-alkyl glutamates, T-methyl-L-glutamate NCA or γ-methyl-D-glucumate is preferred from the viewpoint of price and film properties.
It is often advantageously selected as the amino acid component of U resin, and in order to obtain a porous membrane, it is important to use a uniform resin composition consisting of a water-soluble solvent system, which improves coating properties and wet film formation. It is advantageous from both gender perspectives. As such a resin composition.

Among PAU resins, a reaction product of optically active γ-alkylglutamic acid (gamma)-NCA and a urethane prepolymer is preferably used. In a mixed solvent system of dioxane and amino acid, the weight ratio of amino acid and urethane becomes uniform over a wide range of 90:10 to 10:90, so the above weight ratio is This is because they can be freely selected.

The amount of PAU resin attached to the fiber base fabric is 3 in pure terms.
g/m or more is desirable, and the adhesion amount is 3 g
/g, the surface unevenness of the wrinkled fabric will not be covered,
It is difficult to obtain sufficient waterproofness.

In the present invention, when applying the above-mentioned PAU resin to a fabric,
For the purpose of improving the peeling resistance between the textile and the film, an isocyanate compound having a high affinity with the fibers is used in the resin solution, and a micropore-forming agent is also used in order to form a film with high moisture permeability. The isocyanate compounds used here include 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.

Triisocyanates obtained by addition reaction of 3 mol of hexamethylene isocyanate or these diisocyanates and 1 mol of a compound containing active hydrogen (eg, trimethylolpropane, glycerin, etc.) are used. The above-mentioned isocyanates may be those in which the isocyanate group is free, or may be stabilized by adding phenol, methyl ethyl ketoxime, etc., and the blocks may be dissociated by subsequent heat treatment. Can be used.

They may be used appropriately depending on workability, purpose, etc.

The isocyanate compound is 0.1 to 0.1 to PAU resin.
It is desirable to use it in a proportion of 10%, preferably 0.5 to 5%. If the amount used is less than 0.1%, the adhesive strength of the resin to the fabric will be poor, and if it exceeds 10%, the texture will be hardened, which is not preferable.

Examples of the micropore-forming agent used in combination include anionic surfactants, nonionic surfactants, hydrophilic polymers, and polyurethane elastomers. The amount used is 0.1 to 10% for anionic surfactants and nonionic surfactants, 0.05 to 5% for hydrophilic polymers, and 0.05 to 5% for polyurethane elastomers, based on the PAU resin used in combination. In this case, it is preferably in the range of 0.3 to 20%. If the amount of these micropore-forming agents used is less than the above range, the pores of the PAU resin film will become too small.
It becomes difficult to obtain contacted microcells.

Moisture permeability becomes poor. Furthermore, if the amount exceeds the above range, the pores become too large and sufficient waterproofness cannot be obtained.

The anionic surfactants used as the above-mentioned micropore-forming agent include conventionally known alkyl sulfate ester salts, alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfonates, fatty acid amide sulfonates, and dialkyl sulfosuccinic acids. salt, etc., or any mixture thereof.

In addition, nonionic surfactants include polyoxyethylene alkyl ether, polyethylene alkylphenyl 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 esters, alkylo-doamides, etc., or any mixture thereof.

Hydrophilic polymers include polyvinylpyrrolidone, polyacrylic acid, polyacrylic acid ester, carboxyvinyl polymer organic amine, polyethyleneimine, etc., and are substances that can be dissolved in polar organic solvents and dispersed or emulsified.
It also refers to a polymer that can be dissolved in water.

A polyurethane elastomer is a polymer obtained by reacting a polyisocyanate and a polyol. As the polyisocyanate, known aliphatic and aromatic polyisocyanates can be used. For example, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, and these. Mention may be made of reaction products of excess with 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 reactants of polyhydric alcohols such as diethylene glycol or 1,4-butanediol and polybasic carboxylic acids such as adipic acid, oxalic acid or cepatic acid. Examples of polyether include ethylene glycol,
Examples include polyhydric alcohols such as propylene glycol to which one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are added.

Polar organic solvents used as solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylenephosphonamide, 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 the fabric resin is coagulated using the wet coagulation method.

Since trace amounts of polar organic solvents present in the resin are also eluted into water, a resin film having countless micropores can be obtained.

The resin solution consisting of the above-mentioned PAU resin, isocyanate compound, micropore-forming agent, and polar organic solvent may be applied to the fiber fabric by a conventional coating method. Generally, the coating thickness of resin is 10 to 30 mm due to the performance of 9 machines.
0A! It is m.

After applying the resin solution to the fiber fabric, the fabric is immersed in water. The water temperature during immersion may be in the range of 0 to 30°C, and the immersion time may be 10 seconds or more.

After coagulating the PAU resin in water, the fabric is washed with hot water to remove any remaining solvent. The hot water washing conditions vary depending on the amounts of the PAU resin, isocyanate compound, and micropore-forming agent used, but may be carried out at a temperature of 30 to 8°C for 3 minutes or more. After washing with hot water, it is dried to complete the second step in the present invention.

Although the present invention consists of one or more two steps, a water repellent may be added to the fabric or resin film to make it water repellent. IΩ
There are various types of liquid agents, such as paraffin type, silicone type, and fluorine thread, and in the present invention, they may be selected as appropriate depending on the intended use. If particularly good water repellency is required, use a fluorine-based water repellent.

After applying IΩ solution and drying, heat treatment is performed. Furthermore, in order to increase the durability of i8 aqueous, a resin such as melamine resin may be used in combination. The water repellent may be applied by one of the commonly used methods such as pupping, coating, and spraying.

Furthermore, for the purpose of imparting flexibility and smoothness to the fabric, it may be further treated with a polysiloxane resin. The polysiloxane applied here includes dimethylpolysiloxane, phenyl group-containing polysiloxane, modified silicone oil such as amino-modified or olefin-modified silicone oil, methylhydrogenpolysiloxane, or molecules of dimethylpolysiloxane and methylhydrogenborylpolysiloxane ff15,000. ~30
,000 is preferably used. This polysiloxane treatment first imparts smoothness to the fabric and can reduce wear and tear on the film due to harsh rubbing between the fabrics.

This smoothing effect also has the advantage of making it easy to put on and take off without using a lining.

Second, the silicone resin adheres between the fabric structures and reduces the friction between the threads that make up the 111 product.

However, in order to prevent treatment spots, use 1.1.1.
-Trichloroethane, trichloroethylene.

Chlorinated hydrocarbons such as perchlorethylene, toluene,
Hexane, mineral turpentine, etc.? Container) May be applied as a liquid. The polysiloxane resin is applied using the commonly used popping method.

This may be done by a coating method or a spray method. The amount of polysiloxane deposited is 0.0% in terms of solid content based on the fiber weight.
1% or more is desirable.

(Function) In the method of the present invention, first, a fabric containing hollow cross-section fibers as constituent fibers is wrinkled using an ordinary wrinkle processing machine. At the time of applying wrinkles, the hollow cross-section fibers constituting the fabric are sharply bent. When action is applied.

The fibers buckle as if a pipe were bent. When heat-fixed in this buckled state, the deformation of the hollow cross-section fibers due to buckling becomes a complete irreversible deformation and remains as it is, and the fabric becomes a durable wrinkled fabric. Even if such a wrinkled fabric is used as a base fabric and wet-coated with PAU resin, the irreversible deformation wrinkles due to buckling will not disappear, so a moisture-permeable waterproof fabric with a perfectly wrinkled shape will not disappear. It becomes possible to produce vapor.

(Example) Next, the present invention will be explained in more detail with reference to Examples.
Performance measurements and evaluations in Examples were performed in the following manner.

(1) Water resistance Pressure: JIS L-1096 (low water pressure method) (2) Moisture permeability: JIS Z-0208 (3) Degree of wrinkles: By visual judgment.

Example 1 A wrinkled fabric was formed in the first step below, and this was used as a base fabric for wet coating with PAU resin in the second step below.

[First step] A plain woven fabric with a warp density of 88 threads/inch and a weft density of 72 threads/inch is made using hollow cross-section polyester fibers of 50 d/24 f with a hollow degree of 50% and a circular hollow cross-sectional shape for the warp and weft. Weaved.

After scouring and drying this fabric in an oven absorber, it was dyed using a jet dyeing machine at 130°C for 30 minutes under normal conditions. Dyeing with iJi dye, followed by reduction washing, soaping, and drying at 180'C with a pin tenter.
Heat fixation was performed for 1 minute.

In the obtained fabric, the hollow fibers were buckled and deformed around the micro-movement one-way weaving point, and due to the rubbing effect of the liquid during jet dyeing, the fabric had a shape similar to that of washed-out wrinkled cotton.

[Second Step] The PA, U resin (polyamino acid urethane resin) used in this example was produced by the following method.

Polytetramethylene glycol (00 value 56.9) 19
70g and 50g of 1-6-hexamethylene diisocyanate
4g was reacted at 90°C for 5 hours.

A urethane prepolymer (NGO 12340) having isocyanate groups at the ends was obtained. 85g of this urethane prepolymer and γ-methyl-L-glucumate-NCA3
5 g of dimethylformamide/dioxane (weight ratio 7
/3) dissolved in 666g of mixed solvent and stirred while stirring.
% triethylamine? Adding 50g of water and carrying out the reaction at 30°C for 5 hours, the viscosity was 32.000cps (25°C).
A yellow-brown milky layer-like PAU resin solution of C) with good fluidity was obtained.

Next, using the above-mentioned PAU resin, a resin solution shown in the following formulation 1 is applied to the wrinkled cloth obtained in the first step using a knife over roll coater ff 160 g/rr? (
After application at 19% solids, 30% solids in a 20°C water bath.
The resin was immersed for a second to solidify, followed by washing in warm water at 50° C. for 10 minutes and drying.

Formulation I PAU resin 100 parts Dimethylformamide 15 parts The obtained coated fabric had no wrinkles and had sufficient commercial value as a wrinkled fabric. Further, when the above-mentioned fabric was washed 10 times in a home washing machine, almost no change in the appearance of wrinkles was observed, and it was found to be durable. This coated fabric has a water pressure resistance of 1800mm and a moisture permeability of 820mm.
0 g/m/24hrs, and had both excellent moisture permeability and waterproof performance.

(Effects of the Invention) The present invention has a configuration in which wet coating processing of PAU resin (polyamino acid urethane resin) is performed on a wrinkled fabric using buckling deformation of hollow cross-section fibers, and according to the present invention having such a configuration, , has enough wrinkles to be commercially valuable as a wrinkled fabric. A moisture-permeable waterproof fabric can be produced using a wet coating process.

Claims (1)

[Claims] (1) The first step of fixing a high-density fabric containing thermoplastic synthetic fibers with a hollow cross section of 30% or more in a bent state to give wrinkles to the fabric, polyamino acid urethane resin, isocyanate compound, micropore formation After applying a resin solution consisting of an agent and a polar organic solvent to the fabric, immersing it in water,
A method for producing a wrinkled moisture-permeable waterproof fabric, comprising a second step of washing with hot water and drying.