JP2003148537A - Rubber vibration isolator member for automobile and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber vibration isolator member having an adhesive strength similar to or more than the conventional one, including no lead compound, and capable of responding to the demand of cost reduction and to provide its manufacturing method. SOLUTION: This rubber vibration isolator member for an automobile is so formed that, at least, two highly rigid support members are stuck together by adhesive via a rubber member. The adhesive is composed of a first adhesive layer to be stuck to the highly rigid support member surface and a second adhesive layer to be stuck to the rubber member surface. The second adhesive layer includes, at least, one of chlorinated polyolefin or chlorinated rubber as a resin component, includes no lead, and includes magnesium compound of 4-10 as a magnesium weight by letting the carbon weight of adhesive solid to 100. It is preferable that the second adhesive layer includes brominated rubber as the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-vibration rubber member for automobiles such as a rubber bush, an engine mount including a liquid ring mount, a body mount and the like, and a manufacturing method thereof.
INDUSTRIAL APPLICABILITY The present invention is particularly suitable for a rubber bush that is required to be low in cost.

[0002]

2. Description of the Related Art An anti-vibration rubber member made of at least two high-rigidity supporting members made of steel, aluminum, glass fiber reinforced resin, etc., which are interposed by bonding a vulcanized rubber member between them, is As is, it is widely used as an anti-vibration rubber member for automobiles in the form of being integrally assembled with other members in a liquid seal mount or the like.

Such an anti-vibration rubber member for automobiles is generally composed of polychloroprene as a main component after blasting the surface of a steel material constituting a metal fitting necessary for mounting on a vehicle body and optionally performing chemical conversion treatment. An undercoat layer containing chlorosulfonated polyethylene as a main component is applied to the undercoat layer after drying and then dried, and a chlorinated rubber is used for applications requiring lower cost than the heat resistance. To an overcoat layer containing chlorinated polyolefin as a main component, then dried, a high-rigidity support member having the at least two adhesive layers is disposed in a mold, and an unvulcanized rubber composition is injected. It is manufactured by the so-called vulcanization bonding method, in which it is cured and then bonded.

A large amount of a lead compound is added as a stabilizer to the above-mentioned known second adhesive.

[0005]

The anti-vibration rubber member for automobiles, particularly the rubber bush, is subject to compressive vibration due to vibration during traveling, vibration due to engine rotation, etc.
The rubber itself generates heat. Therefore, in addition to the adhesive strength in a room temperature environment, it is required to have a high durable adhesive strength in a high temperature environment to some extent, and at the same time, it is strongly required to be low cost, and an adhesive is also required to be low cost. To be

On the other hand, a vibration-proof rubber member which does not contain lead has been demanded due to environmental problems. However, when a lead-free adhesive is simply used as the conventional adhesive, the heat-resistant adhesive strength is lowered. there were.

An object of the present invention is to provide an anti-vibration rubber member for automobiles which has adhesive strength equal to or higher than conventional ones, does not contain a lead compound, and can meet the demand for cost reduction, and a manufacturing method thereof. To do.

[0008]

The present invention comprises at least two aspects.
A high-rigidity support member is an automobile anti-vibration rubber member adhered with an adhesive via a rubber member, wherein the adhesive is
It comprises a first adhesive layer that adheres to the high-rigidity support member surface and a second adhesive layer that adheres to the rubber member surface, and the second adhesive layer contains at least one of chlorinated polyolefin and chlorinated rubber as a resin component. It is characterized in that it contains 4 to 10 as a magnesium weight of magnesium compound based on 100 carbon weight of the adhesive solid content without containing lead.

The vibration-damping rubber member for automobiles having such a structure is a vibration-damping rubber member for automobiles that has adhesive strength equal to or higher than that of conventional ones, does not contain a lead compound, and can meet the demand for cost reduction. is there.

In the above-mentioned vibration-damping rubber member for automobiles, the second adhesive layer further contains a bromine-containing rubber, and chlorine and bromine in the solid content are Cl / Br = 4 to 9 (weight ratio).
Is preferred.

By using the brominated polybutadiene rubber in combination,
An anti-vibration rubber member for automobiles having a better adhesive force between rubber and a highly rigid support member can be obtained.

Further, the present invention is a method for manufacturing an anti-vibration rubber member for an automobile, in which at least two high-rigidity supporting members are adhered to each other with an adhesive via a rubber member. A first adhesive applying step of applying an adhesive, a second adhesive applying step of applying a second adhesive on the first adhesive layer, and disposing the high-rigidity support member in a mold, A vulcanization step of injecting vulcanized rubber into the mold cavity, adhering it to a high-rigidity support member, and curing it to form a vibration-proof rubber member,
The second adhesive contains at least one of a chlorinated polyolefin and a chlorinated rubber as a resin component, does not contain lead, and contains 4 to 10 of a magnesium compound as a magnesium weight with respect to 100 carbon weight of the solid content of the adhesive. It is characterized by

By the manufacturing method having such a constitution, it is possible to obtain an anti-vibration rubber member for an automobile which has an adhesive strength equal to or higher than the conventional one, does not contain a lead compound, and can meet the demand for cost reduction. .

In the above-mentioned method for manufacturing a vibration-damping rubber member for automobiles, the second adhesive further contains a bromine-containing rubber, and chlorine and bromine in the solid content are Cl / Br = 4-9.
(Weight ratio) is preferable.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As the material used as the high-rigidity support member in the present invention, known materials used for automobile vibration-proof rubber members can be used without limitation. Specific examples include steel materials, metal materials such as stainless steel and aluminum, and high-rigidity thermoplastic resins. Examples of the high-rigidity thermoplastic resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polycarbonate resins,
Examples thereof include polyphenylene sulfide and polyphenylene oxide. It is also preferable that a reinforcing material such as glass fiber, carbon fiber, metal fiber or whisker is used in combination with the high-rigidity thermoplastic resin.

The rubber member constituting the vibration isolating rubber member of the present invention is a rubber material known as a vibration isolating rubber material for automobiles,
It can be used without limitation. Specifically, natural rubber (N
R), styrene butadiene rubber (SBR), butadiene rubber (BR), ethylene propylene rubber (EPDM),
Chloroprene rubber (CR), isoprene rubber (II
R), butyl rubber, halogenated butyl rubber, etc. are exemplified, and these rubber materials may be used alone, or 2
You may use together 1 or more types. When using a vibration-proof rubber member with excellent heat resistance, natural rubber / butadiene rubber = 60/4
It is preferable to use a raw material rubber having a composition of 0 to 100/0, and it is also preferable to use at least one of natural rubber, styrene-butadiene rubber and butadiene rubber in combination.

In particular, when natural rubber and butadiene rubber are used in combination within the above range, the dynamic spring value in the vibration-damping property can be reduced, and at the same time the adhesive strength can be increased, which is preferable.

The above raw material rubber is kneaded with a filler such as carbon black, process oil, zinc oxide and silica, a cross-linking agent such as sulfur, a vulcanization accelerator and an antioxidant according to a conventional method. As an unvulcanized rubber composition, it is used for forming a rubber member of an anti-vibration rubber member for automobiles.

As the vulcanization accelerator, known vulcanization accelerators can be used without limitation, but N-cyclohexyl-2-
Benzothiazolylsulfenamide (Noccellar CZ,
Ouchi Shinko Chemical Industry Co., Ltd., Nt-butyl-2-benzothiazolyl sulfenamide (Nocceller NS, Ouchi Shinko Chemical Industry Co., Ltd.), and other sulfenamide vulcanization accelerators, tetramethylthiuram disulfide (Noccellar TT, Suitable examples include thiuram-based vulcanization accelerators such as Ouchi Shinko Chemical Industry Co., Ltd.) and tetramethylthiuram monosulfide (Nocceller TS, Ouchi Shinko Chemical Industry Co., Ltd.). The vulcanization accelerator is
They may be used alone or in combination of two or more.

As the anti-aging agent, known anti-aging agents can be used without limitation, and they are appropriately selected and used according to the purpose. Specifically, N- (1,3-dimethylbutyl)-
N'-phenyl-p-phenylenediamine (Nocrac 6C, Ouchi Shinko Chemical Industry Co., Ltd.), N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine (Ozonone 35, Seiko Kagaku), etc. are exemplified. . Anti-aging agent,
They may be used alone or in combination of two or more.

As the adhesive, a first adhesive applied to the surface of the high-rigidity support member and a second adhesive applied on the first adhesive and adhered to rubber are used.

As the resin constituting the first adhesive, a solution type adhesive containing polychloroprene as a main component is used. If necessary, a metal oxide such as zinc oxide or magnesium oxide is added to the first adhesive. As the first adhesive, use of a commercially available product is also suitable, and MEGUM 3270, MEGU
M 3276, MEGUM 3351 (CHEMTAL
L company) and the like are exemplified.

Also as the first adhesive, it is preferable to use one containing no harmful heavy metal such as lead.

The thickness of the first adhesive layer after drying is 1 to 20.
The thickness is preferably μm, more preferably 3 to 10 μm.

As the resin constituting the second adhesive, at least one selected from chlorinated polyolefin and chlorinated rubber is used. Chlorinated polyolefin is a known polyolefin,
For example, it is produced by chlorinating polyethylene, polypropylene, an ethylene / propylene copolymer, an ethylene / propylene / diene copolymer or the like by a method of contacting with chlorine. Chlorinated polyolefin has a chlorine content of 6
It is preferably 5 to 75% by weight. The molecular weight is 1
It is preferably about 000 to 7,000.

The content of the magnesium compound in the second adhesive layer is more preferably 6 to 9 in terms of the weight of the magnesium compound relative to 100 of the carbon weight of the adhesive solid content.

The magnesium compound contained in the second adhesive component is added in the form of, for example, an inorganic compound such as magnesium oxide or magnesium hydroxide or an organic acid salt such as magnesium acetate.

Examples of preferable bromine-containing rubber preferably added to the second adhesive layer include brominated polybutadiene, brominated butyl rubber, and brominated poly (1,3-dichloro-1,3-butadiene). To be done.

It is preferable to add a vulcanization accelerator to the second adhesive in order to strengthen the adhesion with the rubber. Commercial products suitable for use as the second adhesive include MEGUM 1
22J (manufactured by CHEMTAL) and the like are exemplified.

The thickness of the second adhesive layer after drying is 5 to 50.
The thickness is preferably μm, more preferably 10 to 30 μm, still more preferably 15 to 25 μm.

The thickness of each of the first adhesive and the second adhesive is appropriately selected depending on the combination of the adhesive material used, the high-rigidity support member constituent material, the rubber member constituent material, and the like. The thickness is also set to the optimum thickness. If the thickness of the adhesive layer is too thin, sufficient adhesive strength may not be obtained, and if it is too thick, the adhesive strength does not change and the cost increases.

As described above, the method of manufacturing the anti-vibration rubber member according to the present invention comprises the first adhesive applying step of applying the first adhesive to the surface of the highly rigid supporting member, and the second adhesive applying step on the first adhesive layer. Second step of applying an adhesive, in which the high-rigidity support member is disposed in a mold, and unvulcanized rubber is injected into the mold cavity to adhere and cure the high-rigidity support member. And a vulcanization step of forming an anti-vibration rubber member.

The high-rigidity support member made of a metal material is subjected to a pretreatment including known degreasing such as blast treatment on at least the adhesive surface, and then the first adhesive is applied and dried. First
The second adhesive is applied onto the dried film of the adhesive and dried to form two adhesive layers on the surface of the high-rigidity support member that is adhered to the rubber member.

The high-rigidity support member having the adhesive layer is placed in a mold forming a cavity having a predetermined shape, and an unvulcanized rubber composition is injected and cured to form a rubber member. The high-rigidity support member is bonded to form a vibration-proof rubber member. The method of injecting the unvulcanized rubber into the mold is a well-known method such as an injection molding method or a transfer molding method.

The obtained anti-vibration rubber member can be mounted on a vehicle as an anti-vibration rubber member for automobiles as it is, such as a rubber bush, and can be used as a component member such as a liquid-sealed mount or the like in combination with other members. An ethylene glycol / water-based liquid or the like may be enclosed and integrated to be used as an anti-vibration rubber member for automobiles.

FIG. 1 shows an example of a rubber bush which is a vibration-proof rubber member for an automobile of the present invention. 1A is a perspective view, FIG. 1B is a vertical side view, and FIG. 1C is an enlarged view of a P portion of FIG. 1B. The double cylindrical rubber bush 30 includes a metal outer cylinder 24 and a metal inner cylinder 12, which are high-rigidity support members.
And an anti-vibration rubber member 16 interposed therebetween.

A first adhesive layer 15 and a second adhesive layer 14 are formed between the metal outer cylinder and the inner anti-vibration rubber member. A similar adhesive layer is formed on the outer surface of the metal inner cylinder, but it is omitted in the figure.

[0038]

EXAMPLES Examples and the like specifically showing the constitution and effects of the present invention will be described below. The evaluation was performed using both the adhesion test piece and the actual product as evaluation samples.

As a real product, a double cylindrical rubber bush 30 having the shape shown in FIG. 1 was prepared and the adhesive strength was measured. The outer cylinder and the inner cylinder, which are high-rigidity support members, are both made of steel, and the outer cylinder has an outer diameter of 40 mm and a length of 32 mm.
The thickness is 2.5 mm, the inner cylinder has an outer diameter of 20 mm, a length of 40 mm, and a thickness of 3 mm.

Adhesion Test The test piece is shown in FIG. 3 as mounted on a measuring jig. Adhesion test test piece 1
Is made of steel, and includes metal fittings 3 and 5 having bolts 36 and 37, and a rubber member 7. Metal fittings 3,
A first adhesive layer and a second adhesive layer are formed on the respective adhesive surfaces 10 and 11 of 5 from the metal fitting surface side.

In all of the evaluation samples, the surface of the metal fitting that was bonded to the rubber was subjected to shot blasting, and the first bonded surface
MEGUM 3270 was applied as an adhesive so that the thickness after drying was 8 μm, and dried at 80 ° C. for 10 minutes.

After the first adhesive is dried, the second adhesive is applied so that the thickness after drying is 15 μm, and the mixture is dried at 80 ° C. for 1 hour.
Dry for 0 minutes.

As the unvulcanized rubber composition for forming the rubber member, the composition having the composition shown in Table 1 below was used.

[0044]

[Table 1] The raw materials were kneaded by a conventional method, formed into a ribbon, and subjected to injection molding.

The manufacturers or suppliers of the raw materials used are as follows. BR: Buna CB22 (Bayer) Carbon black: Niteron # 10S (Shin Nikka Carbon Co., Ltd.) As the second adhesive, in Examples 1 and 3 and Comparative Examples 1 and 2, chlorinated polyethylene was used as a resin component and magnesium was used. An adhesive prepared by adding a predetermined amount of the compound was used, and in Example 2, MEGUM 122J was used for evaluation. Table 2 shows the amount of Mg in each adhesive solid,
The content ratio of Cl and Br is shown as a weight ratio with carbon as 100.

Elemental analysis is performed by a scanning electron microscope JEOL equipped with an energy dispersive X-ray microanalyzer Phoenix / Falcon (manufactured by Edax Japan).
It was performed using JSM-T330A (manufactured by JEOL Ltd.). Lead (Pb) was not detected in any of the adhesives.

[0047]

[Table 2] <Evaluation> FIG. 2 shows the evaluation method of the rubber bush of the actual product, and FIG. 3 shows the evaluation method of the adhesion test piece. The actual rubber bush was heated in an oven at 80 ° C. for 240 hours, taken out, cooled, and measured. The adhesion test piece is 20%
Heat in the oven for 240 hours in the stretched state,
The measurement was performed after taking out and cooling.

In the evaluation of the actual product shown in FIG. 2, the jig 40 holding the sample is moved in the X direction and the lower jig 42 is moved in the opposite downward direction Y, and shear stress is applied between the rubber and the metal fitting. And the strength at which the bond breaks was measured. Actually, the lower jig is fixed and the upper jig 40 is moved upward by 100 mm / s.
It was moved by ec. The measurement was performed at n = 4. Similarly, for the adhesion test piece, the peel strength was measured by moving the upper and lower jigs in the opposite directions as indicated by the arrows. The test piece was evaluated according to JIS K6301. The measurement was performed at n = 4.

<Results> 1) Evaluation Results of Adhesion Test Test Pieces With respect to the adhesion test test pieces, the average value of the measurements of n = 4 samples was obtained. Among the adhesives for automobile rubber bushes, the adhesive strength required for the adhesion test piece is 10 MPa or more and R = 100, and those satisfying this requirement are ○, those satisfying this requirement but having no margin are Δ,
Those not filled were marked with x. R = 100 indicates 100% of the rubber material destruction, and RC indicates the ratio (%) of the rubber material destruction and the peeling of the adhesive interface, of which the rubber material destruction occurs. The evaluation results are shown in Table 3.

2) Evaluation result of actual product For the actual product sample, the average value of the measurement of n = 4 was obtained. The adhesive strength required for the actual product is 1200 kg or more and R = 100, and those satisfying this requirement are ○, those satisfying this requirement but having no margin are △, and those not satisfying are ×.
And When R = 100, the rubber material is 100% broken,
In RC, destruction of the rubber material and peeling of the adhesive interface occur,
The ratio (%) in which the rubber material is broken is shown. The evaluation results are shown in Table 3.

[0051]

[Table 3] From the results in Table 3, it is understood that the adhesive strength of the rubber bush using the second adhesive of the present invention satisfies the numerical values required for actual products. Further, it is understood that the blending amount of sulfur of rubber also affects the adhesive strength, and that the blending amount of sulfur is preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the rubber material.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a rubber bush.

FIG. 2 is a diagram showing a method for evaluating adhesion of a rubber bush.

FIG. 3 is a diagram showing an evaluation method of an adhesion test piece.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F16F 15/08 F16F 15/08 K // C08L 21:00 C08L 21:00 F term (reference) 3J048 AA01 BA19 EA01 EA15 3J059 AD04 AD06 AE05 BA42 BA54 BB01 BC06 BD01 CA14 CB15 EA06 EA13 GA07 4F071 AA11B AA12B AA13A AA71B AA79A AB03B AB04B AB11CA AB08 CA01 CA08A CAB06CA08A05B58A58B58A58B58A58J AF58A AF05B AF20A AF45B AF20A AF45B AF20A AF45B AF20A AF45B AF20A AF45B

Claims (4)

[Claims] 1. An anti-vibration rubber member for an automobile, wherein at least two high-rigidity support members are bonded by an adhesive through a rubber member, wherein the adhesive adheres to the high-rigidity support member surface. 1 adhesive layer and a second adhesive layer adhered to the rubber member surface, the second adhesive layer contains at least one of chlorinated polyolefin and chlorinated rubber as a resin component, does not contain lead, An anti-vibration rubber member for an automobile, characterized by containing 4 to 10 of a magnesium compound in terms of magnesium weight based on 100 carbon weight of solid content. 2. The second adhesive layer further contains a bromine-containing rubber, wherein chlorine and bromine in the solid content are Cl / Br =
The antivibration rubber member for an automobile according to claim 1, which has a weight ratio of 4 to 9. 3. A method of manufacturing an anti-vibration rubber member for an automobile, wherein at least two high-rigidity support members are bonded with a rubber member with an adhesive, wherein the high-rigidity support member has a first adhesive on its surface. A first adhesive applying step of applying, a second adhesive applying step of applying a second adhesive on the first adhesive layer, the high-rigidity supporting member is disposed in a mold, and unvulcanized rubber A vulcanization step of injecting into a mold cavity to bond with a high-rigidity support member and curing to form a vibration-proof rubber member, wherein the second adhesive is at least one of chlorinated polyolefin and chlorinated rubber. Is contained as a resin component and does not contain lead, and a magnesium compound is added as a magnesium weight of 4 to 1 with respect to 100 carbon weight of the solid adhesive.
0 is contained, The manufacturing method of the vibration-proof rubber member for motor vehicles characterized by the above-mentioned. 4. The second adhesive further contains a bromine-containing rubber, and chlorine and bromine in the solid content are Cl / Br = 4.
The manufacturing method of the anti-vibration rubber member for automobiles according to claim 3, wherein the vibration-damping rubber member is 9 to 9 (weight ratio).