JPS6312502B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition for bonding textile materials and rubber. Rubber is often used in tires, belts, hoses, waterproof sheets, etc. by bonding reinforcing fibers and rubber. Resorcin formaldehyde resin aqueous liquid (hereinafter referred to as RF liquid) has traditionally been used to bond natural rubber, styrene-butadiene copolymer rubber (hereinafter referred to as SBR), etc. to fibers.
Compositions of natural rubber latex, SBR latex, or styrene-butadiene-vinylpyridine ternary copolymer rubber latex are so-called
Used as RFL adhesive. However, a terpolymer rubber consisting of ethylene, an α-olefin higher than ethylene, and a non-conjugated diolefin,
Compared to highly unsaturated rubber such as natural rubber and SBR, which are conventionally used mainly in tires and belts,
Although it has far superior weather resistance, ozone resistance, heat resistance, etc., it has poor adhesion to fibers and is unable to provide sufficient adhesive strength even when using the above RFL adhesive. It has limited uses.
Further, isobutylene isobrene copolymer rubber (butyl rubber hereinafter abbreviated as IIR) has similar circumstances. Therefore, the present inventors have conducted intensive studies on methods of adhering fibers to terpolymer rubber made of ethylene, α-olefin higher than ethylene, and non-conjugated diolefin, and found that RF liquid and sulfohalogenated polymer ( We discovered that an excellent adhesive effect can be obtained by using an organic solvent solution or an aqueous dispersion of SHP (hereinafter abbreviated as SHP) and applied for a patent. (Japanese Patent Application No. 55-180822) Furthermore, we continued to study this adhesive method, especially an adhesive method using SHP aqueous dispersion, and found that by using polyvinyl alcohol in combination, the adhesive strength was significantly improved. (Japanese Patent Application No. 56-62847), a method of adding zinc compounds and magnesium compounds to RFL for the purpose of preventing deterioration of adhesive strength due to high-temperature baking treatment (Japanese Patent Application No. 58-20246), and a method of adding sulfochlorinated polyolefin to RF liquid. (hereinafter abbreviated as SCP) and a specific rubber vulcanization modifier, the company learned that a composition with the addition of a specific rubber vulcanization modifier exhibits strong adhesive strength even during baking treatments at high temperatures, and filed a patent application for the method. (Special application 1982-
Application No. 208048). As a result of further investigation into a good composition for bonding textile materials and rubber more firmly, the inventors of the present invention have formulated a composition containing specific amounts of three components: RF liquid, SCP aqueous dispersion, and natural rubber latex. did
We discovered that RFL liquid exhibits strong adhesive strength and arrived at the present invention. The RFL liquid as used in the present invention consists of an RF liquid, an SCP aqueous dispersion, and natural rubber latex. RF liquid is an aqueous solution prepared by reacting a substance that easily generates formaldehyde, such as formaldehyde or paraformaldehyde, with a phenolic compound, such as dihydroxybenzenes such as resorcinol, using an appropriate known method, for example, in the presence of an alkali metal hydroxide. It is a liquid and is prepared using 0.5 to 4 moles of formaldehyde per mole of the phenolic compound, and the resin concentration is generally adjusted to 5 to 40% by weight. The SCP aqueous dispersion is an aqueous dispersion that generally contains about 5 to 70% by weight of a sulfochlorinated polymer. Examples of sulfochlorinated polymers include ethylene, propylene, n-butylene, isobutylene,
Homopolymers such as butadiene and isoprene, non-conjugated dienes such as ethylidenenorbornene and dicyclopentadiene, or styrene,
A polymer with a structure thought to be produced by treating a copolymer of vinyl chloride, vinyl acetate, acrylic acid, methacrylic acid, methacrylic acid ester, etc. with chlorine and sulfur dioxide or sulfuryl chloride. . The chlorine content in the polymer is 5~
70% by weight, and the sulfur content is often between 0.1 and 10% by weight. Although any commercially available natural rubber latex can be used, it is common to use one that has been concentrated to 60% using methods such as centrifugation and stabilized with ammonia. The RFL liquid is prepared so that the total solid content of the sulfochlorinated polymer and natural rubber latex is 10 to 5000% by weight per 1 solid content in the RF liquid. A viscosity modifier, an antioxidant, etc. may be added as necessary, and it is also effective to add a zinc compound, a magnesium compound, or a vulcanization modifier as described above. The present invention provides a composition that can improve the adhesion of textile materials to rubber by using the above-mentioned RFL liquid, and its characteristics include an SCP aqueous dispersion and natural rubber latex as components of the RFL liquid. The process consists of mixing in a specified proportion. The amount of natural rubber latex used depends on its solid content.
The amount of the SCP aqueous dispersion is 3% by weight or more and 80% by weight or less, preferably 10% by weight or more and 60% by weight or less, based on the total solid content of the natural rubber latex. If it is less than 3% by weight, there is no effect of improving the adhesive strength when mixing natural rubber latex with SCP water dispersion and using it as an adhesive, and even if it is more than 80% by weight, the adhesive strength will be lower than that of the SCP water dispersion alone. Adhesion strength is reduced and does not give desirable results. Natural rubber latex can be used by adding SCP water dispersion to RF liquid and then mixing natural rubber latex, or by adding a mixture of SCP water dispersion and natural rubber latex to RF liquid in advance. The aqueous dispersion of SCP can be obtained by sulfochlorination of an aqueous dispersion of raw material polymer or by dispersing SCP in water, but the latter method is usually adopted. In other words, a dispersion consisting of an SCP solution phase and an aqueous phase is prepared using a method such as high-speed stirring containing an appropriate emulsifier, and then heated at an appropriate pressure under pressure, normal pressure, or reduced pressure to separate the solution phase. Part or all of the solvent is removed by vaporization distillation, and if necessary, some of the water is removed by vaporization distillation or by using centrifugal force. Adjust the concentration to an appropriate concentration of about 70% by weight. In this case, SCP solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and halogenated hydrocarbons such as carbon tetrachloride, ethylene tetrachloride, ethane tetrachloride, and various fluorinated chlorinated hydrocarbons. Hydrogen solutions are often used. In the SCP aqueous dispersion, an emulsifier is usually used as a dispersion stabilizing agent, as shown in the above production method. These emulsifiers include fatty acid soaps, rosin acid soaps, alkyl ether sulfonates, alkyl sulfonates, alkyl sulfates, alkenesulfonates, alkyl ether sulfonates, dialkyl sulfosuccinates, and polyoxyethylene alkyl phenyl ethers. Sulfuric ester salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl allyl esters, fatty acid sucrose esters, naphthalene sulfonic acid soda formalin condensate, tetraalkyl Ammonium salts, alkylpyridinium salts,
Various anionic surfactants, nonionic surfactants, cationic surfactants such as alkylbenzylammonium salts, polyethylene polyamine tetraacetic acid salts, alkyl betaines, as well as amphoteric surfactants are used. Among these, anionic surfactants are generally preferred from the viewpoint of adhesive strength. These emulsifiers are generally 0.01 to
20% by weight is used, preferably 0.1-10% by weight.
If it is less than 0.01%, the dispersion stabilizing effect will not be sufficient, resulting in a reduction of 20%.
Even if you use more than 20%, the effect is almost the same as when using 20%. Further, for this water dispersion, it is also possible to use a small amount of an emulsification aid such as isopropanol, which is soluble in both water and an organic solvent. Examples of fibers to which the present invention is applied include natural fibers and synthetic fibers such as cotton, nylon, vinylon, polyester, and aromatic polyamide. The fibers subjected to the RFL surface treatment of the present invention can be used as belts,
Ethylene propylene diene copolymer rubber (hereinafter abbreviated as EPDM),
Ethylene propylene copolymer rubber (hereinafter abbreviated as EPR), isobutylene isobrene copolymer rubber, sulfochlorinated polyethylene rubber, styrene propylene butene copolymer rubber, ethylene propylene butene copolymer rubber, ethylene butene copolymer rubber, ethylene butene diene copolymer rubber In addition to rubber, it is used after bonding with other rubbers such as natural rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and chloroprene rubber. The shapes of the fibers vary widely depending on their purpose, such as cords, canvas, short fibers for reinforcement, and short fibers for flocking. The method of bonding textile materials and rubber using the adhesive composition of the present invention usually involves first dipping,
A textile material is impregnated with RF liquid using an appropriate method such as coating, spraying, or roll treatment, and then it is applied directly to the textile material that has been treated in advance, such as by drying or heat treatment as necessary. By an appropriate method such as coating, spraying, or rolling,
There is a method of impregnating a mixture of SCP water dispersion and natural rubber latex, drying, heat treatment, etc., and contact vulcanization with rubber such as EPDM containing various additives. After impregnating the fiber material with an RFL liquid composition prepared by pre-mixing the mixed liquid with the RF liquid using an appropriate method such as dipping, coating, spraying, or rolling, the mixture is dried, heat treated, etc., and various additives are added. compounded
There is a method of contact vulcanization treatment with rubber such as EPDM, and as a result, it is possible to firmly bond the fiber material and the rubber. Among these methods, the method of treating textile materials using a premixed composition of RF liquid, SCP water dispersion, and natural rubber latex is industrially advantageous because the process is simplified. be. When using the RFL liquid in the method of the present invention, the RFL liquid is impregnated into textile materials by an appropriate method such as dipping, coating, spraying, or rolling, and then dried at an appropriate temperature between room temperature and 250°C. , After heat treatment, it is laminated or sandwiched with rubber that has been mixed with a suitable vulcanization compound such as a vulcanizing agent, vulcanization accelerator, anti-aging agent, reinforcing agent, etc. The adhesive is completed by adding a finishing treatment to the rubber, such as vulcanization under normal vulcanization conditions, such as under pressure at 130-160° C. for several minutes to two hours. In the composition of the present invention, latexes such as SBR latex or styrene butadiene vinyl pyridine terpolymer latex or conventional
It goes without saying that RFL adhesives can be used in combination in any desired manner, often with good results. In addition, a method of adding the above-mentioned zinc compounds and magnesium compounds to the RFL liquid (patent application 1983-
It is also clear that even better results can often be obtained by the method of adding a specific rubber vulcanization agent (Japanese Patent Application No. 58-208048). Examples of the present invention will be shown below, but the present invention is not limited thereto. As mentioned above, EPDM is used as an adherend for fibers.
This is because EPDM is considered to be the most difficult to adhere to fibers. Γ Preparation of SCP aqueous dispersion For example, polyethylene (hereinafter abbreviated as PE) (density
The solution was dissolved in 12 kg of sulfochlorinated polyethylene (chlorine content: 35%, sulfur content: 1%) prepared from 0.96 g/cm ³ ). On the other hand, 1.2 kg (purity 30%) of polyoxyethylene (4 moles of EO added), octyl phenyl ether sulfate ester soda salt (manufactured by NOF Corporation, trade name TRAX H-45), and 40 kg of water were added to 40 kg of water. (addition of 30 moles of EO), nonyl phenyl ether sulfate ester soda salt [manufactured by NOF Corporation, trade name Trax N-300], prepared by dissolving 690 g (purity 35%) and 84 g of caustic potassium, two solutions were prepared. Emulsifying machine (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.)
was sufficiently emulsified. The emulsion obtained in this way was transferred to a stainless steel container of 150 ~
The jacket was heated by circulating hot water at 70°C under a reduced pressure of 100 mmHg, and toluene and other substances were distilled off. After cooling, 30Kg of product was obtained. The solid content of the product is
It was 40%. In addition, polypropylene (hereinafter abbreviated as PP) (density
Sulfochlorinated polypropylene (chlorine content 26%, sulfur content 1%) manufactured from 0.90g/cm ³ ),
Sulfochlorinated EPDM (chlorine content 23%, sulfur content 1%) manufactured from EPDM (density 0.86 g/cm ³ ),
A latex of a sulfochlorinated polymer of sulfochlorinated ethylene propylene rubber (chlorine content 28%, sulfur content 1%) made from ethylene propylene rubber (density 0.87 g/cm ³ ) can be prepared in the same manner as described above. Preparation of Γ RF liquid A solution prepared by dissolving 0.4 g of caustic soda in 242 g of water was mixed with 11 g of resorcin and 16.2 g of a 37% formalin aqueous solution, and left to mature at room temperature for 5 hours. Preparation of Γ RFL liquid SCP water dispersion and natural rubber latex (product name
Mix SOCTEX LATEX-HA (solid content: 60%, manufactured by Nomura Trading) with 20g of RF liquid, and
It was left to mature for some time. Γ Compound of adhered rubber EPDM*E502 70 parts EPDM*E512F 30 parts Zinc white 5 parts Stearic acid 1 part MAF carbon 110 parts Diana Process NM280 70 parts N-cyclohexyl-2-benzothiazylsulfenamide 1.5 parts Tetramethylthiuram Disulfide 0.5 part dipentamethylenethiuram tetrasulfide
0.7 parts Zinc dibutyldithiocarbamate 1.5 parts Sulfur 1 part The above composition is prepared using a Banbury mixer or the like. * Sumitomo Chemical Co., Ltd. Esprene (ethylene propylene ethylidene norbornene ternary copolymer rubber) Γ Measurement of adhesion After immersing a 1260 denier nylon cord in the above RFL solution, dry it for 3 minutes in a constant temperature dryer at 150°C. I did some baking. The treated cord thus prepared was embedded in the above-mentioned unvulcanized adhered rubber compound and vulcanized at 150°C for 30 minutes to prepare an H-test specimen. Adhesive strength was measured by the "H-pull test" described in P. (1946). The results are shown in Table-1. 【table】

Claims (1)

[Claims] 1 For 1 mol of resorcin, formaldehyde
It consists of a mixture of an aqueous resorcinol-formaldehyde resin liquid prepared using 0.5 to 4 mol, an aqueous dispersion of sulfochlorinated polyolefin, and natural rubber latex. A fiber in which the total solid content of the natural rubber latex is 10 to 5000% by weight, and the solid content in the natural rubber latex is 3 to 80% by weight based on 1 of the total solid content of the sulfochlorinated polyolefin aqueous dispersion and the natural rubber latex. Adhesive composition for adhering to rubber. 2. The composition according to claim 1, wherein the sulfochlorinated polyolefin is sulfochlorinated polyethylene. 3. The composition according to claim 1, wherein the rubber is an ethylene propylene diene copolymer rubber.