JPH026128A - Rubberized fabric - Google Patents

Abstract

PURPOSE:To improve moisture permeability, weather resistance, cold resistance and abrasion resistance by laminating a composition mainly comprising a two-dimensional or three-dimensional copolymer rubber using propylene oxide, ethylene oxide and aryl glicidyl ether as ingredients onto a fabric base and heating and vulcanizing the composition. CONSTITUTION:A composition mainly comprising a two-dimensional or three- dimensional copolymer rubber, in which propylene oxide, ethylene oxide and aryl glycidyl ether are contained respectively at 50-99mol%, 40-0mol% and 10-1mol%, is laminated onto one surface of a fabric base, and heated and vulcanized. A fibrous fabric base is employed normally as the fabric base laminated onto the rubber composition. A natural organic fiber and an inorganic fiber such as glass fiber, asbestos fiber, etc., are used as a fiber. A rubberized fabric having such constitution can be used in a wide field as the component of various bags, a flexible container, waterproof clothing, a tent, a belt, a hood for a truck, a sheet for an open freighting article, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a rubberized fabric formed by laminating a rubber composition on a base fabric, and more specifically, to a rubberized fabric having improved moisture permeability and weather resistance. The invention also relates to a rubberized fabric that has a well-balanced combination of heat resistance, cold resistance, abrasion resistance, etc.

(Prior art and problems to be solved by the invention) Conventionally, rubber was applied to one or both sides of cloth, or HE
Rubber-coated fabrics bonded with rubber are well known and are used in a wide range of fields such as various bags, flexible containers, waterproof clothing, tents, belts, truck canopies, and sheets for covering open goods. The rubber layer of the rubberized fabric is made of natural rubber or isoprene rubber.

Styrene-butadiene rubber (SBR), chlorosulfonated polyethylene rubber (C3M), polyurethane rubber, etc. are used.

However, these conventional rubber materials do not fully satisfy the various properties required for rubberized fabrics.

For example, when used in waterproof clothing, rubberized fabric exhibits a waterproof function, but since it is also non-breathable, it cannot release moisture from sweat into the outside air and has the disadvantage of becoming stuffy. When used, when the outside temperature falls and the temperature of the rubberized cloth also drops, the water vapor contained inside the canopy or tent will accumulate on the inner surface of the rubberized cloth and become water droplets, which will fall on the items inside the canopy or tent and cause these to fall. There were disadvantages such as getting the area wet or dirty.

Furthermore, rubberized fabrics are generally used outdoors or in similar environments, and in such cases, in addition to water resistance and moisture permeability, they also require mechanical strength such as kneading resistance.

Weather resistance 1 Color stability, heat resistance, cold resistance, abrasion resistance.

It is also required to have mineral oil resistance, animal and vegetable oil resistance, etc. However, it has been difficult for conventional rubber materials to meet these various properties in a well-balanced manner.

(Objective of the Invention) The present inventors have developed a new rubberized fabric that meets the above-mentioned requirements.
This invention was completed as a result of intensive research for the purpose of

(Structure of the Invention) The present invention has propylene oxide, ethylene oxide, and allyl glycidyl ether as constituent components, and their constituent proportions are 50 to 99 mol%, 40 to 0 mol%, and 10 to 0 mol%, respectively.
A rubberized fabric characterized in that a composition containing 1 mol% of a binary or ternary copolymer rubber as a main component is laminated on at least one side of a base fabric and then heated and vulcanized. This is what we provide.

Although the binary or ternary copolymer rubber used in the present invention and its vulcanization process are known, there is no description or suggestion as to whether it is particularly suitable for the rubberized fabric of the present invention or its properties. (For example, US Pat. No. 3,135,705)
.

The propylene oxide constituting the copolymer rubber of the present invention has properties such as kneading resistance of rubberized cloth, weather resistance, color stability, cold resistance, water resistance, moisture permeability, and mineral oil resistance.

It is responsible for various properties such as vegetable oil resistance, and the above-mentioned ethylene oxide is introduced to impart particularly excellent moisture permeability, copper mineral oil resistance, vegetable oil resistance, etc. in addition to these properties.

Furthermore, allyl glycidyl ether is introduced as a vulcanization site in the copolymer rubber of the present invention.

In the copolymer rubber of the present invention, the constituent proportions of propylene oxide, ethylene oxide, and allyl glycidyl ether are 50 to 99 mol%, 40 to 0 mol%, and 10 to 10 mol%, respectively.
It is 1 mol%. Propylene oxide 90-99 mol%
A binary copolymer rubber consisting of 50-89 mol% of propylene oxide, 40-10 mol% of ethylene oxide, and 10-1 mol% of allyl glycidyl ether can be used. Original copolymer rubber is more preferred. Further, if desired, a mixture of binary and terpolymer rubbers can be used.

In the above copolymer rubber, if the propylene oxide content is less than 50 mol%, or the ethylene oxide content is more than 40 mol%, the water resistance decreases, causing problems such as the rubberized fabric being swollen by rainwater and increasing in weight. . Furthermore, if the allyl glycidyl ether content is less than 1 mol %, a sufficient crosslinking density cannot be obtained, resulting in stickiness of the rubberized fabric and a decrease in oil resistance. On the other hand, if it exceeds 10 mol%, the crosslinking density becomes too high and the original flexibility of the rubberized fabric is lost.

The degree of polymerization of the copolymer rubber of the present invention is expressed as M in Mooney viscosity.
Lt+a (100°C) of about 20 to 100 is preferable. If it is below this range, roll adhesion becomes severe during processing, and the physical properties of the vulcanizate tend to deteriorate. On the other hand, if it exceeds this range, the kneading processability with other compounding ingredients will decrease.

As the vulcanizing agent for the copolymer rubber of the present invention, known vulcanizing agents for unsaturated rubbers can be used. Examples of such agents include sulfur, sulfur-donating compounds, and so-called resin vulcanizing agents.

Examples include so-called oxime vulcanizing agents, and vulcanization accelerators used in combination with these include sulfur compound accelerators,
Examples include amine-based accelerators, as well as vulcanization retarders and metal compounds that serve as vulcanization accelerators. Specific examples of these drugs include morpholine polysulfides such as morpholine disulfide, tetramethylthiuram disulfide,
thiuram sulfides such as dipentamethylenethiuram tetrasulfide, alkylphenol formaldehyde resin as a so-called resin vulcanizing agent, and p-quinone dioxime as a so-called oxime vulcanizing agent.

p,p'-dibenzoylquinone dioxime, etc., thiuram monosulfide promoters such as tetramethylthiuram monosulfide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, etc. as sulfur compound promoters;
Benzothiazole accelerators such as zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-penzothiazylsulfenamide, N-oxydiethylene-2-
Sulfenamide accelerators such as benzothiazyl sulfenamide, sodium dimethyldithiocarbamate.

Dithiocarbamate accelerators such as zinc dibutyl dithiocarbamore, sodium isopropyl xanthate,
Examples include xanthate accelerators such as zinc butyl xanthate; examples of amine accelerators include guanidine accelerators such as diphenylguanidine and ortho-tolyl biguanide;
Examples include aldehyde ammonia type accelerators such as hexamethylenetetramine, aldehyde amine type accelerators such as n-butyraldehyde/aniline condensate, and the like. Examples of the vulcanization retarder include Nalityl Shun, Anhydrophthal M, N-cyclohexylthiophthalimide, 14-phenyl-N-trichloromethylthiobenzenesulfonamide, and D1
1 Metal compounds that can be used as sulfur accelerators include zinc oxide, magnesium oxide, litharge, red lead, dispersed lead, cadmium oxide, calci oxide, calcium hydroxide, stannous chloride, zinc stearate, etc. can be mentioned.

The amount of these vulcanizing chemicals added depends on the composition of the rubber, the type of chemicals,
Although it is determined depending on the intended use of the rubber component, it is usually about 0.05 to 40 parts by weight, preferably about 0.1 to 20 parts by weight, per 100 parts by weight of the rubber component.

In the present invention, the rubber composition can be mixed with various other rubbers in addition to the copolymer rubber of the present invention, thereby making it possible to enhance various properties. These other types of rubber are not particularly limited, but those that can be vulcanized using the same vulcanization system as the copolymer rubber of the present invention are preferred. Examples of such preferred polymers include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene-nonconjugated diene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, acrylonitrile-butadiene rubber, and partially hydrogenated acrylonitrile-based rubber. Examples include butadiene rubber, shrimp chlorohydrin-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. be able to. In order to exhibit the characteristics of the copolymer rubber of the present invention, the mixing ratio of these other types of rubber is preferably 70% by weight or less of rubber density in the rubber composition.

The present rubber composition further contains various reinforcing agents necessary for processing or for adjusting various physical properties in practical use.

Fillers, plasticizers, processing aids, stabilizers, anti-aging agents.

Ultraviolet absorbers, pigments, flame retardants, etc. can be optionally added.

In the present invention, a fibrous base fabric is preferably used as the base fabric to be laminated with the rubber composition. These fibers include natural organic fibers, inorganic fibers such as glass fibers and asbestos fibers, regenerated fibers such as viscose rayon, cupro, etc., semi-synthetic fibers such as G and tri-Aze-1 fibers, and synthetic fibers such as nylon 6 and nylon. 66. Polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers.

It is made of at least one kind selected from polyolefin fibers and polyvinyl alcohol fibers made insoluble or hardly soluble in water.

The fibers in the base fabric may be in any form such as short fiber spun yarn, filament (long fiber) yarn, split yarn, or tape yarn. Either is fine.

In the present invention, as a method for laminating the rubber composition on the base fabric, the rubber composition is laminated in sheets 1 to 1 using a calendar roll.
Examples include a method of laminating the base fabric by pressing it onto one or both sides of the base fabric at the same time as forming, or a method of forming the sheet into a sheet using a calendar roll or an extruder and then pressing the sheet and the base fabric with a roll to laminate them.

Lamination can also be carried out by dissolving the rubber composition in a solvent-containing solvent and coating the base fabric with this solution, or by dipping the base fabric in the solution and then drying it. Examples of organic solvents include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, and chlorinated hydrocarbon solvents such as carbon tetrachloride, or a mixture of two or more organic solvents. can be mentioned.

Furthermore, in order to improve the adhesion between rubber and cloth, it has often been conventional to use cloth that has been pre-starched. The base rubber glue used for this purpose often contains the same type of rubber as the sheet laminated to 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, an organic solvent solution of a rubber composition can be used as the subbing rubber paste. It may also be 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, and acrylic adhesives. Copolymer adhesives such as adhesives, polyamide adhesives, vinyl acetate-vinyl chloride adhesives, and vinyl acetate-ethylene adhesives are mentioned.

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

The adhesive interface can be formed by a calendering method, an extrusion method, a coating method, a dipping method, or the like.

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

There are no particular restrictions on the heating method, but press vulcanization using a hot platen or normal pressure vulcanization using a hot air oven is preferably used.

(Effects of the Invention) The rubberized fabric of the present invention is characterized in that at least one of the base fabrics is coated with a composition containing a binary or ternary copolymer rubber containing propylene oxide, ethylene oxide, and allyl glycidyl ether as a main component. It is made by laminating it on a surface and heating and vulcanizing it, making it waterproof.

It has a well-balanced combination of excellent physical properties such as moisture permeability, kneading resistance, weather resistance, heat resistance, cold resistance, abrasion resistance, mineral oil resistance, animal and vegetable oil resistance, and color stability. It can be used in a wide range of fields as a constituent material for flexible containers, waterproof clothing, tents, belts, truck canopies, sheets for covering open goods, etc.

Examples 1-4. Comparative Examples 1 to 3 Aliphatic polyamide fibers (nylon) having the following structure were immersed in a subbing rubber paste having the following composition and dried at 90°C for 10 minutes.

hr Copolymer rubber (1) 1002-Mercaptobenzimidazole (antiaging agent) 0,5 Zinc white 5 Tetramethylthiuram disulfide 1N-Cyclohexyl-
2-benzothiazylsulfenamide 1 Sulfur 1.5 Toluene 400 notes (1) Propylene oxide/ethylene oxide/allyl glycidyl ether constituent mole % 62/34/4 Mooney viscosity ML1+-4 (100°C> 67 Next, the first The composition shown in the table was mixed, rolled and pressed uniformly to a thickness of 100 μm using a calendar roll on the undercoating base fabric, and then passed continuously in a hot air oven at 160°C for 20 minutes at normal pressure to be vulcanized. Table 2 shows the results of measuring the physical properties of the rubberized fabric obtained.

Comparative Examples 1 to 3 were tested in the same manner as in Example 1, except that the compositions shown in Table 1 were used. The results are also shown in Table 2.

As a result, the rubber-coated fabric of the present invention sufficiently satisfies the various properties normally required of the article. In particular, in terms of strength properties such as kneading resistance and abrasion resistance, moisture permeability, copper mineral oil resistance, heat resistance, weather resistance, etc.
It can be seen that the performance is far superior to that of the combination of DM and base fabric.

Example 5. Comparative Example 4 Table 2 shows the results of a test conducted in the same manner as in Example 1, except that no subbing rubber paste was used and the composition shown in Table 1 was used.

As Comparative Example 4, a test was carried out in the same manner as in Example 5 except that the composition shown in Table 1 was used, and the results are also shown in Table 2.

Example 6. Comparative example 5 Polyester fiber base fabric with the following structure: Table 2 shows the results of measuring the physical properties of the cloth.

As Comparative Example 5, a test was conducted in the same manner as in Example 6 except that the composition shown in Table 1 was used, and the results are also shown in Table 2.

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

A 50% ethyl acetate solution of polyurethane adhesive (100 parts of "Niraporan 3105" and 15 parts of "Coronate" manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was applied to one side of the film using a 50% (1/20 cm) suspension and dried.

Claims (1)

[Claims] Contains propylene oxide, ethylene oxide and allyl glycidyl ether as constituent components, each with a composition ratio of 5.
A composition mainly composed of 0 to 99 mol %, 40 to 0 mol %, and 10 to 1 mol % of a binary or ternary copolymer rubber is laminated on at least one side of the base fabric and then heated. A rubberized fabric characterized by being vulcanized.