JPH0637106B2 - Rubberized cloth - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubberized fabric obtained by laminating a rubber composition on a base fabric, and more specifically, it has improved moisture permeability and weather resistance. However, the present invention also relates to a rubberized cloth having a good balance of heat resistance, cold resistance, wear resistance and the like.

(Prior Art and Problems to be Solved by the Invention) Conventionally, a rubberized cloth in which rubber is applied to one side or both sides of a cloth material or a thin layer rubber is laminated is known, and various bags, flexible containers, waterproof clothing. It is used in a wide range of fields such as tents, belts, hoods for trucks, and sheets for covering field products. Then, the rubber layer of the rubberized cloth has natural rubber, isoprene rubber, styrene-butadiene rubber (SBR),
Chlorosulfonated polyethylene rubber (CSM), polyurethane rubber, etc. are used.

However, these conventional rubber materials do not sufficiently satisfy various properties required for rubberized cloth.

For example, when used for waterproof clothing, the rubberized cloth exerts a waterproof function, but since it is also impermeable to moisture, it cannot release moisture due to perspiration to the outside air, and has the drawback that it easily gets damp. When used, when the outside air temperature decreases and the temperature of the rubberized cloth also decreases, the water vapor contained in the inside of the hood or tent condenses on the inside surface of the rubberized cloth to form water droplets that fall on the articles inside the hood or tent. There were drawbacks such as getting wet and dirty.

In addition, rubberized cloth is generally used outdoors or in an environment close to it. In such cases, in addition to water resistance and moisture permeability, mechanical strength such as scuff resistance, weather resistance, coloring stability,
It is also required to have heat resistance, cold resistance, abrasion resistance, mineral oil resistance, animal and vegetable oil resistance, etc. However, it has been difficult for conventional rubber materials to meet these characteristics in a well-balanced manner.

(Purpose of the Invention) The present inventors have completed the present invention as a result of intensive studies for the purpose of obtaining a novel rubberized fabric that meets the above-mentioned various requirements.

(Structure of the invention) The present invention comprises propylene oxide, ethylene oxide and allyl glycidyl ether as constituent components, and the composition ratios thereof are respectively 50 to 99 mol%, 40 to 0 mol% and 10 to 1 mol%.
To provide a rubberized fabric, characterized in that the composition containing a binary or ternary copolymer rubber as a main component is laminated on at least one surface of a base fabric, and post-vulcanized by heating. Is.

It is known that the binary or ternary copolymer rubber used in the present invention and that it can be vulcanized, but it is neither described nor suggested as being particularly suitable for the rubberized fabric of the present invention or its characteristics ( For example, U.S. Pat. No. 3,135,705).

The propylene oxide constituting the copolymer rubber of the present invention has various properties such as rubbing resistance, weather resistance, coloring stability, cold resistance, water resistance, moisture permeability, mineral oil resistance, vegetable oil resistance, etc. In addition to these, the above ethylene oxide is introduced to impart particularly excellent moisture permeability, mineral oil resistance, vegetable oil resistance and the like. Allyl glycidyl ether is introduced as a vulcanization site of the copolymer rubber of the present invention.

In the copolymer rubber of the present invention, the composition ratios of propylene oxide, ethylene oxide and allyl glycidyl ether are 50 to 99 mol%, 40 to 0 mol% and 10 to 1 mol%, respectively.
Is. A binary copolymer rubber consisting of 90 to 99 mol% of propylene oxide and 10 to 1 mol% of allyl glycidyl ether can be used, but 50 to 89 mol% of propylene oxide, 40 to 10 mol% of ethylene oxide and 10 mol of allyl glycidyl ether. A terpolymer rubber consisting of ˜1 mol% is more preferred. If desired, the binary and ternary copolymer rubbers may be mixed and used.

In the above-mentioned copolymer rubber, when propylene oxide exceeds 50 mol%, that is, ethylene oxide exceeds 40 mol%, water resistance is lowered and problems such as swelling of rubberized cloth due to rain water and increase of weight occur. On the other hand, if the amount of allyl glycidyl ether is less than 1 mol%, a sufficient cross-linking density cannot be obtained and stickiness of the rubberized cloth and deterioration of oil resistance may occur.
On the other hand, when it exceeds 10 mol%, the crosslink density becomes too high and the original flexibility of the rubberized cloth is lost.

The degree of polymerization of the copolymer rubber of the present invention is M in terms of Mooney viscosity.
L _{1 + 4} (100 ° C.) 20 to 100 is preferable. If the amount is less than this range, the roll adhesion tends to be great at the time of processing, and the physical properties of the vulcanized product tend to deteriorate. On the other hand, when it exceeds this range, the kneading processability with other compounding agents deteriorates.

As the vulcanizing agent for the copolymer rubber of the present invention, known vulcanizing agents for unsaturated rubber can be used. Examples of such agents include sulfur, sulfur donating compounds, so-called resin vulcanizing agents, so-called oxime vulcanizing agents, etc. as vulcanizing agents, and vulcanization accelerators used in combination with these. Examples thereof include sulfur compound type accelerators, amine type accelerators and the like, and other examples include vulcanization retarders, and further metal compounds and the like serving as vulcanization acceleration aids. Specific examples of these agents include morpholine polysulfides such as morpholine disulfide as a sulfur donating compound or thiuram sulfides such as tetramethylthiuram disulfide and dipentamethylene thiuram tetrasulfide as a sulfur donating compound, and an alkylphenol formaldehyde resin as a so-called resin vulcanizing agent. Etc., so-called oxime vulcanizing agents such as p-quinone dioxime, p, p'-dibenzoylquinone dioxime, etc., as sulfur compound-based accelerators, thiuram monosulfide-based accelerators such as tetramethyl thiuram monosulfide, 2-mercaptobenzo Thiazole, dibenzothiazyl disulfide,
Benzothiazole accelerators such as zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazylsulfenamide, N-oxydiethylene-2-
Examples include sulfenamide accelerators such as benzothiazyl sulfenamide, dithiocarbamate accelerators such as sodium dimethyldithiocarbamate and zinc dibutyldithiocarbamate, and xanthate accelerators such as sodium isopropylxanthate and zinc butylxanthate. As an amine-based accelerator, diphenylguanidine,
Examples thereof include guanidine-based accelerators such as orthosultryl biguanide, aldehyde ammonia-based accelerators such as hexamethylenetetramine, and aldehyde amine-based accelerators such as n-butyraldehyde / aniline condensates. Examples of the vulcanization retarder include salicylic acid, phthalic anhydride, N-cyclohexylthiophthalimide, N-phenyl-N-trichloromethylthiobenzenesulfonamide, and the like. As the metal compound serving as a vulcanization accelerator, zinc oxide, Magnesium oxide, litharge, red lead, lead peroxide, cadmium oxide,
Examples thereof include calcium oxide, calcium hydroxide, stannous chloride and zinc stearate.

The additives for these vulcanizing agents are rubber composition, type of agent,
The amount is usually 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the rubber component, although it is determined depending on the purpose of use of the rubberized cloth.

In the present invention, the rubber composition may contain various other rubbers in addition to the copolymer rubber of the present invention to enhance various properties. These other rubbers are not particularly limited, but those capable of being vulcanized in the same vulcanization system as the copolymer rubber of the present invention are preferable. Examples of such preferable polymers include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, ethylene-propylene-non-conjugated diene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, acrylonitrile-butadiene rubber, partially hydrogenated acrylonitrile- Butadiene rubber, epichlorohydrin-allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer rubber, epichlorohydrin-propylene oxide-allyl glycidyl ether copolymer rubber, unsaturated group-containing acrylic rubber, etc. it can. The mixing ratio of these other rubbers is preferably 70% by weight or less in the rubber content of the rubber composition in order to exhibit the characteristics of the copolymer rubber of the present invention.

The rubber composition further includes various reinforcing agents, fillers, plasticizers, processing aids, stabilizers, anti-aging agents, and ultraviolet absorbers necessary for processing or adjusting physical properties for practical use. , Pigments, flame retardants, etc. can be arbitrarily mixed.

In the present invention, a fibrous base cloth is usually preferably used as the base cloth laminated with the rubber composition. These fibers include natural organic fibers, inorganic fibers such as glass fibers and asbestos fibers, recycled fibers such as viscose rayon and cupra,
Semi-synthetic fibers such as di- and tri-acetate fibers and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers and water insolubilized or It is composed of at least one selected from poorly soluble polyvinyl alcohol fibers and the like.

The fibers in the base cloth may be any shape such as a short fiber spinning system filament, a filament (long fiber) system filament, a split yarn, a tape yarn, etc. The base fabric may be a woven fabric, a knitted fabric, a non-woven fabric or a composite fabric thereof. Either may be used.

In the present invention, as a method for laminating the rubber composition on the base cloth, a method of forming the rubber composition into a sheet by a calender roll and simultaneously laminating by pressing on one side or both sides of the base cloth, or once using a calender roll or an extruder. A method of laminating the sheet and the base fabric by pressing them with a roll and laminating them after the sheet is formed.

Alternatively, the rubber composition can be laminated by a method such as dissolving the rubber composition in an organic solvent and coating the solution on a base cloth, or immersing the base cloth in the solution and then drying. As the organic solvent, one or a mixture of two or more of aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and organic solvents such as chlorinated hydrocarbon solvents such as carbon tetrachloride. Can be mentioned.

Further, conventionally, a cloth which has been pre-sized is often used for the purpose of improving the adhesiveness between the rubber and the cloth. The undercoat rubber paste used for this purpose is often composed mainly of the same type of rubber as the sheet laminated on the cloth, but it is not limited to the same type of rubber as long as it can achieve the purpose.

Also in the present invention, the organic solvent solution of the rubber composition can be used as the undercoat rubber paste. It is useful to interpose other useful adhesive materials between the fabric and the rubber composition. Examples of such adhesive substances include melamine adhesives, phenolic adhesives, epoxy adhesives, polyester adhesives, polyethyleneimine adhesives, polyisocyanate adhesives polyurethane adhesives, acrylic adhesives. Examples thereof include polyamide-based adhesives, vinyl acetate-vinyl chloride adhesives, vinyl acetate-ethylene adhesives and other copolymer adhesives.

These adhesive substances can be used alone or in admixture with the rubber composition or the undercoat rubber paste of the present invention.

The formation of the adhesive interface can be performed by a calendar method, an extrusion method, a coating method, a dipping method, or the like.

The rubberized fabric of the present invention is produced by laminating the rubber composition on at least one surface of the base fabric, and then heat vulcanizing at 100 to 200 ° C. for 1 minute to 2 hours.

The heating method is not particularly limited, but press vulcanization with a hot platen or atmospheric vulcanization with a hot air oven is preferably used.

(Effects of the Invention) The rubberized fabric of the present invention comprises a composition containing a binary or terpolymer rubber containing propylene oxide, ethylene oxide and allyl glycidyl ether as a main component as at least one of the base fabrics. It is laminated on the surface and heat-vulcanized, and is waterproof, moisture permeable, chaffing resistance, weather resistance, heat resistance, cold resistance, abrasion resistance, mineral oil resistance, animal and vegetable oil resistance, coloring stability, etc. It has excellent physical properties in a well-balanced manner and can be used in various bags, flexible containers, waterproof clothing,
It can be used in a wide range of fields as a constituent material for tents, belts, truck hoods, and sheets for covering field products.

Examples 1 to 4 and Comparative Examples 1 to 3 are aliphatic polyamide fiber (nylon) base fabrics having the following structures: It was immersed in an undercoat rubber paste having the following composition and dried at 90 ° C. for 10 minutes.

phr Copolymer rubber (1) 100 2-Mercaptobenzimidazole (anti-aging agent) 0.5 Zinc flower 5 Tetramethyl thiuram disulfide 1 N-Cyclohexyl-2-benzothiazyl sulfenamide 1 Sulfur yellow 1.5 Toluene 400 Note (1) Propylene oxide / ethylene oxide / allyl glycidyl ether composition mol% 62/34/4 Mooney viscosity ML _{1 + 4} (100 ° C.) 67 Next, the compounding compositions shown in Table 1 were mixed, and the mixture was placed on the subbing base cloth. Table 2 shows the physical properties of the rubberized cloth obtained by vulcanizing by uniformly rolling and calendering with a calender roll to a thickness of 100 μm and continuously passing through a hot air oven at 160 ° C for 20 minutes at atmospheric pressure. It was shown to.

As Comparative Examples 1 to 3, the results of the same tests as in Example 1 except that the compounded compositions shown in Table 1 were used are also shown in Table 2.

As a result, the rubberized fabric of the present invention has the result that the properties normally required for the article are sufficiently satisfied. In particular, SBR and EP, which have been conventionally known in terms of strength characteristics such as chafing resistance and abrasion resistance, and moisture permeability, mineral oil resistance, heat resistance, weather resistance, etc.
It can be seen that it shows much better performance than the combination of DM and substrate.

Example 5, Comparative Example 4 Table 2 shows the results of the same tests as in Example 1 except that the undercoat rubber paste was not used and the compounding composition shown in Table 1 was used.

As Comparative Example 4, the results of the same tests as in Example 5 except that the compounded composition shown in Table 1 was used are also shown in Table 2.

Example 6, Comparative Example 5 Polyester fiber base fabric having the following structure: Polyurethane adhesive (100 parts of Nippon Polyurethane Industry "Nipporan 3105" and "Coronate L") on one side of
15 parts) of 50% ethyl acetate solution was applied in an amount of 5 g / m ² and dried.

Next, the compounding compositions shown in Table 1 are mixed, and uniformly rolled and calendered to a thickness of 100 μm on the above base fabric with a calendar roll, and continuously passed through a hot air oven at 160 ° C for 20 minutes at normal pressure. Table 2 shows the results of measuring the physical properties of the rubberized fabric obtained by vulcanizing at least.

As Comparative Example 5, the results of the same tests as in Example 6 except that the compounded composition shown in Table 1 were used are also shown in Table 2.

As a result, the rubberized fabric of the present invention is significantly superior to the rubberized fabrics using other rubbers in the resistance to chaffing, moisture permeability, mineral oil resistance, heat resistance, cold resistance, weather resistance and abrasion resistance. I understand.

Continuation of the front page (72) Inventor Yasuo Matoba 2-1-1 Shojo, Toyonaka City, Osaka Prefecture (56) References JP-A-63-74638 (JP, A)

Claims (1)

[Claims] 1. A binary or ternary copolymer comprising propylene oxide, ethylene oxide and allyl glycidyl ether as constituent components and having respective constituent proportions of 50 to 99 mol%, 40 to 0 mol% and 10 to 1 mol%, respectively. A rubberized cloth, characterized in that a composition containing rubber as a main component is laminated on at least one surface of a base cloth and then vulcanized by heating.