JP3222956B2 - Metal / rubber composite vibration insulator - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal / rubber composite vibration isolator in which a metal fitting is adhered to a vibration isolating rubber body exhibiting a vibration isolating effect, and relates to a vibration isolator for an automobile such as a mount for an engine or a bush for a suspension link. Used as a body or as an anti-vibration support for other machinery.

[0002]

2. Description of the Related Art As a metal / rubber composite vibration isolator, a surface of a metal fitting made of aluminum or an alloy thereof is subjected to a chromate treatment to form a chromate film, and the surface of the film is coated with a simultaneous vulcanizing adhesive. It is known that a vibration-proof rubber body is simultaneously vulcanized and bonded (see Japanese Patent Application Laid-Open No. 4-115943).

Japanese Patent Application Laid-Open No. 55-66951 discloses that a silicone resin, an organopolysiloxane, an organic silane compound, A material containing a material and a curing catalyst is described.

[0004]

However, in the case of a metal / rubber composite vibration insulator using the above-mentioned chromate-treated metal fittings, the chromating treatment can prevent the metal fittings from rusting, but the chromium ion causes pollution. There is a problem of occurrence.

Further, in order to enhance the adhesion stability between the metal fitting and the vibration-proof rubber body, a cationic electrodeposition coating is performed after the above-mentioned chromate treatment. However, the chromate treatment itself is performed by alkali degreasing the metal fitting → water washing → It requires a number of steps of pickling, washing with water, removing smut, washing with water, chromate treatment, washing with water, washing with hot water, and drying.In addition, the above electrodeposition coating is required, so the number of steps is very large, It is disadvantageous in terms of productivity.

[0006] On the other hand, in the case of the silicone rubber-based primer, even if it is effective for bonding the silicone rubber to the metal fitting, it is not possible to expect the rust-preventing effect of the metal fitting.

[0007] That is, an object of the present invention is to prevent rust of metal fittings without causing a problem of pollution and difficulties in manufacturing, and to improve adhesion stability between the metal fittings and the vibration-proof rubber body. is there.

[0008]

SUMMARY OF THE INVENTION The present invention provides
As a result of intensive studies on such problems, it has been found that treating the surface of a metal fitting with a silane coupling agent can solve the above-mentioned problems, and has completed the present invention.

That is, a means for solving the above-mentioned problem is a metal / rubber composite vibration isolator in which a metal member is adhered to a vibration-isolating rubber member exhibiting a vibration-proof action, and the surface of the metal member is made of a silane coupling agent. An organic silane compound film is formed, and an adhesive cured layer formed by thermosetting a thermosetting adhesive is formed on the surface of the organic silane compound film bonded to the vibration-proof rubber body, The surface-activated bonding surface of the vibration-proof rubber body is bonded to the cured adhesive layer of the metal fitting with an isocyanate-based adhesive.

According to this means, the corrosion resistance of the metal fitting is obtained by the organosilane compound film on the surface of the metal fitting, and the adhesive stability of the adhesive layer to the metal fitting surface is obtained. That is, the organic silane compound has a hydrolyzable substituent such as an alkoxy group or a halogen, and a group that easily reacts with an organic substance such as a vinyl group, an epoxy group, or an amino group. While bonding protects the fitting from corrosion, the latter is bonded to the adhesive layer by a group that easily reacts with the organic substance, thereby improving the adhesion of the adhesive layer to the surface of the fitting.

As the above-mentioned metal fittings, those made of non-ferrous metal, for example, made of aluminum, aluminum alloy, or magnesium alloy are preferably used. An oxide film or the like bonded to this non-ferrous metal and an organic silane compound (silane coupling agent)
And a silane coupling reaction is performed between the two to form an organic silane compound film.

As the vibration-proof rubber member, natural rubber (N
R) and synthetic rubber (for example, styrene butadiene rubber (S
(BR) or butadiene rubber (BR), etc., or by blending natural rubber and styrene butadiene rubber (NR / SBR) or blending natural rubber and butadiene rubber (NR / BR). It can also be molded.

The organic silane compound includes XR-
Various silane coupling agents represented by the general formula of Si- (OR ') 3 can be used. In this case, X is a methacryloxy-based, amine-based, epoxy-based, or mercapto-based active group, and R and R 'are alkyl groups. For example,
γ-methacryloxypropyltrimethoxysilane, γ-
It is preferable to use aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, or the like.

As the thermosetting adhesive, a two-part curable adhesive such as a phenolic resin-based or chlorinated rubber-based adhesive, or a one-part curable adhesive can be used.

The surface activation treatment of the vibration-proof rubber body is for activating the vulcanized rubber surface with an organic acid, an inorganic acid or a physical treatment, and includes a halogenation treatment, a nitration treatment, and a cyclization treatment. , Methylene iodide treatment or plasma treatment.

In the case of the above-mentioned halogenation treatment, halogenated isocyanuric acid, halogenated succinimide,
Among halogenated isocyanates, N-halogensulfonamides or halogenated hydantoins, etc., a halogenation treating agent such as hydrochloric acid, hypochlorous acid, sodium hypochlorite, iodine chloride or iodine bromide as an inorganic acid. select. Among them, isocyanate iodide, dichloroisocyanuric acid, trichloroisocyanuric acid, N-dichloro-P-toluenesulfonamide and the like are preferable in terms of surface treatment performance, processing safety, treatment speed and the like. The selected halogenating agent is dissolved in a suitable organic solvent and diluted to a concentration of 0.1 to 30%, preferably 1 to 20% to obtain a halogenated solution. As the organic solvent, toluene, xylene, isooctane, dimethyl ether, ethyl acetate, methyl ethyl ketone, carbon tetrachloride, industrial thinner, or the like may be used. Then, after degreased the surface of the vibration-isolating rubber body which is a vulcanized rubber, it is immersed in the halogenated solution or sprayed or coated with the halogenated solution for a relatively short time (for example, a few seconds or more). 3 minutes). In this case, rinsing of the surface is often not necessary.

In the case of the above-mentioned nitration treatment, a nitrating agent is selected from among iodine nitrate, iodine azide, bromine azide, nitric acid and mixed acid. Then, a low-concentration nitrating solution is applied to the surface of the vibration-proof rubber body for a short time, and then the applied surface is sufficiently washed with water. In the case of this nitration treatment, since the reactivity is relatively large, it is necessary to perform the treatment in a sufficient safety facility.

In the case of the above cyclization treatment, a concentrated sulfuric acid solution is used as a cyclization treatment solution, and the surface of the rubber vibration insulator is immersed or coated in the cyclization treatment solution at room temperature for 2 to 20 minutes. The attached concentrated sulfuric acid is washed away with water.

In the case of the above-mentioned methylene iodide treatment, methylene iodide is dissolved in an appropriate solvent to form 0.1 to 10%
To a methylene iodide-treated solution, and this solution is applied to the surface of the rubber vibration insulator.

Further, in the case of the plasma treatment, a low-temperature plasma of 100 to 60,000 Wsec / l is irradiated on the surface of the rubber vibration insulator.

The metal / rubber composite vibration isolator is manufactured by, for example, a base treatment of a metal fitting (alkali degreasing → water washing → hot water washing → drying).
After that, an organic silane treatment with a silane coupling agent is performed, and then a thermosetting adhesive is applied to the surface of the organic silane compound film and dried, while an activation treatment is performed on the surface of the vibration-proof rubber body. An isocyanate-based adhesive is applied to the activation-treated surface, and the thermosetting adhesive layer of the metal fitting is superimposed on and bonded to the adhesive layer. In the above-mentioned organic silane treatment, immersion of a metal fitting in a silane coupling agent solution, brush coating or spray coating of the solution with the metal fitting can be adopted.

[0022]

Thus, according to the present invention, an organic silane compound film is formed on the surface of the metal fitting by the silane coupling agent, and the surface of the organic silane compound film adhered to the vibration-proof rubber body is heat-curable. An adhesive cured layer formed by heat curing of the adhesive is formed, and the activated surface of the vibration-proof rubber body is bonded to the cured adhesive layer with an isocyanate-based adhesive. Without complicating the process and without causing a problem of pollution, the corrosion resistance of the metal fitting is obtained, and the adhesive stability of the adhesive layer to the metal fitting surface is obtained. It is possible to maintain strong adhesion between the metal fitting and the vibration-proof rubber body for a long period of time.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Prior to the embodiment of the present invention, a reference example will be described.

<Reference Example> FIG. 1 shows a metal / rubber composite vibration isolator (engine mount of an automobile) according to a reference example of the present invention. In FIG. 1, reference numeral 1 denotes a cylindrical anti-vibration rubber body, and reference numerals 2 and 2 denote aluminum alloy fittings bonded to both ends of the anti-vibration rubber body 1. An organic silane compound film made of a silane coupling agent is formed on the entire surface of the metal fitting 2. As shown in FIG. 2, the vibration-proof rubber body 1 is simultaneously applied to the surface of the organic silane compound film 3 of the metal fitting 2. They are bonded via a lower layer 4 and an upper layer 5 made of a sulfur type adhesive.

The lower layer 4 is made of a phenol resin-based primer adhesive, and the upper layer 5 is made of a chlorinated rubber-based adhesive containing chlorosulfonated polyethylene as a main component.

The production of the above-mentioned metal / rubber composite vibration insulator was carried out by the following steps.

-Base treatment of metal fitting 2-Base treatment of metal fitting 2 was performed in the following order.

Alkaline degreasing (70-80 ° C. × 5 minutes) →
Rinse (1 minute) → Rinse (1 minute) → Rinse (60-70 ° C)
× 1 minute) → Drying (100 ° C. × 20 minutes) -Organic silane treatment- By immersing the undercoated metal fitting 2 in a silane coupling agent solution, an organic silane compound film 3 was formed on the surface of the metal fitting 2. . The composition of the silane coupling agent solution is as follows.

Alcohol 1 liter Silane coupling agent 20 ml Water 10 ml The immersion condition was room temperature for 30 minutes, and the drying condition after immersion was 100 ° C. × 20 minutes.

-Adhesive application- The phenolic resin-based primer adhesive is applied to the surface of the organic silane compound film 3 to be bonded to the vibration-proof rubber body 1, and after this is dried, the chlorinated rubber-based adhesive is applied. And dried. The drying conditions are all 70 ° C. × 5 minutes.

-Vulcanized Adhesive- The metal fitting 2 coated with the above adhesive is put into a vulcanizing mold, and the unvulcanized rubber for the vibration isolating rubber body 1 is injected, and then heated to heat the vibration isolating rubber body 1. Was vulcanized and bonded to the metal fitting 2.

(Test) The following test was performed to confirm the effect of the above reference example.

-Specimens-Specimens were prepared for each of Reference Examples a to d and Comparative Examples a to c in accordance with Section 8.3.1 of JIS K6301. The composition of the rubber part corresponding to the vibration-proof rubber body 1 in each test piece is as shown in Table 1.

[0034]

[Table 1]

The material of the metal part corresponding to the metal fitting 2 in each of the test pieces of Reference Examples a to d is aluminum alloy (JIS
A5052, 6063 or 7 in H4000
003), and γAPS is used as the silane coupling agent.
(Γ-aminopropyltriethoxysilane) or γMP
S (γ-methacryloxypropyltrimethoxysilane)
Was used. That is, in Reference Examples a to d, the material of the metal part or the type of the silane coupling agent was different from each other, and these are listed in Table 2. In Comparative Examples a to c, only the chromate treatment or the above-described base treatment was performed instead of the organosilane treatment. Also in this comparative example, the material of each metal part and the aspect of the metal surface treatment are listed in Table 2.

For each of the test pieces of the reference example and the comparative example, Chemlock 205 (trade name, manufactured by US Road Co., Ltd.) was used as a phenolic resin-based primer adhesive for the lower layer 4.
As the chlorinated rubber-based adhesive for the upper layer 5, Chemlock 252 (trade name, manufactured by Road Co., USA) was used.

-Contents of Test- Each of the above test pieces was subjected to a 90 degree peel test based on 8.3 of JIS K6301. The peel test was performed in combination with a salt spray test (SST) according to JISZ2371. That is, the peel test was carried out at the initial stage (without salt spray), 600 hours after salt spray, 720 hours after salt spray, and 1000 hours after the salt spray.

-Test results- The test results are shown in Table 2. In the same table, the meaning of each symbol of R-RC-CP-M in the item of the peeled state is as follows.

R: Breakage of rubber part RC: Breakage between rubber part and adhesive CP: Breakage of adhesive part M: Breakage between metal and adhesive

[0040]

[Table 2]

According to Table 2, Reference Examples a to d and Comparative Examples a and
With respect to b, there is hardly any difference in the peeling resistance including the breakage (M) between the metal and the adhesive. In Reference Examples a to d, no harmful white rust was generated on the metal part. From this, when the organosilane compound film 3 is formed on the surface of the metal fitting 2 by the silane coupling agent as in the present invention, the same corrosion resistance and adhesion stability as those obtained by the conventional chromate treatment can be obtained. It is understood that it is possible.

Example Next, an example of the present invention will be described.

The metal / rubber composite vibration isolator of this embodiment is a cylindrical bush and is shown in FIGS. In the figure, reference numeral 21 denotes a cylindrical vibration-proof rubber body, and reference numeral 22 denotes a vibration-proof rubber body 21.
Aluminum alloy inner tube fitting adhered to the inner peripheral surface of the
Reference numeral 23 denotes an aluminum alloy outer metal fitting adhered to the outer peripheral surface of the vibration-proof rubber body 21. The same vulcanization bonding as that of the reference example is employed for bonding the inner cylinder fitting 22 to the vibration-proof rubber body 21.

On the other hand, an organic silane compound film made of a silane coupling agent is formed on the entire surface of the outer sleeve 23, and as shown in FIG.
A lower layer 25 and an upper layer 26 formed by thermosetting a thermosetting (simultaneously vulcanizing) adhesive on the surface of the surface 4 which is bonded to the vibration-proof rubber body 21 are formed. In addition, the vibration isolating rubber body 2
A predetermined surface activation treatment has been applied to the outer peripheral surface of 1.
Thus, the surface of the vibration-proof rubber body 21 that has been subjected to the surface activation treatment is adhered to the adhesive cured layer 26 of the outer tube fitting 23 by the isocyanate-based adhesive layer 27.

The bonding between the vibration-proof rubber body 21 and the outer sleeve 23 was carried out by the following steps.

The base treatment and the organic silane treatment of the outer shell 23 were performed in the same manner as in the reference example.

-Formation of a cured adhesive layer- The above-mentioned Chemlock 205 is applied as a lower layer 25 to the surface (inner peripheral surface) of the organic silane compound film 24 of the outer cylindrical metal member 23 which adheres to the vibration-proof rubber member 21 and dried. After, upper layer 2
As No. 6, Chemlock 220 (chlorinated rubber-based adhesive) manufactured by US Road Co., Ltd. was applied and dried. The drying conditions are all 70 ° C. × 5 minutes. Then, these adhesives were thermally cured at 150 ° C. for 20 minutes to form the cured adhesive layers 25 and 26.

-Surface Activation Treatment- After the outer peripheral surface of the vibration-isolating rubber body 21 is degreased with a solvent, a 3% solution of trichloroisocyanuric acid (a diluent is an organic solvent) is applied to the outer peripheral surface. Was activated.

-Adhesion- After an isocyanate-based adhesive is applied to the outer peripheral surface of the vibration-proof rubber body 21, the vibration-proof rubber body 21 is press-fitted into the cylindrical hole of the outer cylinder 23 and compressed radially inward. The isocyanate-based adhesive was cured under a heating condition of 120 ° C. for 20 minutes while the elastic restoring force of the rubber was applied. As a result, the isocyanate-based adhesive layer 27 was formed, and the vibration-proof rubber body 21 and the outer sleeve 23 were integrated.

(Test) The following test was conducted to confirm the effects of the above embodiment.

-Test piece-The test piece is the above-mentioned cylindrical bush, and was prepared for each of Examples e and f and Comparative examples d and e according to the method described above. Table 1 shows the rubber composition of the vibration-isolating rubber body in each test piece
The material of the metal fittings 22 and 23 is an aluminum alloy (A5052 in JIS H4000). For the silane coupling agent, the above-mentioned γA
PS was used, and γMPS was used in Example f. Comparative example d
Was subjected to a chromate treatment instead of the organosilane treatment, and Comparative Example e was subjected to only the above-described undercoat treatment.

Each of the test pieces of the above Examples and Comparative Examples was provided with the above Chemlock 2 for the adhesive cured layers 25 and 26.
No. 05 and No. 220 were used, and a urethane bond was used as an isocyanate adhesive.

-Contents of test- For each of the above test pieces, the outer cylinder 23 is held, and an axial load is applied to the anti-vibration rubber body 21 and the inner cylinder 22 to punch them out. The test was performed.
The punching test was also performed in combination with the salt spray test similarly to the test in the reference example.

-Test results- The test results are shown in Table 3. In the same table, the meaning of each symbol in the item of the peeled state is the same as in the case of Table 2.

[0055]

[Table 3]

According to Table 3, in Examples e and f and Comparative example d, in both the breaking load and the breaking state,
Almost no difference is observed. In Examples e and f, no harmful white rust was generated on the metal part. This confirms the usefulness of the present invention.

In particular, instead of directly bonding the vibration-isolating rubber body 21 to the surface of the aluminum alloy fitting 23 with an isocyanate-based adhesive, an organic silane compound film 24 and thermally cured adhesive cured layers 25 and 26 are used. Since the isocyanate-based adhesive is applied after covering the ground, the anti-vibration rubber body 21 as a vulcanized rubber is firmly bonded without performing chromate treatment or cationic electrodeposition on the metal fitting. Is what you can do.

In this case, the organic silane compound film 24
23 made of inorganic material and phenolic adhesive cured layer 2
5 to form a bridge between them, and between the phenol-based adhesive cured layer 25 and the chlorinated rubber-based adhesive cured layer 26, and between the chlorinated rubber-based adhesive cured layer 26 and the isocyanate-based adhesive layer 27. , And isocyanate-based adhesive layer 2
Since a strong connection is obtained between the metal member 7 and the activation-treated surface of the vibration-proof rubber body 21, it is recognized that the metal fitting 23 and the vibration-proof rubber body 21 are firmly connected as a result.

The method of manufacturing the vibration isolator described in the above embodiment is merely an example, and the conditions of each step can be appropriately changed according to the material of the metal fittings, the type of the adhesive used, and the like. is there.

In the above embodiment, the isocyanate-based adhesive may be applied to the metal fitting, or may be applied to both the metal fitting and the vibration-proof rubber body.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing a vibration isolator of a reference example.

FIG. 2 is a cross-sectional view of a bonding portion of a vibration isolator according to a reference example.

FIG. 3 is an exploded sectional view of the vibration isolator of the embodiment.

FIG. 4 is a sectional view of a bonding portion of the vibration isolator according to the embodiment.

[Explanation of symbols]

 1,21 Anti-vibration rubber body 2,22,23 Metal fittings 3,24 Organosilane compound film 4,5 Simultaneous vulcanization type adhesive layer 25,26 Adhesive cured layer 27 Isocyanate adhesive layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 5/12 F16F 15/00-15/36

Claims (1)

(57) [Claims] 1. A metal / rubber composite vibration isolator having a metal member adhered to a vibration-isolating rubber member exhibiting a vibration-proof action, wherein an organic silane compound film is formed on a surface of the metal member by a silane coupling agent. In addition, an adhesive cured layer formed by thermosetting a thermosetting adhesive is formed on the surface of the organosilane compound film bonded to the vibration-proof rubber body, and the adhesive cured layer of the metal fitting is formed on the adhesive cured layer of the metal fitting. A metal / rubber composite vibration isolator, wherein the surface of the vibration isolating rubber body that has been subjected to the surface activation treatment is adhered with an isocyanate-based adhesive.