JPH0639746B2 - Method for producing moisture-permeable waterproof fabric having wrinkles - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a moisture-permeable waterproof fabric having wrinkles.

(Prior Art) Conventionally, a wrinkle-finished cloth using a woven fabric is well known, and wrinkle-finishing of a nylon material is generally used. It is difficult to obtain a preferable wrinkle like a normal wrinkled cloth. In addition, even with a woven fabric made of high Young's modulus fiber such as polyester fiber or vinylon fiber, it is difficult to obtain a woven fabric having unevenness by wrinkling. On the other hand, in the method of forcibly giving wrinkles to the coated fabric later, it is feared that the performance of the coated fabric itself may be deteriorated, so such a method is not actually adopted at present. .

(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned present circumstances, and is a moisture-permeable waterproof material having permanent wrinkles without impairing the moisture-permeable performance and waterproof performance. The purpose is to produce a woven fabric.

(Means for Solving Problems) In order to achieve the above-mentioned object, the present invention has the following configuration. That is, the present invention is the first step of fixing a high-density woven fabric containing a thermoplastic synthetic fiber having a hollow cross section with a hollowness of 30% or more in a bent state to give wrinkles to the woven fabric, polyamino acid urethane resin, isocyanate compound, fine A method for producing a moisture-permeable waterproof fabric having wrinkles, which comprises a second step in which a resin solution comprising a pore-forming agent and a polar organic solvent is applied to the above-mentioned cloth, which is then immersed in water, washed with hot water and dried. Is the gist.

Hereinafter, the present invention will be described in detail.

The hollowness referred to in the present invention is the ratio of the area of the hollow voids to the area including the hollow voids in the fiber cross section. In the present invention, the hollowness must be 30% or more. Is. If the hollowness is less than 30%, it is difficult to give wrinkles, especially in the case of high Young's modulus fiber,
When such fibers are coated, the degree of wrinkles is reduced, and a moisture-permeable waterproof fabric having wrinkles, which is the object of the present invention, cannot be obtained.

In the present invention, a hollow-section thermoplastic synthetic fiber filament yarn having a hollowness of 30% or more (hereinafter referred to as a hollow-section fiber) is used. The thermoplastic synthetic fiber in the present invention means a polyester-based fiber or a polyamide-based fiber. Fiber, polyacrylonitrile-based fiber, polyethylene-based fiber, polypropylene-based fiber, acetate-based fiber, etc. means a fiber that is easily deformed by applying heat and maintains its deformed state even when cooled. It does not limit the type of. The filament yarn having a hollow cross section is a long fiber yarn having a hollow portion in the fiber cross section, and the hollow shape thereof may be any of round, square, triangular and the like. Further, the number of hollow voids may be any number as long as it is 1 or more, but the hollowness of the whole needs to be 30% or more.

The high-density woven fabric in the present invention means a woven fabric in which fibers are arranged to the extent that resin leakage does not occur in a normal coating process. For example, in the case of a nylon plain woven fabric, the total number of warp and weft yarns is 70 denier. A woven fabric having a density of 200 pieces / inch or more corresponds to this. It is natural that the total number of warp threads and weft threads will differ depending on the type of fiber and the apparent thickness of the yarn, but when hollow fibers are used, the apparent thickness of the yarn is large, so high density woven fabrics Even a lightweight fabric is obtained.

The woven fabric of the present invention is woven using hollow cross-section fibers, but it is not necessary that all warps and wefts are hollow cross-section fibers, and any fibers that do not have hollows depending on the desired wrinkle shape and wrinkle amount. Can be used in combination. When a hollow cross-section fiber is used for all of the warp yarns and the weft yarns and subjected to wrinkling after weaving, sufficient wrinkles are exhibited when the hollowness is about 30 to 40%. In addition, the wrinkle form becomes a woven fabric with better uneven wrinkles as the hollowness increases. When weaving is performed by using only a yarn consisting of a hollow cross-section fiber for either warp or weft, and using a yarn consisting of an arbitrary fiber having no hollow in the other, and performing wrinkling on this, a hollow cross-section fiber is obtained. Only the part is heat-fixed in the bent state, and wrinkles due to the bending of the hollow fiber appear.

As described above, wrinkles can be imparted with good reproducibility by using the fibers together with fibers having a large or small hollowness or no hollow.

In order to develop the wrinkles by heat-fixing the woven fabric in a bent state, an ordinary wrinkle processing method may be adopted. For example, by applying a wrinkle by a jet dyeing machine or a washer,
It is possible to adopt a method of fixing wrinkles thermally and mechanically such as stuffing wrinkles by over-meier and rope wrinkles by winching.

In the present invention, after wrinkling the fabric as described above as the first step, a resin solution containing a polyamino acid urethane resin, an isocyanate compound, a fine pore-forming agent and a polar organic solvent is then applied to the fabric as the second step. After coating, it is immersed in water, washed with hot water, and dried. The polyamino acid urethane resin (hereinafter referred to as PAU resin) used here is a copolymer composed of amino acid and polyurethane, and as the amino acid, DL-alanine, L-aspartic acid, L-cystine, L-glutamic acid, Glycine, L-lysine, L-methionine, L-leucine and its derivatives are mentioned, and when synthesizing a polyamino acid,
An amino acid N-carboxylic acid anhydride (hereinafter, N-carboxylic acid anhydride is referred to as NCA) obtained from an amino acid and phosgene is generally used. In the polyurethane, aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate are used alone or a mixture thereof as an isocyanate component. For example, tolylene 2.4-
Diisocyanate, 4.4'-diphenylmethane diisocyanate, 1.6-hexane diisocyanate, 1.
4-cyclohexane diisocyanate etc. are mentioned.
As the polyol component, polyether polyol or polyester polyol is used. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and as the polyester polyol, a reaction between a diol such as ethylene glycol and propylene glycol and a dibasic acid such as adipic acid and sebacic acid. Examples include products and ring-opening polymers such as caprolactone. The amines used in the copolymerization of amino acid and polyurethane include ethylenediamine, diethylamine,
Triethylamine, ethanolamine, etc. are used.

Thus, the PAU resin is obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymer having an isocyanate group at the terminal. PAU
As the amino acid component constituting the resin, optically active γ-alkyl-glutamate-NCA is preferably used from the viewpoint of film performance, and among the optically active γ-alkyl-glutamates, γ-methyl is also preferred from the viewpoint of cost and film physical properties. −
In many cases, L-glutamate NCA or γ-methyl-D-glutamate is advantageously selected as the amino acid component of the PAU resin, and in order to obtain a porous membrane, a uniform resin composition consisting of a water-soluble solvent system is used. To use things,
It is advantageous in terms of both coatability and wet film formation. As such a resin composition, among the PAU resins, particularly the optically active γ-
A reaction product of an alkyl-glutamate-NCA and a urethane prepolymer is preferably used, which is a solvent system in which the reaction product is mainly a polar organic solvent, for example, a mixed solvent system of dimethylformamide and dioxane, and the amino acid thereof. 90:10 to 1 in weight ratio of urethane to urethane
Since a uniform resin solution is obtained in a wide range of 0:90,
This is because the weight ratio can be freely selected in consideration of the required physical properties of the film.

The amount of PAU resin attached to the fiber base cloth is 3 g in pure
/ M ² or more is desirable, and if the amount of adhesion is less than 3 g / m ² , the surface irregularities of the wrinkle fabric are not covered and it is difficult to obtain sufficient waterproofness.

In the present invention, when the above PAU resin is applied to the cloth,
For the purpose of improving the peeling resistance between the woven fabric and the film, an isocyanate compound having a high affinity for the fiber is used together with the resin solution, and further a micropore forming agent is used together for forming a film with high moisture permeability. As the isocyanate compound used here, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene isocyanate or 3 mol of these diisocyanates and a compound containing active hydrogen (eg, trimethylolpropane, glycerin, etc.) )
Triisocyanates obtained by addition reaction with 1 mol are used. The above-mentioned isocyanates may be in a form in which the isocyanate group is free, or in a form in which the block is dissociated by the subsequent heat treatment, which is stabilized by addition of phenol, methylethylketoxime, or the like. You can use either
It may be properly used depending on workability and purpose.

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

Examples of the fine pore forming agent used in combination include anionic surfactants, nonionic surfactants, hydrophilic polymers and polyurethane elastomers. The amount used is 0.1-10% for anionic surfactants and nonionic surfactants, 0.05-5% for hydrophilic polymers, and for polyurethane elastomers based on the PAU resin used in combination. In this case, it is desirable to be in the range of 0.3 to 20%. If the amount of these fine pore forming agents used is less than the above range, the pores of the PAU resin film become too small, and it becomes difficult to obtain connected microcells, resulting in poor moisture permeability. On the other hand, if the amount exceeds the above range, the pores become too large and sufficient waterproofness cannot be obtained.

The above-mentioned anionic surfactant used as the fine pore forming agent is a conventionally known alkyl sulfate ester salt, alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfonate, fatty acid amide sulfonate, dialkylsulfosuccinic acid. It is a salt or the like, or any mixture thereof.

The nonionic surfactants include polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, oryoxyethylene polyhydric alcohol fatty acid ester, The fatty acid sucrose ester, alkylodamide, etc., or any mixture thereof.

Hydrophilic polymers include polyvinylpyrrolidone, polyacrylic acid, polyacrylic acid ester, carboxyvinyl polymer organic amine and polyethyleneimine, which are substances that can be dissolved, dispersed or emulsified in polar organic solvents.
And it is 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 The reaction product of an excess and a polyhydric alcohol is mentioned. As the polyol, it is possible to use a known one used for usual polyurethane resin production, such as polyether or polyester.
Examples of polyesters include reaction products of polyhydric alcohols such as ethylene glycol, diethylene glycol or 1,4-butanediol and polybasic carboxylic acids such as adipic acid, oxalic acid or sebacic acid.
Examples of the polyether include those obtained by adding one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to a polyhydric alcohol such as ethylene glycol and propylene glycol.

Examples of the polar organic solvent used as the solvent include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylenephosphonamide. These substances are very soluble in water. When a polar organic solvent solution of a water-insoluble resin is immersed in water, only the polar organic solvent is dissolved in water and the resin is solidified in water. The resin coagulation method by such a method is generally called a wet coagulation method. When the cloth resin is coagulated by the wet coagulation method, a trace amount of the polar organic solvent present in the resin is also dissolved in water, so that a resin film having innumerable fine pores can be obtained.

The resin solution comprising the PAU resin, the isocyanate compound, the fine pore-forming agent and the polar organic solvent described above may be applied to the fiber cloth by a usual coating method or the like. Generally, the resin coating thickness is 10 to 30 in view of machine performance.
It is 0 μm.

After applying the resin solution to the fiber cloth, the cloth is immersed in water. The water temperature for the 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 cloth is washed with hot water to remove the residual solvent. The conditions for washing with hot water differ depending on the amounts of the PAU resin, the isocyanate compound and the fine pore forming agent used, but may be carried out at a temperature of 30 to 80 ° C. for 3 minutes or more. After washing with hot water and drying, the second step in the present invention is completed.

Although the present invention comprises the above two steps, a water repellent agent may be added in order to impart water repellency to the cloth or the resin film. There are various types of water repellent such as paraffin type, silicon type and fluorine type, and in the present invention, they may be appropriately selected according to the application. If particularly good water repellency is required, use a fluorine-based water repellent, apply the water repellent, and perform heat treatment after drying. In addition, a resin such as a melamine resin may be used together in order to improve the durability of water repellency. The water repellent may be applied by a commonly used padding method, coating method, spray method, or the like.

Furthermore, for the purpose of imparting flexibility and smoothness to the cloth, a polysiloxane resin treatment may be further performed. Examples of polysiroquinsan to be applied here include dimethylpolysiloxane, phenyl group-containing polysiloxane, modified silicone oil such as amino-modified or olefin-modified, methylhydrogenpolysiloxane, or a mixture of dimethylpolysiloxane and methylhydrogenpolysiloxane. It can be used and may be appropriately selected depending on the application, but in the present invention, dimethylpolysiloxane having a molecular weight of 5,000 to 30,000 is preferably used. This polysiloxane treatment firstly imparts smoothness to the cloth and can reduce abrasion damage of the film due to friction between the cloths. This smoothing effect also has the advantage that it can be attached and removed smoothly without using a lining. Secondly, the silicone resin is adhered between the fabrics to reduce the friction between the yarns constituting the fabric, so that the texture becomes soft. This polysiloxane treatment may be applied in the form of an aqueous dispersion, emulsion, etc., but for the purpose of not causing treatment spots, chlorinated hydrocarbons such as 1.1.1-trichloroethane, trichloroethylene, and perchlorethylene, and toluene. , Hexane, mineral terpene, etc. may be applied as a solvent solution. The polysiloxane resin may be applied by a commonly used padding method, coating method, spray method, or the like. The amount of polysiloxane deposited is preferably 0.1% or more in terms of solid content with respect to the fiber weight.

(Operation) In the method of the present invention, first, wrinkles are imparted to a woven fabric containing hollow cross-section fibers as constituent fibers by using an ordinary wrinkle processing machine. When the wrinkles are imparted, the hollow cross-section fibers constituting the woven fabric are bent sharply. When acted upon, the fibers buckle as if the pipe were bent. When heat set in this buckling state, the deformation due to buckling of the hollow cross-section fibers remains as irreversible deformation and the woven fabric becomes a durable wrinkled woven fabric. Even if such a wrinkled fabric is used as a base fabric and the PAU resin is subjected to wet coating, the irreversible deformation wrinkles due to buckling do not disappear. It becomes possible to manufacture a woven fabric.

(Examples) Next, the present invention will be described in more detail with reference to Examples.
The performance was measured and evaluated in the examples by the following methods.

(1) Water pressure resistance: JIS L-1096 (low water pressure method) (2) Moisture permeability: JIS Z-0208 (3) Wrinkle degree: According to the naked eye judgment.

Example 1 A wrinkle fabric was formed by the following first step, and using this as a base fabric, a wet coating process of a PAU resin was performed by the following second step.

[First step] A plain weave having a warp density of 88 / inch and a weft density of 72 / inch was woven by using hollow cross-section polyester fibers 50d / 24f having a hollowness of 50% and a circular hollow cross-section shape as warps and wefts. .

This fabric is scoured with an open soaper and dried, then dyed with a disperse dye under normal conditions at 130 ° C for 30 minutes using a jet dyeing machine, followed by reduction washing and soaping, drying, and pin tenter. At 180 ° C. for 1 minute, heat setting was performed.

The resulting fabric had hollow fibers that were deformed by bending around the texture points of the fabric, and had a shape similar to the wrinkled appearance of washed cotton due to the effect of kneading the liquid during jet dyeing.

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

Polytetramethylene glycol (OH value 56.9) 1970
g and 1-6-hexamethylene diisocyanate 504 g
Was reacted at 90 ° C. for 5 hours to obtain a urethane prepolymer having an isocyanate group at the end (NCO equivalent 2340). 85 g of this urethane prepolymer and γ-methyl-
85 g of L-glutamate-NCA was dissolved in 666 g of a mixed solvent of dimethylformamide / dioxane (weight ratio 7/3), and a 2% triethyleneamine solution 5 was added with stirring.
When 0 g was added and the reaction was carried out at 30 ° C for 5 hours, the viscosity was 32,0
00cps (25 ℃) yellowish brown emulsion with good fluidity
A U resin solution was obtained.

Next, using the above-mentioned PAU resin, the resin solution shown in the following prescription 1 was applied to the wrinkle-processed cloth obtained in the first step using a knife over roll coater to obtain a coating amount of 60 g / m ² (solid content 1
9%) and then immersed in a water bath at 20 ° C. for 30 seconds to solidify the resin component, followed by washing in warm water at 50 ° C. for 10 minutes and drying.

Strategy 1 The obtained coated fabric had no wrinkle disappearance and had a sufficient commercial value as a wrinkled woven fabric. When the above-mentioned fabric was washed 10 times in a home washing machine, there was almost no change in the appearance of wrinkles, and it was durable. This coated fabric has a water pressure resistance of 18
300 mm, has a moisture permeability 8200g / m ² / 24hrs, were combines excellent moisture permeability and waterproof performance.

(Effects of the Invention) The present invention has a constitution in which a wrinkled woven fabric utilizing the buckling deformation of a hollow cross-section fiber is subjected to wet coating with a PAU resin (polyamino acid urethane resin). It is possible to manufacture a moisture-permeable waterproof fabric by a wet coating process, which has wrinkles having a sufficient commercial value as a wrinkle fabric.

Claims (1)

[Claims] 1. A first step of fixing a high-density woven fabric containing a thermoplastic synthetic fiber having a hollow cross section with a hollowness of 30% or more in a bent state to give wrinkles to the woven fabric, a polyamino acid urethane resin,
A moisture-permeable waterproof fabric with wrinkles, characterized in that it comprises a second step of applying a resin solution consisting of an isocyanate compound, a fine pore-forming agent and a polar organic solvent to the above-mentioned cloth, immersing it in water, washing it with hot water, and drying it. A method of manufacturing a woven fabric.