JPS63248884A - Production of composite consisting of rubber and metal - Google Patents

Abstract

PURPOSE:To obtain the titled composite to be used in automobile parts such as damper pulleys or bushings, requiring no primer and giving high adhesiveness even under corrosive environment, by nitrogen treatment followed by oxidation treatment of the surface of a metal and then bonding between the resultant surface and a rubber using an adhesive. CONSTITUTION:A metal 1 such as hot rolled steel plate is immersed in e.g. a potassium cyanate bath at 580-660 deg.C to perform a nitrogen treatment of the adhesive surface 1a of said metal 1 followed by immersing said surface in e.g. a nitrate bath at 230-400 deg.C to carry out oxidation treatment of said surface The resultant surface is coated with e.g. a one-pack adhesive consisting mainly of chlorosulfonated polyethylene as the chlorinated polymer followed by heating to bond between said surface 1a and the adhesive surface 3a of a rubber 3, thus obtaining the objective composite.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a method of manufacturing a rubber-metal composite used for automobile parts such as damper pulleys and bushings.

(Prior Art) Anti-vibration rubber conventionally used as automobile parts and the like is composed of a combination of rubber and metal. In order to withstand harsh usage conditions, this type of anti-vibration rubber is first treated with a plastic coating on the metal surface, then a phenolic resin adhesive is applied as an undercoat adhesive (primer), and then a halogen-based adhesive is applied as a topcoat adhesive. It was manufactured by applying a chemically modified elastomer adhesive, overlapping it with rubber, and bonding it.

(Problems to be Solved by the Invention) In the above-mentioned conventional technology, it is necessary to blast the metal surface for adhesion, a brimer is required, and the rubber and metal cannot be bonded together in an environment where water or salt water may come into contact with the metal surface. There was a problem that the adhesiveness between the two was thick (decreased).

Structure of the Invention (Means for Solving the Problems) In order to solve the above problems, the present invention has a structure in which the surface of the metal is nitrided and then oxidized, and then an adhesive is applied to bond it to rubber (hereinafter referred to as The metal surface is nitrided and then oxidized, and the metal surface is further subjected to lapping and oxidation treatment, and then adhesive is applied to bond it to rubber (hereinafter referred to as the second invention). .

(Function) By adopting the configurations of the first invention and the second invention, metal nitrides are formed on the metal surface, and in addition, metal oxides are also formed, and when adhesive is applied, they become water resistant. Or, the adhesion between rubber and metal is sufficiently maintained even in an environment where salt water is present.

[Examples and Comparative Examples] Examples embodying the first invention and the second invention will be described below with reference to the drawings.

As shown in the figure, the rubber-metal composite obtained in Examples 1 and 2 below has both upper and lower adhesive surfaces 3a of the rubber 3 bonded to the adhesive surface 1a of the metal 1 via the adhesive layer 2. There is. A gripping portion 4 is formed on both the upper and lower end surfaces 1b of both the upper and lower metal parts 1.

(Example 1) Next, an embodiment embodying the first invention will be described.

First, the bonding surface 1a of a hot rolled 84 plate (SPHC) serving as the metal 1 is subjected to nitriding treatment. The nitriding treatment is a method of hardening the surface layer of steel by putting it in a high nitrogen state. Specifically, it is carried out by a liquid nitriding method in which the metal 1 is immersed in a potassium cyanate salt bath at a temperature of 580 to 660°C. . At that time, nitrogen is produced by the following reaction, which combines with iron to produce iron nitride. Therefore, the adhesive surface 1 of metal 1
Iron nitride (Fe2 N, Fe3 N, Fe4
A film of N) is formed.

3KOCN-KCN+ is followed by 2CO3+C+2N, and then oxidation treatment is performed thereon. The oxidation treatment is carried out at 230-400℃
This is done by immersion in a nitrate bath at a temperature of .

The oxidation treatment can be performed using an inorganic acid salt bath such as sulfate or hydrochloride in addition to a nitrate bath.

Next, Chemlosoku 252 (trade name, manufactured by Lord Corporation), which is a one-component adhesive whose main component is chlorosulfonated polyethylene as a chlorinated polymer, is applied to the surface of the adhesive surface 1a treated in this way, and heated. By doing so, the adhesive surface 1a and the adhesive surface 3a are joined.

As the above-mentioned molding adhesive, an adhesive containing a chlorinated polymer as a main component is suitably used, and examples of the chlorinated polymer include chlorinated rubber, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chloroprene rubber, and chlorinated polymer. Examples include vinyl elastomers.

Now, the initial adhesion and water resistance between the metal 1 and the rubber 3 were measured as follows.

First, metal 1 and rubber 3.1! : Explain how to prepare a test piece of the composite.

■Remove oil etc. adhering to the adhesive surface 1a of the metal 1 with trichloroequene.

(2) The adhesive surface 1a is treated by the liquid nitriding method described above.

(2) Subsequently, the adhesive surface 1a is subjected to the oxidation treatment using the nitrate bath described above.

(2) Next, as a rubber adhesive, the above-mentioned Chemronok 252 is spray-coated on the adhesive surface 1a, and dried at 50°C for 10 minutes to form an adhesive layer 2. The thickness of the adhesive Fi2 is approximately 10 μm. In addition, the application of Chemurosoku 252 is as follows:
You may also use a brush, roller, etc.

Next, a rubber 3 made of an unvulcanized natural rubber material having the composition shown in Table 1 below was prepared, and the rubber 3 was placed between the two metal sheets 1 and pressed at 150°C for 30 minutes. heating,
Pressure is applied to bond the rubber 3 and metal 1 by vulcanization.

Table-1 Note 1) Product name “Sunnock 1” manufactured by Ouchi Shinko Kagaku Co., Ltd. Note 2) Product name “TSUKRAK-” manufactured by Ouchi Shinko Chemical Co., Ltd.
224J (poly(2,2,4-)dimethyl-1,
2-Dihydroquinoline] Note 3) Product name “Tsukrac-” manufactured by Ouchi Shinko Kagaku Co., Ltd.
81ONaJ (N-phenyl-N-isopropyl-
p-phenylenediamine) Note 4) Manufactured by Ouchi Shinko Kagaku Co., Ltd. (N-cyclohexyl-2-benzothiazolyl sulfonamide) Test of the composite of rubber 3 and metal 1 prepared as above The piece was pulled vertically at a speed of 25 mm/min by holding the grip 4 in a universal tensile tester to examine adhesive strength and fracture state. In addition, regarding water resistance, adhesive strength and fracture state were similarly investigated.

The results are shown in Table 2 below.

The meanings of the terms in Table 2 are as follows.

Initial adhesion: adhesive area 1. la+I, tensile speed 251I
I11/ll1in, unit of adhesive strength is kg/cA
It is.

Water resistance: The adhesive surface was 811.1 coi, and after being immersed in warm water at 60° C. for 10 days in a state of 10% elongation, the adhesive strength was measured and the state of destruction was examined.

Destruction state: R...Rubber 3 is destroyed RC...Destroyed between rubber 3 and adhesive WI2 M...Adhesive IW2 and gold! Destruction between 1 (Example 2) Next, an embodiment embodying the second invention will be described.

Following the oxidation treatment in Example 1, a lapping treatment was performed. The lapping process is a type of precision finishing, and is a finishing method used when more precision than normal grinding is required. A lapping agent such as silicon carbide is placed between a tool called a lamp and the workpiece and rubbed. A smooth surface is obtained by utilizing the abrasive action between the two. The wrapping process can be done by hand or by using a lapping machine.

After such lapping treatment, the above-described oxidation treatment is performed again.

The adhesiveness of the composite of rubber 3 and metal 1 obtained as described above was evaluated in the same manner as in Example 1 above. The results are shown in Table 2 below.

(Comparative Example 1) Only grid blasting was performed on the adhesive surface 1a of the metal 1.

The grid blasting process uses iron powder of about 0.2 mm to polish the adhesive surface 1a.
It creates minute irregularities on the surface.

The adhesiveness of the thus obtained composite of Rubber 3 and Metal 1 was evaluated in the same manner as in Example 1 above. The results are shown in Table 2 below.

(Comparative example 2) Only the nitriding treatment was performed on the adhesive surface 1a of the metal 1.

The nitriding treatment was performed in the same manner as in Example 1 above.

The adhesiveness of the thus obtained composite of rubber 3 and metal 1 was evaluated in the same manner as in Example 1. The results are shown in Table-2.

/'' Table-2 As is clear from Table-2 above, when the adhesion surface 1a of gold N1 is treated only with glysoto blasting (comparative example 1) or only with nitriding treatment (comparative example 2), gold Ws1 has poor water resistance. In contrast, Examples 1 and 2 exhibited sufficient adhesive strength to the extent that the rubber 3 was destroyed in terms of water resistance, whereas the adhesive strength was 0 due to peeling between the adhesive surface 1a and the adhesive M2.

As described above, the reason why the adhesive strength, particularly the water resistance, is improved by the first or second invention is that iron nitride (Fe3 N, Fe4 N, etc.) or iron oxide (Fe3
This is presumed to be due to the fact that hydroxide ions (OH-) are less likely to be generated from the surface of the metal 1 even in the presence of moisture because a strong film of 04, etc.) is formed.

The present invention is not limited to the above embodiments, but can also be configured as follows.

(1) The nitriding process includes a gas nitriding method performed at a temperature of about 500°C in a mixture of carbon oxide (CO), methane (CH4), and ammonia (NH3), and a 1-10 mmHH
An ion nitriding method has also been adopted in which the furnace wall is used as an anode and the steel to be treated is used as a cathode in a mixed gas of nitrogen (N2) and hydrogen (1 x 2) under reduced pressure, and the surface of the steel is heated by glow discharge. Ru.

(2) As the oxidation treatment, an oxidation method using high temperature air is also adopted, and the same oxidation method is performed when a gas nitridation method is used as the nitridation treatment. According to the same oxidation method, a layer of triiron tetroxide (Fe304) is formed on the surface of iron, for example.

(3) To bond the rubber 3 and metal 1, the rubber 3 is vulcanized in advance, and then the surface is nitrided and then oxidized, or the surface is nitrided and then oxidized, and then wrapped and oxidized. Apply adhesive to the metal 1 and attach the rubber 3.
It can also be carried out by heating and pressurizing the metal 1 and the metal 1 on top of each other.

(4) As the rubber 3, various synthetic rubbers other than natural rubber (NR) such as chlorinated butyl rubber, chloroprene rubber (C
R), chlorosulfonated polyethylene, ethylene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene terpolymer rubber (EPDM), ethylene-propylene copolymer rubber (EPM), etc. are used. .

(5) Rubber 3 and gold I7 obtained by the first invention or the second invention
! The composite material with 1 may be used in any member in which the rubber 3 and the metal 1 are bonded with adhesive, but specifically it is used in anti-vibration rubber in automobile parts such as engine mounts, bushings, damper pulleys, and bodies. Examples include mounts.

Effects of the Invention According to the first and second inventions, there is no need to blast the metal surface during adhesion, no need for a brimer, and the resulting composite of rubber and gold mud has excellent adhesive properties, especially It has the excellent effect of providing sufficient adhesive strength between rubber and metal even in corrosive environments exposed to water or salt water.

[Brief explanation of drawings]

The figure is a sectional view showing a composite of rubber and metal.

Claims (1)

[Claims] 1. A composite of rubber and metal, characterized in that the surface (1a) of metal (1) is nitrided and then oxidized, and then adhesive is applied to bond it to rubber (3). manufacturing method. 2. The method for producing a composite of rubber and metal according to claim 1, wherein the adhesive is a one-component adhesive containing a chlorinated polymer as a main component. 3. Rubber and metal, characterized in that the surface (1a) of metal (1) is nitrided and then oxidized, further subjected to lapping treatment and oxidation treatment, and then adhesive is applied to bond it to rubber (3). A method for producing a composite. 4. The method for producing a composite of rubber and metal according to claim 3, wherein the adhesive is a one-component adhesive containing a chlorinated polymer as a main component.