JPS6255981B2 - - Google Patents

Description

[Detailed description of the invention]

It is an object of the present invention to provide a solvent-resistant rubberized fabric, specifically a dry-cleanable rubberized fabric. Conventionally, rubberized fabrics used as materials for waterproof clothing, waterproof clothing, or winter clothing have not been dry-cleanable. This is because there were no polymer compositions that could be rolled into rubberized fabrics that were resistant to the solvents used in dry cleaning. The following four types of solvents are currently used for dry cleaning. A Industrial gasoline (JIS No. 5) B Tetrachlorethylene C Fluorinated solvent D 1.1.1. Trichloroethane On the other hand, nitrile rubber, acrylic rubber, silicone rubber, etc. have been well known as oil-resistant elastomers for a long time, but in particular 1.1 .1. There is no resistance to trichloroethane, and no matter how much research was carried out on compounding agents, it was not possible to obtain dry-cleanable rubberized fabrics from compositions containing trichloroethane as the main ingredients. In addition, fluorine-based elastomers, which have the potential to be dry cleaning resistant due to their basic properties, are often used in oil-resistant parts for automobiles, etc., but the minimum temperature required for vulcanization is 180°C to 200°C, and the vulcanization time is high. The upper temperature limit for rubberized fabric manufactured using a vulcanization method using a dyed base fabric without hot air processing is limited due to the need to protect the dye fastness of the base fabric, heat shrinkage, and surface oxidation of the rubber. It is difficult to maintain a temperature of about 160°C and a vulcanization time of several tens of minutes or more, and short-time vulcanization is a requirement from the viewpoint of the manufacturing process, so it is practically difficult to manufacture rubberized fabrics made of fluorocarbon polymers. It is also well known that epichlorohydrin rubber has recently been attracting attention as an elastomer with high solvent resistance, but it is mainly used in mold-cured products such as automobile parts, and although it has high basic properties, it has two major problems. There were flaws. One is that because it is amorphous, its green strength is low and its adhesion to rolls is excessive, and its rolling processability as a rubberized fabric is quite poor, making it impossible to roll topping with a calender roll. Furthermore, in the current normal manufacturing process for rubberized fabric, which involves topping with calender rolls and then continuous vulcanization in a short period of time under normal pressure in hot air, it is difficult to increase the crosslinking density of epichlorohydrin rubber, which causes the main chain ether bonds to dissociate. It was easy to use, softened and became sticky due to deterioration, and it was difficult to obtain repeated dry cleaning resistance. In addition, as a method to overcome the above-mentioned drawbacks, a method of mixing acrylonitrile butadiene rubber or chlorosulfonated polyethylene rubber with epichlorohydrin elastomer has been proposed, but these do not have complete solvent resistance and are particularly suitable for dry cleaning, which has recently been improved. Repeated resistance to tetrachlorethylene and trichloroethane, which are frequently used as solvents, could not be obtained. Focusing on this point, the present invention has a basic structure consisting of epichlorohydrin rubber as a main component, and a reinforcing fatty acid surface with an average particle size (0.2 to 0.5 μm), which is considered to have too large a particle size for rubber and has no reinforcing effect. They discovered that treated calcium carbonate was effective in improving rolling formability, and they also discovered that the main cause of softening and deterioration, which had previously been thought to be a heat factor, was caused by ultraviolet rays, and that the most suitable ultraviolet absorber was benzene. It is a triazole type anti-aging agent, and it was completed by discovering that it is most effective to use it together with an emidazole type anti-aging agent. The epichlorohydrin elastomer, which is the main polymer used in the present invention, is an epichlorohydrin homopolymer, a copolymer of epichlorohydrin and ethylene oxide, a copolymer of epichlorohydrin and allyl glycidyl ether, a copolymer of epichlorohydrin, ethylene oxide, and allyl glycidyl ether, and a copolymer of epichlorohydrin, ethylene oxide, and allyl glycidyl ether. A terpolymer is used, and
As shown in Table 1, there are many known non-carbon colorable reinforcing fillers for use in rubber for rolling uniform pinhole-free rubber sheets with a thickness of 50 to 150 μm, but none of them are satisfactory. Ta. For rubber, it is said that the smaller the particle size, the greater the reinforcing effect, but surprisingly, fatty acid-treated calcium carbonate with a relatively large primary particle size of 0.2 to 0.5 μm is mainly used for vinyl chloride paint, etc. They discovered that it has good reinforcing properties, dispersion pinhole properties, and non-adhesive sheeting processability compared to epichlorohydrin rubber.

[Table] Next, anti-aging agents are often used for rubber, and amine-based anti-aging agents, which are relatively effective, have staining properties, so they are unsuitable for rubber-coated fabrics for raincoats, which require light coloring. There are many amine reaction products, ketone-amine reaction products, phenolic products, etc., but none satisfy the performance of epichlorohydrin rubber as a roll-molded, dry-cleaning resistant, rubberized fabric.
It has been found that among the UV absorbers known mainly for use in plastics, benzotriazole-based UV absorbers are the most effective, and even higher effects can be obtained by using them in combination with emidazole-based anti-aging agents.
Table 3 shows test results showing the combined effects of benzotriazole-based, salicylic acid derivative-based, and benzophenone-based ultraviolet absorbers and emidazole-based and phenol-based anti-aging agents.

[Table] Next, to describe the examples in detail, a base paste of the following composition was mixed and stirred in the usual manner, dissolved, and then applied and dried on a nylon or polyester base fabric.

[Table] Next, the following compounded composition was mixed in the usual manner, and rolled and pressed onto the undercoat base fabric to a uniform thickness of 70 micrometers using a calendar roll, and the mixture was heated to a temperature of 160 m at normal pressure.
Vulcanize by continuous passage through a hot air chamber at 10°C for 20 minutes.

[Table] The rubberized fabric thus obtained has good processability, has a uniform thin film without pinholes, has an excellent appearance and feel, is excellent in solvent resistance and weather resistance, and can be repeatedly dry-cleaned. This makes it possible to provide materials for waterproof, cold-proof, and sports leisure clothing that satisfy the demand for high-performance luxury fashion that has not been available in the past. The first invention is that rolled molded rubber mainly composed of epichlorohydrin polymer is attached to one or both sides of the base fabric or between the laminated base fabrics, so it can withstand all the solvents currently used in dry cleaners and can be used in rain gear, for example. The second invention improves rolling workability by adding a surface-treated reinforcing filler with an average primary particle size of 0.2 to 0.5 micrometers to the first invention. In the third invention, the prevention of softening and deterioration can be further increased by using benzotriazole, which is an ultraviolet absorber, and in the fourth invention, by adding an emidazole-based anti-aging agent. We were able to obtain something that could withstand repeated dry cleaning.

Claims (1)

[Scope of Claims] 1. A solvent-resistant rolled-molded rubber coated fabric comprising rolled-molded rubber containing an epichlorohydrin polymer as a main component attached to one or both sides of the base fabric or between the base fabrics. 2. Solvent resistance made by attaching rolled molded rubber containing an epichlorohydrin-based polymer as a main component and a surface-treated reinforcing filler with an average primary particle size of 0.2 to 0.5 micrometers to one or both sides of the base fabric or between the base fabrics. Roll molded rubberized fabric. 3. On one or both sides of the base fabric or between the base fabrics, roll molded rubber containing an epichlorohydrin polymer as a main component, a surface-treated reinforcing filler with an average primary particle size of 0.2 to 0.5 micrometers, and a benzotriazole ultraviolet absorber is applied. A solvent-resistant rolled-molded rubber coated fabric. 4. On one or both sides of the base fabric or between the base fabrics, a surface-treated reinforcing filler with an average primary particle size of 0.2 to 0.5 micrometers based on an epichlorohydrin polymer as a main component, a benzotriazole-based ultraviolet absorber, and an emidazole-based anti-aging agent are added. A solvent-resistant rolled-molded rubber-coated fabric coated with rolled-molded rubber containing a solvent-resistant rolled-molded rubber.