JPH0364633B2 - - Google Patents

Description

[Detailed Description of the Invention] <Field of Industrial Application> The present invention is applicable in the field of clothing for workers who handle flammable materials, as explosion-proof clothing to prevent explosions and fires caused by electrostatic discharge, and in microelectronics. In the field of clothing for workers, it relates to the production of antistatic, breathable, and waterproof fabrics that are used as antistatic clothing to prevent the generation of static electricity that can cause equipment malfunctions and destroy microchips. <Prior art> The method of imparting antistatic properties to fabric is to use polyester,
A method using a modified fiber (antistatic fiber), which is a blend of a hydrophilic polymer or the like with a synthetic fiber such as nylon, is known. However, these techniques require a relative humidity of 50
Although it has practical antistatic performance under high humidity conditions of 30% or higher, its antistatic performance is insufficient under low humidity conditions of 30% or lower. The conductivity is also at a level of 10 ⁸ to ^{10 9} Ω·cm, which is not necessarily sufficient. The second method is to add a hydrophilic polymer through post-processing, but
In this case as well, the antistatic performance is insufficient under low humidity. In addition, the performance deteriorates with repeated washing, resulting in lack of washing durability. A third method is to coat fibers with a conductive substance such as carbon, or to use conductive fibers spun in composite with a polymer containing a conductive substance. In this method, if the conductive fiber is used only partially, the level of antistatic properties is not necessarily sufficient, but if the amount used is large and used over the entire surface, antistatic properties can be obtained, but the conductive fiber is expensive. The cost will increase,
Practical value is significantly reduced. Moreover, when used for clothing, the texture is hard and the feeling of wearing is poor. A fourth method is to apply a conductive substance to the fiber surface by chemical treatment (electroless plating).
This method is difficult to chemically treat uniformly, is expensive to manufacture, and lacks durability in use, making it unsatisfactory for use in applications such as explosion-proof clothing and antistatic work clothes. In order to eliminate the above drawbacks, it is possible to apply conductive paint to the fabric or to laminate a conductive film to the fabric, but if the coating is applied to a level that satisfies the durability, the texture becomes hard and When used for clothing due to loss of transparency, stuffiness occurs when worn. Furthermore, if a film is simply pasted onto a fabric, not only will the texture be hard, but the adhesive strength will be insufficient and the film will peel off. <Object of the invention> The present invention eliminates the above-mentioned drawbacks, has suitable drapability and flexibility, satisfies the functional aspects of antistatic property, transparency, and waterproofness, and also has adhesiveness with fabrics, The object of the present invention is to provide a method for producing clothing fabrics by a dry method, which also has excellent mechanical properties such as abrasion strength of the film. <Structure of the Invention> That is, the present invention provides a method for producing a moisture-permeable waterproof fabric in which a fabric is coated with a resin mainly composed of a polyurethane polymer,
A resin composition in which a conductive substance is added to a one-component moisture-permeable polyurethane resin is formed into a thin film, and then a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate,
A method for producing an antistatic, moisture-permeable, waterproof fabric, which comprises coating the fabric with a resin composition (A) comprising a crosslinking catalyst, and laminating the fabric through the resin composition (A).'' The fiber material used for the fabric here may be any of polyester, polyamide, polyolefin, polyurethane, etc., but polyester fibers are particularly preferred. The fabric may be in the form of a woven or knitted fabric, a non-woven fabric, or a combination thereof. The one-component moisture-permeable polyurethane resin referred to herein includes a polyester polyol containing a polyoxyalkylene glycol unit, a urethane prepolymer obtained by reacting a polyether polyol with a polyvalent isocyanate, and a polyfunctional chain extender having active hydrogen. For example, polyurethane obtained by reacting a polyhydric amine or a polyhydric alcohol can be used. The conductive substances referred to here include conductive carbon such as carbon black and acetylene black,
Refers to metal powders such as copper, silver, and nickel. These conductive materials may be used alone or in appropriate combinations as required. The two-component polyether polyol-modified polyurethane resin herein refers to (a) polyoxyalkylene glycol with an average molecular weight of 500 to 3,000, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, or ethylene oxide or propylene oxide of trimethylolpropane; 5 to 60 parts by weight, preferably 10 to 40 parts by weight, of polyoxyalkylene glycols such as adducts, or mixtures or copolymers thereof, and (b) polyesters with an average molecular weight of 500 to 5,000, such as succinic acid, adipic acid, sebacic acid, Polyesters produced by polycondensation of organic polybasic acids such as maleic acid and terephthalic acid and organic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, diethylene glycol, and glycerin, and lactonic acid. 95 to 40 parts by weight, preferably 90 to 60 parts by weight of a polyester or a mixture or copolymer thereof produced by ring polymerization; and (c)
Reaction of an organic polyisocyanate such as diphenylmethane 4,4'-diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or a mixture thereof with 5 to 25 parts by weight. Refers to polyurethane resin obtained by If the polyoxyalkylene glycol is less than 5 parts by weight, the moisture permeability will be poor, and if it is more than 60 parts by weight, the adhesion to the fabric will be low and the polyurethane film will become wet when wet with water. If the amount of organic polyisocyanate is less than 5 parts by weight, the mechanical properties of the polyurethane film will be insufficient,
If the amount is more than 20 parts by weight, the polyurethane film becomes rough and hard and its adhesive strength with the fabric decreases. Melamine derivatives are compounds represented by the following general formula. However, R ₁ to _{R 6} in the formula are -H, -CH ₂ OH, -
CH ₂ OC _o H2 _o+1 (where n is an integer from 1 to 16), -
It is a group selected from the group consisting of CH ₂ CH ₂ OH, -CONH ₂ and -CONHCH ₂ OH. In addition, it includes an initial condensate of the compound represented by the above general formula or an acid colloid compound. The amount of these melamine derivatives to be used is preferably 2% by weight or more, preferably 5 to 20% by weight, based on the two-component polyether polyol-modified polyurethane resin. If it is less than 2% by weight, the adhesive strength will be insufficient, and if it exceeds 20% by weight, the texture of the film will be rough and hard. Examples of the organic polyisocyanate compound as a two-component polyurethane crosslinking agent include hexamethylene diisocyanate, o-, m- or p-phenylene diisocyanate, 2,4- or 2,
6-tolylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate with hydrogenated aromatic ring, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate Isocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, ω,ω'-diisocyanate-4,
Examples include 4-dimethylbenzene and ω,ω'-diisocyanate-1,3-dimethylbenzene, which can be used alone or in combination. The amount of organic polyisocyanate used is 2
It is preferable to use 3 to 20 parts by weight per 10 parts by weight of the liquid polyether polyol-modified polyurethane resin and melamine derivative. The crosslinking catalyst consists of a melamine crosslinking catalyst and a urethane crosslinking catalyst, and an acidic catalyst is used as the melamine crosslinking catalyst. For example, aliphatic carboxylic acids such as formic acid and acetic acid, olefin carboxylic acids such as acrylic acid, saturated carboxylic acids such as oxalic acid and succinic acid,
Oxycarboxylic acids such as malic acid and tartaric acid, aromatic dicarboxylic acids such as phthalic acid and their ammonium acids, organic amine salts, sulfonic acids and their ammonium salts such as dodecylbenzenesulfonic acid and p-toluenesulfonic acid, sulfuric acid, Examples include inorganic acids such as hydrochloric acid, phosphoric acid, and nitric acid, and their ammonium salts. These catalysts are preferably used in an amount of 0.1 to 20% by weight based on the melamine derivative. As the urethane crosslinking agent, for example, organic metal compounds such as dibutyltin dilaurate and stannath octoate, and organic amines such as triethylenediamine and N-methylmorpholine are used. The amount used is preferably 0.1 to 10% by weight based on the organic polyisocyanate. Next, a method for producing the antistatic, moisture-permeable, waterproof fabric will be described below. An organic solvent solution of a resin composition in which a conductive substance is added to transparent one-component polyurethane is used as a skin layer on polypropylene coated paper or silicone coated paper.
Using a regular coating machine such as a knife coater, comma coater, kiss roll coater, etc., apply the coating to a solid content of 3 to 20 g/m2, and dry it to 80 g/ ^m2 .
Dry at a temperature range of ~120°C. Next, a resin composition (A) consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst is further applied as an adhesive layer on the moisture-permeable one-component polyurethane film formed on the release paper. The organic solvent solution is coated using a coating machine so that the solid content is 5 to 25 g/m ^{2 ,} and the organic solvent is semi-dry or completely dried using a dryer at a temperature range of 60 to 100°C. Next, the crosslinked film (A) and the base fabric were laminated, and the temperature was 100°C.
Heat-compression bonding is performed using a hot roll at ~130°C and a pressure of 3~30Kg/ ^cm2 . Then, the release paper is peeled off to obtain an antistatic, moisture permeable, waterproof fabric. Further, if necessary, the obtained fabric is impregnated with a water repellent solution, preferably a silicone-based or fluorine-based water repellent, and then dried to impart water repellency to the fabric. At that time, the base fabric may be treated to be water-repellent before lamination. <Effects of the Invention> The antistatic, moisture permeable and waterproof fabric obtained by this method is highly flexible and has antistatic properties, moisture permeability and waterproof properties, and has excellent mechanical properties such as adhesion to the base fabric and strong polyurethane coating. It has excellent properties and is a suitable material for clothing for special environments that require antistatic properties. <Examples> The present invention will be specifically described below with reference to Examples. In the Examples, the values of moisture permeability, water resistance, film abrasion resistance, and peeling strength between the film and the base fabric were determined as follows. Moisture permeability (g/m ² /24hr) Water pressure resistance (mmH ₂ O) according to JIS-K-6328 method Water repellency (points) according to JIS-K-1092 method Peel strength (g /cm) Membrane resistance to rubbing according to the method of JIS-K-6328 Using a Gakushin type friction fastness tester, overlap the polyurethane surfaces and rub together 100 times under a load of 500 g. 5 if the polyurethane surface is completely undamaged.
Grade: 4 for cases where the polyurethane surface is slightly damaged.
Grade: 3 when the polyurethane surface is damaged by about 1/3
Grade 1 is indicated when the polyurethane surface is completely peeled off. Antistatic property Charge amount (μc/m ² ) According to the method of JIS-K-1094 In the examples, parts and % represent parts by weight and % by weight, respectively. Example 1 One-component moisture-permeable polyurethane: Crisbon 3314
A polyurethane solution prepared by mixing 100 parts of conductive carbon paste (manufactured by Dainippon Ink and Chemicals Co., Ltd.) with 80 parts of Elteik EC8013 was coated on polypropylene coated paper using a comma coater so that the solid content was 8 g/ ^m2 . Coat and heat dry at 100℃ for 2 minutes to form a skin layer. Next, 20 parts of polyethylene glycol with an average molecular weight of 1500, 80 parts of polybutylene adipate diol with an average molecular weight of 2000, and tolylene diisocyanate.
15 parts to 105 parts of toluene and 68 parts of dimethylformamide
React in 173 parts of a mixed solvent with 40% resin concentration.
A two-component polyether polyol-modified polyurethane resin solution was obtained. To this solution was added 10 parts of trimethylolmelamine (87% based on the two-component polyether polyol modified polyurethane resin), and further 15 parts of hexamethylene diisocyanate, 0.5 part of p-toluenesulfonic acid,
0.5 part of dibutyltin dilaurate was added to obtain a two-component polyether polyol-modified polyurethane resin. This was applied as an adhesive to the skin layer obtained earlier so that the adhesive solid content was 18g/ ^m2 , and the temperature was 30℃ at 60℃.
It was dried for seconds to obtain a resin thin film. Next, a plain fabric using polyethylene terephthalate filament yarn (75 denier/72 filament) for the warp and weft was fabricated using disperse dye (CI) using a conventional method.
After dyeing with No. Desperse Blue 139), water repellency treatment was performed by impregnation using a 5% aqueous solution of water repellent agent Asahi Guard AG710 (manufactured by Meisei Chemical Co., Ltd.), followed by calendering and camfit treatment. The obtained dark blue water-repellent plain fabric (warp density: 116 threads/2.54 cm, weft thread density: 94 threads/2.54 cm) and the resin thin film were pasted together through a heated roll at 120°C, aged for 2 days, and then the release paper was peeled off. . The resulting antistatic, waterproof, breathable, and water-repellent fabric was flexible and had excellent moisture permeability, waterproofness, and water repellency. The main characteristic values were as shown in the table below. 【table】

Claims (1)

[Claims] 1. In a method for manufacturing a moisture-permeable waterproof fabric in which a fabric is coated with a resin mainly composed of a polyurethane polymer, a resin composition in which a conductive substance is added to a one-component moisture-permeable polyurethane resin is formed into a thin film, and then the A thin film is coated with a resin composition (A) consisting of a two-component polyether polyol-modified polyurethane resin, a melamine derivative, an organic polyisocyanate, and a crosslinking catalyst, and a fabric is laminated via the resin composition (A). A method for producing an antistatic, moisture-permeable, waterproof fabric.