JPH09221552A - Production of binder rubber/metal composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for bonding a metallic part of a product to a rubber part of the product tightly after separately producing both parts in the production of an article constituting a bonded rubber/metal composite. SOLUTION: In the production of a bonded rubber/metal composite, a part obtained by subjecting the surface of a pregalvanized metal part to surface treatment with a metal surface treating agent comprising either a yellow chromate of zinc or olive chromate of zinc is bonded to a vulcanized rubber chlorinated with an organohalogen compound by using a synthetic resin adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite of rubber and metal, and more particularly, to a variety of rubber-metal bonded composite products by firmly bonding vulcanized rubber and metal to form a composite. The invention can be applied to the manufacture of

[0002]

2. Description of the Related Art As a method for producing an adhesive composite of rubber and metal, generally, the surface of the metal is subjected to an appropriate surface treatment,
A method has been adopted in which a chlorinated rubber-based vulcanizing adhesive is applied to the surface of the metal, and an unvulcanized rubber is brought into contact with the metal for vulcanization adhesion.

[0003]

Since the vulcanization adhesion of the unvulcanized rubber and the metal is carried out simultaneously with the rubber vulcanization reaction and the rubber-metal adhesion reaction, the adhesive composite in the mold for vulcanizing the unvulcanized rubber is used. The body is manufactured. However, the vulcanization bonding technology, which is a conventional technology for simultaneously performing these two chemical reactions, is a very economical method for manufacturing a bonding composite that can obtain a reliable bonding quality of a rubber-metal composite. However, it also has the following drawbacks.

When the shape of the rubber-metal bonded composite becomes complicated, rubber vulcanization using a vulcanization mold often becomes difficult in terms of mold design. In such a case, the geometrically complicated portions of rubber or metal are joined after the production of the adhesive composite, but the production cost therefor is significantly high. The anticorrosive function of the metal part of the adhesive composite is generally exhibited by applying metal plating or painting after manufacturing the composite, but the adhesive quality of the rubber itself and the rubber / metal composite deteriorates or the characteristics of the rubber change. To avoid this, coating involving heat treatment at high temperature, for example, epoxy resin-based electrodeposition coating for baking at 170 ° C to 190 ° C, or metal plating involving chemical treatment with strong acid or strong alkali has a high rust prevention function. However, it does not apply to adhesive composites. Therefore, in general,
A coating system having a low rust preventive power, which has a dry baking temperature of about 100 to 120 ° C. after coating, is selected and applied. When the product (rubber-metal adhesive composite) is large, the vulcanization adhesion by applying the vulcanization mold naturally requires a large mold corresponding to the size of the product.

Moreover, when the rubber portion occupies a small volume of the product, the disadvantage of preparing a large mold corresponding to the size of the product becomes remarkable, and specifically, the cost for producing a large mold, The decrease in productivity due to the production in place and large mold greatly increases the manufacturing cost of the product.

In order to solve the above problems, when manufacturing a product forming a rubber-metal adhesive composite, a lot of studies have been conducted to develop a technique of separately manufacturing a metal part and a rubber part of the product and then bonding them. The present invention has solved the above problems.

[0007]

[Means for Solving the Problems] That is, as described in claim 1, in the method for producing a rubber-metal bonded composite, the surface of the metal part, which has been electrogalvanized in advance, is attached to the surface of the metal part.
Further, as a metal surface treatment agent, either one of zinc yellow chromate treatment or zinc olive chromate treatment is applied, and on the other hand, vulcanized rubber is subjected to chlorination treatment by applying an organic halogen compound. , And are bonded and joined together using a synthetic resin adhesive, to provide a method for producing a rubber-metal bonded composite body. Further, as described in claim 2, there is provided a method for producing a rubber-metal adhesive composite, wherein the synthetic resin adhesive is adhesively bonded using an epoxy resin-based or urethane resin-based adhesive.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Structural adhesives are commonly applied to bond dissimilar materials. However, it is difficult to bond the vulcanized rubber and the dissimilar material to each other even if a typical epoxy resin-based adhesive or urethane resin-based adhesive is applied. Induces a peeling between. In order to improve this, in order to improve the adhesiveness of the surface of the vulcanized rubber, it is indispensable to modify the surface and enhance the reactivity with the adhesive as one means.

The details of the present invention will be described below. First, regarding the rubber component applied in the present invention, natural rubber,
Alternatively, a synthetic rubber having a carbon-carbon double bond in the structural formula alone or a blend of two or more kinds, or a blend of a natural rubber and the above synthetic rubber can be preferably used. As a method of modifying the surface of these vulcanized rubbers, the following method is generally applied. 1) Removal of adhesion-inhibiting substances (for example, buffing, degreasing with a solvent, etc.) 2) Cyclization method (immersing in concentrated sulfuric acid to create fine cracks that promote adhesion on the surface of vulcanized rubber) 3) Chlorination method ( Chlorine groups are introduced on the surface of vulcanized rubber to improve the adhesive strength by reacting with the adhesive.)

Further, as the chlorination treatment of the surface of the vulcanized rubber molded body, the following methods (1) to (4) can be adopted. A method of immersing a vulcanized rubber molded product in an aqueous solution of sodium hypochlorite and hydrochloric acid. A method of treating a vulcanized rubber molding by exposing it to a chlorine gas atmosphere. A method in which a solution obtained by dissolving an organic compound capable of giving chlorine to a vulcanized rubber is dissolved in an organic solvent is applied to a vulcanized rubber molded body to perform treatment. Among these, the method (3) is most advantageous in terms of safety of processing operation, adhesion effect and the like.

According to the present invention, a vulcanized rubber / metal adhesive composite can be produced by adopting the chlorination method of 3) of the above "0009" among the surface treatment methods for various vulcanized rubbers. Becomes In particular, as described in "0010",
The generally adopted "method of treating a vulcanized rubber surface by applying a solution in which an organic halogen compound is dissolved in an organic solvent" exhibits the highest adhesive quality, and among various organic halogen compounds, TCCA (trichloroisocyanurium) is used. Acid) develops the best adhesion.

On the other hand, steel, aluminum, etc. are recommended as the material of the metal parts usable in the present invention.
Then, as the pretreatment for adhesion of the metal component material, galvanized one is used, but in the present invention, the chromate treatment of zinc applied on the electrogalvanized surface is yellow chromate treatment or olive (green) Limited to chromate treatment.

Similarly, as the structural adhesive used in the present invention, an epoxy resin adhesive or a urethane resin adhesive can be preferably applied. In the production of a rubber / metal adhesive composite, the present invention separately prepares a metal part that has been subjected to a pre-adhesion treatment and an anticorrosion treatment, and a vulcanized rubber that has been chlorinated by applying an organic halogen compound. However, by bonding these with a synthetic resin adhesive, preferably an epoxy resin-based or urethane resin-based adhesive, the high rust resistance required for the product and the conventional vulcanizing adhesive applied to the metal side. However, it is possible to obtain a bonding quality equal to or higher than the rubber-metal bonding quality when the unvulcanized rubber and the metal are bonded by vulcanization. Especially when an epoxy resin adhesive is applied, the adhesive durability is improved when the adhesive composite is used in a corrosive environment.

[0014]

EXAMPLES The present invention will be described below with reference to examples, but of course the present invention is not limited to these examples. Example 1 The composition of the rubber composition used in this example is shown in Table 1.
Shown in The metal member used in this example was a steel material.

[0015]

[Table 1]

In order to prepare a round type vulcanized rubber-metal adhesive "FIG. 1" specified in JIS-K6256 (93), a rubber composition having a composition shown in Table 1 is vulcanized. After vulcanization,
A 3% acetone solution of trichloroisocyanuric acid was applied to the surface of the vulcanized rubber for chlorination treatment. On the other hand, the metallic member is subjected to zinc yellow chromate treatment (manufactured by Nippon Surface Chemical Co., Ltd .: “Rohmate # 62”) on the electrogalvanized layer. Commercially available epoxy resin adhesive (TH
Product made by E DEXTER CORPORATION, HY
SOL “EA9460”) was used, applied, and heated and cured at 100 ° C. for 20 minutes in a pressure-bonded state to produce an adhesion test piece.

Example 2 The same rubber composition, vulcanization and surface treatment as in Example 1 were carried out, and the metal member was plated with zinc yellow chromate of zinc (manufactured by Nippon Surface Chemical Co., Ltd .:
"Romate # 62" treatment was applied, and in place of commercially available epoxy resin adhesives, urethane resin adhesives ("KU6611 / 662" manufactured by Konishi Co., Ltd.) were used in place of the commercially available epoxy resin adhesives in a pressure-bonded state. A test piece was manufactured in the same manner as in Example 1 except that the material was heated and cured at 120 ° C. for 30 minutes.

[Example 3] In Example 1, the metal member was electro-galvanized and zinc (olive (green) chromate (manufactured by Nippon Surface Chemical Co., Ltd.): "Strong phosphorus #"
A test piece was prepared in the same manner as in Example 1 except that it was treated with 333 ″).

[Example 4] Example 3 was repeated except that a urethane resin adhesive ("KU661 / 662" manufactured by Konishi Co., Ltd.) was used for the member instead of the epoxy resin adhesive. A test piece was prepared in the same manner as in.

Comparative Example 1 Example 1 is the same as Example 1 except that the metallic member is electrogalvanized and treated with a bright chromate of zinc (manufactured by Japan Surface Chemical Co., Ltd .: “Romate # 60”). A test piece was prepared in the same manner as.

[Comparative Example 2] In Example 1, a metallic member was electrogalvanized and then treated with a bright chromate of zinc (manufactured by Japan Surface Chemical Co., Ltd .: "Romate # 60") to obtain an epoxy resin adhesive. Urethane resin adhesive instead of (Kunishi Co., Ltd., "KU6611 / 662")
A test piece was prepared in the same manner as in Example 1 except that was used.

Comparative Example 3 Example 1 is the same as Example 1 except that the metal member is electrogalvanized and then treated with black chromate of zinc (manufactured by Nippon Surface Chemical Co., Ltd .: “MF-323”). A test piece was prepared in the same manner as.

Comparative Example 4 The same as Comparative Example 3 except that a urethane resin adhesive (“KU661 / 662” manufactured by Konishi Co., Ltd.) was used in place of the epoxy resin adhesive in Comparative Example 3. Then, a test piece was prepared.

[Comparative Example 5] The metal member was subjected to the same surface treatment as in Example 1, and a commercially available two-component coating type vulcanizing adhesive ("Chemlock 220" and "Chemlock 205" manufactured by USA Road Co., Ltd.) was used. ) Was used to vulcanize and bond an unvulcanized rubber to prepare an adhesive test piece.

[Comparative Example 6] The metal member was subjected to the same surface treatment as in Example 3, and a commercially available two-component coating type vulcanizing adhesive ("Chemlock 220" and "Chemlock 205" manufactured by USA Road Co., Ltd.) was used. ) Was applied and the unvulcanized rubber was vulcanized and adhered to produce an adhesion test piece.

[Comparative Example 7] Each of the metal members was subjected to the same surface treatment as in Comparative Example 1, and a commercially available two-component coating type vulcanizing adhesive ("Chemlock 220" and "Chemlock 220" manufactured by USA Road Corporation) was used. 205 ") was applied to vulcanize and bond an unvulcanized rubber to produce an adhesive test piece.

The evaluation results of the production conditions, the rubber adhesiveness, and the rust preventive power of the adhesive in each of the above Examples and Comparative Examples are shown in "Table 2-1" and "Table 2-2".

[0028]

[Table 2-1]

[Table 2-2]

The evaluation of the adhesiveness between the rubber and the metal (steel material) was carried out by the method specified in JIS-K6256 (93), and the evaluation was made by the rubber breakage ratio during the test. Further, the rust preventive power of the adhesive body was evaluated by a salt spray test in which a 5% sodium chloride / neutral aqueous solution was sprayed, and was evaluated by the time until rusting of the metal part.

[0030]

As described above, the details thereof have been described and studied. As a result, by adopting the method for producing a vulcanized rubber / metal composite of the present invention, high rust preventive power of metal and vulcanized rubber / metal can be obtained. Adhesive composites with reliable and strong adhesive properties can be realized, such as vibration-proof rubber for automobiles, industrial use, engine mounts, belts, hoses, crawlers, etc. If products such as soundproofing and vibration damping materials are manufactured using the method of the present invention, their utility value is extremely high as a manufacturing method having simplicity and superiority as compared with conventional manufacturing methods of these products.

[Brief description of drawings]

FIG. 1 Cross-sectional view of vulcanized rubber / metal bonded body

[Explanation of symbols]

 1 metal member 2 rubber

Claims (2)

[Claims] 1. A method for producing a rubber-metal adhesive composite, wherein the metal part is preliminarily electrogalvanized on the surface of the metal part, and further, as a metal surface treating agent, zinc yellow chromate treatment or zinc olive chromate treatment is performed. Characterized by the fact that one of them is treated and the other is a vulcanized rubber that is treated with an organohalogen compound and chlorinated, and the two are bonded together using a synthetic resin adhesive. And a method for producing a rubber-metal bonded composite. 2. The method for producing a rubber / metal adhesive composite according to claim 1, wherein the synthetic resin adhesive is adhesively bonded using an epoxy resin-based or urethane resin-based adhesive.