JPH0116665B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fiber structure whose peel strength is improved by graft polymerization treatment of fibers. It is known to form a synthetic resin film on the surface of a fabric to make it waterproof, or to attach paper to it for use as wall material, sliding door paper, etc. However, in order to obtain a durable product, there are limits to the combinations of fabric fibers, adhesives, synthetic resin coating materials, etc., and the scope of its application has been limited. Particularly in the case of fabrics using filament systems, it has been difficult to obtain products with sufficient peel strength, and further improvements have been required. The present invention improves the drawbacks of the prior art as described above by graft polymerizing a specific monomer to fibers, and provides a fiber structure with a wide range of applications. The fiber structure of the present invention is a fabric made of fibers having active hydrogen, and the fibers include N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-methylenebis-α
- at least one selected from the group consisting of ethylamide and triacryloylhexahydrotriazine
The seed monomer has a grafting rate of 0.1 to 2%,
A sheet material made of a rubber or resin film is bonded to at least one side of a graft-polymerized fabric. Typical fibers containing active hydrogen include polyamide fibers, silk, and wool. In addition, fabrics include woven fabrics, knitted fabrics, and non-woven fabrics.
It is not limited to those made of a single fiber, but also includes blended products, mixed woven fabrics, mixed knitted fabrics, etc. Graft polymerization to fabric fibers may be carried out on yarns before fabric formation, or may be carried out after fabric formation. The treatment liquid for graft polymerization contains the above-mentioned monomer, acid, and, if necessary, a polymerization initiator. The concentration of the monomer in the treatment liquid is selected to be various depending on the amount of monomer attached to the fibers, but it is usually used in a range of 0.01 to 15% by weight. Also, if used, the polymerization initiator should be
It is about 0.1 to 10% by weight. The acid is used to adjust the pH of the processing solution, and the processing solution is usually used at a pH of 5.5 or lower. The treatment liquid can be easily obtained by dissolving the monomer in a solvent such as water, methanol, or ethanol, and then adjusting the pH of the liquid with an acid. Graft polymerization involves uniformly applying such a treatment solution to fibers by dipping, impregnating, spraying, etc.
This can be achieved by moist heat treatment at 100℃ for 10 to 60 minutes. The bath ratio in the immersion method is 1:5 to 1:
Around 100 is sufficient. Examples of acids to be included in the treatment solution include phosphoric acid,
Examples include hydrochloric acid, acetic acid, formic acid, oxalic acid, tartaric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and the like. For the immersion method, formic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, sulfuric acid, and hydrochloric acid are preferred, and for the impregnation method, formic acid, acetic acid, monochloroacetic acid, sulfuric acid, hydrochloric acid, and the like are preferred. Polymerization initiators used as necessary include:
Peroxides such as ammonium persulfate, potassium persulfate, benzoyl peroxide; cerium salts such as ceric ammonium sulfate and ceric ammonium nitrate; 4,4'-azobis-4-cyanovalerate sodium salt, 4,4 '-azobis-4-cyanovaleric acid ammonium salt, 2,2'-azobis(2-
Examples include water-soluble azo compounds such as acydinopropane (acidinopropane) hydrochloride. Next, the sheet-like material can be bonded to the graft-polymerized fabric by (i) bonding the sheet-like material to the fabric using an adhesive, or (ii) using a solvent between the fabric and the sheet-like material. There is a method of joining by heating and pressurizing, and (iii) a method of applying a synthetic resin liquid onto the fabric to form a sheet-like material. The method (i) is applied to pre-manufactured rubber or resin films, and bonding is preferably carried out by heating and pressurizing. As a synthetic resin film,
Polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, acrylic resin, natural rubber,
Films such as NBR and SBR are mainly used.
As the adhesive, any conventional adhesive such as one-component or two-component polyurethane, polyamide, polyvinyl chloride, ethylene vinyl acetate copolymer, epoxy resin, acrylic resin, etc. can be used depending on the purpose. The method (ii) is suitable for bonding a fabric and a rubber or resin film, but the solvent is preferably one that dissolves or swells the graft polymer and/or resin film polymerized to the fabric, especially the resin film. Dimethylformamide, methyl ethyl ketone, dioxane, toluene, trichloroethylene, methyl isobutyl ketone, carbinol, etc. are mainly used. Method (iii) mainly involves applying a synthetic rubber or synthetic resin solution to a fabric using a conventional coating method to form a resin film directly on the fabric. When adhering porous materials such as textile products, in addition to chemical bonding force or intermolecular force, physical bonding force can be used to separate the two materials. In the present invention, despite the relatively large molecular weights of N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-methylenebis-α-ethylamide and triacroylhexahydrotriazine, Because a highly polar and active water-soluble monomer is graft-polymerized onto the fabric fibers, it significantly improves the chemical bonding strength between the fabric and the sheet-like material without damaging the original texture of the fabric. Furthermore, in the present invention, by graft polymerizing the above monomer at a graft ratio within a predetermined range, fine irregularities are uniformly formed on the fiber surface, and physical bonding between the fabric and the sheet material (or adhesive) is achieved. Power also increases greatly. In addition, if the grafting rate is less than 0.1%, the unevenness of the fiber surface will be insufficient and the intended purpose cannot be achieved, and if the grafting rate exceeds 2%, the texture will be poor and practical use will be lost. Such unevenness on the fiber surface formed by graft polymerization in the present invention exhibits the effect of a hook or anchor. For example, when an adhesive or a synthetic resin coating liquid is applied to a fabric, the adhesive, etc. Penetrates into the tissue of the fabric and hardens into the shape of countless hooks, trees, and grass roots, conforming to the irregularities on the surface of the fibers. Thus, in extreme cases, the peel strength necessary to break the adhesive may be obtained without any chemical bonding of the adhesive. The fiber structure of the present invention has extremely excellent peel strength, so it can be used not only for normal purposes such as raincoats, leather wear, gloves, tablecloths, diaper covers, shower curtains, umbrellas, shoes, bags, and tents, but also for lifesaving purposes. It can also be used very effectively on vests, rubber boats, aquariums, etc. Further, in the present invention, by laminating with cardboard, it is possible to manufacture a clothing box having a cloth surface, which has been difficult in the past. Next, examples of the present invention will be shown. In the examples, peel strength was measured in accordance with JIS K6328-1977.
The numerical value is expressed as the average value of two test pieces. Example 1 Scoured and heat set 6-nylon oxford (210d/24fil, basis weight 110g/m ² , width 112
cm) was immersed in a treatment bath containing 1% N,N'-methylenebisacrylamide and 0.15% acetic acid, and then squeezed to a pick-up rate of 100% using a Nipprol and heated to 100°C.
The mixture was steamed for 1 hour. After washing the treated fabric in hot water at 60℃ for 20 minutes and then in water, the treated fabric and 60μ thick polyurethane (manufactured by Nippon Matai Co., Ltd.) were combined with adhesive (Adcoat 527 (manufactured by Toyo Morton Co., Ltd.) - 100 parts) and Adcoat.
9L1-10 parts mixture) at a pressure of 5Kg/
cm ² , was heated and pressed with a heating roll at 130°C, and bonded together. The peel strength of the product after being left at 60° C. for 24 hours and then at room temperature for 2 days was 3.4 kg/2.5 cm. The grafting rate in this example was 0.25%, but for comparison, 6-nylon oxford which was not graft polymerized and 6-nylon oxford grafted with a grafting rate of 0.07% were treated with polyurethane in the same manner as described above. The peel strength of the product to which the film was attached was measured. The results are shown in the following table in comparison with the results of this example.

[Table] Example 2 6-nylon oxford was subjected to graft polymerization treatment in the same manner as in Example (1), and one side of the treated cloth was coated with Crisbon 7616 SL (manufactured by Dainippon Ink & Chemicals).
A polyurethane resin solution consisting of 30 parts dimethylformamide, 30 parts methyl ethyl ketone, 30 parts and 10 parts toluene was applied to a thickness of about 200 g/m ² using a knife over roll coater and dried at 80 to 100°C. The peel strength of this product was 3.0 kg/2.5 cm. The grafting rate in this example was 0.24%, but for comparison, 6-nylon oxford which was not graft polymerized and 6-nylon oxford grafted with a grafting rate of 0.07% were treated with polyurethane in the same manner as described above. The peel strength of the product coated with the resin solution was measured. The results are shown in the following table in comparison with the results of this example.

[Table] Example 3 Scoured and heat set brushed nylon
40d/10fil, weft 20/1 Seradal yarn, weight 115g/
m ² , width 100 cm) containing N,N'-methylenebisacrylamide (20% of the fiber weight), ammonium persulfate (2% of the N,N'-methylenebisacrylamide), formic acid (adjust the pH of the bath to 2). The sample was immersed in a treatment bath, and then the treatment bath was gradually heated to 80° C. over 20 minutes. After treatment at 80°C for 30 minutes with occasional stirring, the temperature was increased to 60°C for 20 minutes.
Washed in hot water for 1 minute, followed by 20 minutes in water. An adhesive consisting of 50 parts of Crisbon 4216 (manufactured by Dainippon Chemical Industry Co., Ltd.), 50 parts of 4070 ( ), 10 parts of toluene, and 15 parts of toluene was applied to one side of the treated fabric thus obtained using a doctor knife. It was applied at a rate of about 70 g/m ² and dried at 70°C for 1 minute and at 120°C for 1 minute. Then, within 24 hours, apply a thick layer of adhesive onto this adhesive layer.
Place 8μ polyvinyl chloride film and heat at 150℃5
The polyvinyl chloride film was bonded onto the nylon base fabric by heating and pressing at kg/cm ² . The peel strength of the product was 3.3 kg/2.5 cm. The grafting ratio in this example was 0.23%, but for comparison, a polyvinyl chloride film was laminated to raised nylon that did not undergo graft polymerization and to raised nylon grafted to a grafting ratio of 0.07% in the same manner as described above. The peel strength of the product was measured. The results are shown in the following table in comparison with the results of this example.

【table】

Claims (1)

[Claims] 1. A fabric made of fibers containing active hydrogen containing N,
At least one monomer selected from the group consisting of N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N,N'-methylenebis-α-ethylamide, and triacroylhexahydrotriazine is added at a grafting rate of 0.1. ~2
%, a sheet-like material made of a rubber or resin film is physically strongly bonded directly or through an adhesive to at least one side of the grafted fabric, which has been graft-polymerized to form fine irregularities on the fiber surface. A fiber structure with excellent peel strength. 2. The fibrous structure according to claim 1, wherein the sheet-like material is bonded to the fabric by heating and pressing via a solvent. 3. The fibrous structure according to claim 1, wherein the sheet-like material is formed by applying synthetic rubber or synthetic resin liquid onto the fabric.