JP2001260171A - Method for preparing rubber vibration insulator, and rubber vibration insulator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a rubber vibration insulator which is prepared by bonding highly strongly a vulcanized rubber member and a rigid member formed of a fiber-reinforced thermoplastic resin reinforced with an inorganic staple fiber. SOLUTION: The rubber vibration insulator consists of the first rigid member 3 consisting of the fiber-reinforced thermoplastic resin containing 30-60 pts.wt. inorganic staple fiber, the second rigid member 4 and a vulcanized rubber member 5 provided between the first rigid member 3 and the second rigid member 4 and the method for preparing the rubber vibration insulator 1 with a vulcanized rubber member molding process for molding the vulcanized rubber member in advance, an adhesive layer forming process for providing vulcanized adhesive layers 13 and 15 containing CSM as a main ingredient on the adhesion layers of the vulcanized rubber member and a resin injection process wherein the fiber-reinforced thermoplastic resin under molten state is injected into a rigid member forming cavity to form the first and second rigid members 3 and 4 and to adhere them with the arranged vulcanized rubber member 5 without preheating is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a vibration-proof rubber member which is a composite in which a vulcanized rubber member and a rigid resin member formed of a fiber-reinforced thermoplastic resin are bonded with high strength. The present invention relates to an anti-vibration rubber member.

[0002]

2. Description of the Related Art A vulcanized rubber, in which a vulcanized rubber member used for an automobile suspension, a machine suspension, and the like, and a resin molded body formed of a highly rigid resin material are integrated.
As a method for producing a thermoplastic resin composite, Japanese Patent Publication No.
The technique described in Japanese Patent No. 5510 is known.

[0003] The technique described in the above publication is that a surface of a vulcanized rubber member is chlorinated, and a vulcanized adhesive mainly composed of an aldehyde-modified resol type phenol resin and polyvinyl alcohol is applied to the chlorinated surface. Forming a layer, disposing it in a mold, injecting a heated and melted thermoplastic resin to produce a vulcanized rubber / thermoplastic resin composite, and chlorosulfonated polyethylene on the surface of the vulcanized rubber member Discloses a method for producing a vulcanized rubber-thermoplastic resin composite by forming a vulcanized adhesive layer containing as a main component, and injecting a heated and melted thermoplastic resin in a state where a vulcanized rubber member is heated. Have been.

[0004]

However, in order to increase the physical strength of the thermoplastic resin, when the inorganic short fibers are added to the thermoplastic resin to such an extent that the reinforcing property to the resin is sufficiently exhibited, the above-mentioned problem is caused. According to the known technique, there is a case where a sufficient adhesive strength between the rubber molded body and the fiber-reinforced thermoplastic resin molded body cannot be obtained.

An object of the present invention is to bond a vulcanized rubber member with a rigid resin member formed of a fiber-reinforced thermoplastic resin reinforced with inorganic short fibers, particularly glass fibers, with high strength, especially An object of the present invention is to provide a method of manufacturing a vibration-proof rubber member having practical adhesive strength as a vibration-proof rubber member for automobiles, and a vibration-proof rubber member manufactured by the manufacturing method.

[0006]

The present invention comprises a first rigid member, a second rigid member, and a vulcanized rubber member provided between the first rigid member and the second rigid member. Wherein at least one of the first rigid member and the second rigid member comprises inorganic short fibers of 30 to 60.
A method for producing a vibration-proof rubber member, which is a rigid resin member made of a fiber-reinforced thermoplastic resin containing parts by weight, and comprising the following steps (1) to (3).

(1) A vulcanized rubber member forming step of vulcanizing and molding the vulcanized rubber member in advance. (2) An adhesive layer forming step of providing a vulcanized adhesive layer containing chlorosulfonated polyethylene as a main component on an adhesive surface of the vulcanized rubber member with the fiber-reinforced thermoplastic resin. (3) disposing the surface-treated rubber member without preheating in the surface-treated rubber member accommodating cavity of a mold having a cavity for accommodating a surface-treated rubber member and a cavity for forming a rigid resin member; A resin injecting step of injecting a fiber reinforced thermoplastic resin into the member forming cavity in a molten state to form the rigid resin member.

[0008] Even when the structural member is made of a fiber-reinforced thermoplastic resin having high rigidity by adding inorganic fibers by the above structure, the vulcanized rubber and the thermoplastic resin are practically used as a vibration damping member for automobiles. An anti-vibration rubber member having an adhesive strength to a structural member made of a plastic material is obtained. When the vulcanized rubber member is preheated, plasticizer, process oil, etc. bleed on the surface of the vulcanized rubber member,
Although the adhesive strength is reduced, it is considered that such a problem can be avoided in the present invention, and the adhesive strength between the rigid resin member and the vulcanized rubber member is improved.

[0009] The first rigid member and the second rigid member are mounted on the apparatus as structural members. At least one of them may be a fiber-reinforced thermoplastic resin, and the other may be a metal material. Both can be made of fiber reinforced thermoplastic resin, further reducing the weight of the vibration-isolating rubber member as a whole,
Further, the manufacturing process is simplified, which is more preferable.

In the above-mentioned manufacturing method, the step of forming the adhesive layer comprises: (2 ') a vulcanization process comprising a chlorosulfonated polyethylene as a main component on the surface of the vulcanized rubber member bonded to the fiber-reinforced thermoplastic resin. After providing the adhesive layer, the surface of the vulcanized adhesive layer is treated with a coupling agent, or the chlorosulfonated polyethylene is used as a main component on the bonding surface of the vulcanized rubber member with the fiber-reinforced thermoplastic resin. An adhesive layer forming step of providing a vulcanized adhesive layer to which a coupling agent has been added. It is preferred that

With the above structure, even when the structural member is made of a fiber-reinforced thermoplastic resin having a high rigidity by adding inorganic fibers, the vibration-proof rubber having more excellent adhesive strength with the vulcanized rubber member. A member is obtained.

In the above-mentioned production method, it is preferable that the coupling agent is a silane coupling agent since particularly excellent adhesive strength can be obtained.

When a metal member is used as the rigid member, the metal rigid member is bonded to a vulcanized rubber molded body in advance and used as a composite member.

A vibration-proof rubber member according to the present invention is manufactured by the manufacturing method according to any one of claims 1 to 3.

In the vibration-proof rubber member, the vulcanized rubber member is cylindrical, and its outer surface is bonded to the inner surface of the first rigid member, and its inner surface is bonded to the outer surface of the second rigid member. It is particularly preferable that the rubber member has at least one cavity at a position opposite to the second rigid member.

By forming such a cavity, the spring constant in the direction of the cavity becomes small, and the spring constant of the vibration-proof rubber member can be easily adjusted according to the purpose.

The term "cylindrical" as used herein means that the cross section is circular, elliptical,
A circle is preferable in the manufacturing process, including an ellipse.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of a vibration-proof rubber member of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing an example of a vibration-proof rubber member having a cylindrical vulcanized rubber member. FIG. 2A is a longitudinal side view of the central portion thereof.
[B] is a bottom view. In the anti-vibration rubber member illustrated in this figure, an example is shown in which both the first rigid member and the second rigid member are formed of a fiber-reinforced thermoplastic resin.

The anti-vibration rubber member 1 comprises a first rigid resin member 3, a second rigid resin member 4, and a vulcanized rubber member 5. The vulcanized rubber member 5 has a cylindrical shape and has a first surface on an outer surface. The inner surface of the cylindrical portion formed on the rigid resin member 3 and the inner surface of the vulcanized rubber member 5 are adhesively fixed to the outer surface of the second rigid resin member 4 which is an inner cylinder. 13,
Reference numeral 15 denotes a vulcanized adhesive layer. Legs 11 and 12 for attachment are formed on the first rigid resin member.
Attachment nuts 7a and 7b are provided integrally with 1 and 12, respectively. A flange is formed on the nut to prevent the nut from dropping off when it is tightened and to prevent the nut from rotating.

The legs 11, 12 are provided with cavities V3, V4, respectively, which contribute to a reduction in the weight of the vibration damping rubber member 1 as a whole. Further, a rib 9 for connecting and strengthening the legs 11 and 12 is formed.

The nuts 7a and 7b for mounting may be bolts. When the nuts 7a and 7b are made of a metal material, the surface of the metal is subjected to an appropriate treatment for improving the adhesiveness to a resin, and is disposed in a mold. It is also a preferable embodiment to provide a molten thermoplastic resin, and to bond and integrate the vulcanized rubber member 5 at the same time.

The vulcanized rubber member 5 has cavities V1, V2 penetrating in the direction of the axis of the cylinder at positions opposite to the second rigid member 4.
Are formed. By forming the cavities V1 and V2, the second
The spring constant in the cavity direction of the rigid resin member 4 is reduced,
This is preferable because the vibration isolation performance is improved and the resonance frequency can be adjusted. The cavity may be penetrating,
It does not have to penetrate. Two or more cavities may be formed on the opposite side with respect to the second rigid member that is the inner cylinder. The cross-sectional shape of the cavity is bilaterally symmetrical in the illustrated example, but may be asymmetrical. The shape of the cavity is set in consideration of a spring constant required as a vibration-proof rubber member, a frequency at which transmission is to be prevented, and the like. As shown in FIG. 2A, in this example, a line connecting the second rigid resin member 4 and the center of the cavity forms an angle θ with the mounting direction of the vibration-proof rubber member 1. This angle is set in consideration of the use of the anti-vibration rubber member and the anti-vibration performance, and may be 0 degree.

As the raw rubber constituting the rubber molded article used in the present invention, those conventionally used in rubber molded articles such as vibration-proof rubber can be used without limitation. In particular,
Nitrile rubber (NBR), styrene butadiene rubber (S
BR), butadiene rubber (BR), isoprene rubber (I
R), diene rubbers such as chloroprene rubber (CR), ethylene propylene rubbers (EPR, EPDM), olefin rubbers such as butyl rubber (IIR), halogenated butyl rubbers such as brominated butyl rubber (Br-IIR), and other polyurethane rubbers. Synthetic rubbers including acrylic rubber, fluorine rubber, silicone rubber, chlorosulfonated polyethylene, and the like, natural rubber, and the like are exemplified, and these are used alone or in combination of two or more.

If necessary, known rubber additives such as antioxidants, waxes, coloring agents, fillers, softeners such as plasticizers and process oils, and tackifiers are added to the rubber material. The goods are manufactured. As a method for crosslinking the rubber raw material composition, a method using a known crosslinking agent such as sulfur crosslinking or peroxide crosslinking can be used without limitation. The hardness of the vulcanized rubber member is preferably from 60 to 95, more preferably from 70 to 90, by Asker A.

In the present invention, the thermoplastic resin forming the rigid resin member includes polyolefin such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, acrylonitrile-styrene resin (AS resin), A
General thermoplastic resin such as BS and acrylic resin, polyamide, polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT)
Thermoplastic resins called engineering plastics such as polyester, polyacetal, modified polyphenylene ether, etc., polyphenylene sulfide, polyether ether ketone (PEEK), polyarylate,
Polysulfone, polyether sulfone, polyketone sulfide, polyetherimide, aromatic polyester,
Resins called super engineering plastics such as polyamino bismaleimide and triazine resin are exemplified. Since the resin molded body becomes a structural member, it is preferable to use a material having high strength and high rigidity.

As the inorganic short fibers to be added to the thermoplastic resin, known thermoplastic resin reinforcing materials can be used without any particular limitation. Specific examples include glass fibers, potassium titanate whiskers, whiskers such as zinc oxide and calcium sulfate, wollastonite, and the like. These inorganic short fibers are subjected to a coupling agent treatment as necessary, and are kneaded and dispersed with a thermoplastic resin.

Injection of the molding cavity of the fiber-reinforced thermoplastic resin can be performed by a known method, for example, transfer molding, flow molding, injection molding and the like. preferable.

As a material constituting the rigid member other than the fiber-reinforced thermoplastic resin, a high-rigidity material such as a metal and a ceramic is used, and a metal material such as iron, stainless steel, aluminum and brass can be used. The use of aluminum and its alloys is particularly preferred in terms of properties.

A vulcanized adhesive formed mainly on chlorosulfonated polyethylene formed on the surface of a vulcanized rubber member is applied to the surface of an adhesive layer of a vulcanized adhesive and treated, or a coupling is added to the vulcanized adhesive. As the agent, as described above, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent can be used, but the use of a silane coupling agent, a titanium coupling agent, and a zirconium coupling agent is possible. Is more preferable, and the use of a silane coupling agent is particularly preferable since an excellent effect of improving the adhesive strength is recognized.

As the silane coupling agent, compounds having at least one or more alkoxysilyl groups and other substituents in one molecule can be used alone or in combination of two or more. For example, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane , N- (β-aminoethyl) -γ
Isocyanate-functional silanes such as aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri (β-oxymethylethoxy) silane, γ-mercaptopropyltrimethoxysilane , Γ-mercaptopropyltriethoxysilane, bis (γ- (triethoxysilyl) propyl) tetrasulfide (trade name: Si-69, manufactured by Degussa Corporation) and the like.

The above-mentioned coupling agent may be used in a neat state, or may be used by dissolving it in an appropriate solvent if necessary. As the solvent, water, alcohols such as ethanol and isopropanol, ketones such as methyl ethyl ketone, esters such as ethyl acetate, cellosolves, hydrocarbons such as n-hexane and cyclohexane can be used as suitable solvents. .

The vulcanized adhesive may be used by dissolving chlorosulfonated polyethylene in an appropriate solvent and adding necessary additives, or a commercially available product may be used. The thickness of the vulcanized adhesive layer is not limited as long as the required adhesive strength is exhibited, but is generally about 5 to 50 μm. As a method for applying the adhesive, known methods such as brush coating, dipping, spray coating, and roll coater can be used.

Before applying a chlorosulfonated polyethylene-based vulcanizing adhesive or an adhesive containing a silane coupling agent, the surface of the vulcanized rubber member may be subjected to a pretreatment such as a plasma treatment or a corona discharge treatment. This is a preferred embodiment.

The vibration damping member, vibration damping member and the like manufactured by the manufacturing method of the present invention are usually interposed between structural members having high rigidity, and the vibration of one structural member is transmitted to another structural member. And a structural member for attaching to each structural member by a known method such as bolting, at least one of which is a fiber-reinforced thermoplastic resin. Other structural members may be metallic materials or the same fiber reinforced thermoplastic. It is preferable that both are made of a fiber-reinforced thermoplastic resin, because the weight of the vibration-proof rubber member and the like can be further reduced.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments and the like specifically showing the configuration and effects of the present invention will be described below. FIG. 3 shows the shape of an adhesion test sample of a vulcanized rubber member / thermoplastic resin composite for measuring the adhesive strength between the vulcanized rubber member and the rigid resin member of the vibration-proof rubber member of the present invention. The bonding sample 31 is composed of a rigid resin member 33, an iron member 35, and a vulcanized rubber member 37. A chlorosulfonated polyethylene vulcanizing adhesive layer is formed on the bonding surface a1-a2 between the vulcanized rubber member 37 and the rigid resin member 33.

The rigid resin member 33 includes a screw portion 39 and a flange portion 4.
The rigid member 33 has the same shape as the rigid member 33.

In this adhesive sample, a known vulcanizing adhesive suitable for bonding metal and rubber is applied to the surface of the iron member 35 bonded to rubber, and a raw rubber composition is supplied. By vulcanizing under heat and pressure by means such as injection molding, a composite member in which the vulcanized rubber member 37 and the iron member 35 are integrated is formed. Next, a predetermined vulcanized adhesive layer described in Example was formed on the a1-a2 surface of the vulcanized rubber member 37 with a chlorosulfonated polyethylene-based vulcanized adhesive, and after disposing in a mold, inorganic short fibers were removed. The adhesion test sample 3 is formed by injection molding of the contained thermoplastic resin to form the rigid member 33.
1 is obtained. The configuration of the vulcanized adhesive layer used and the presence or absence of preheating of the vulcanized rubber member are shown in Examples and Comparative Examples.

(Preparation of vulcanized rubber member) An unvulcanized rubber composition is prepared by a usual method using the compounding composition shown in Table 1 and injection molding of a predetermined resin is performed by the above-described process. A composite member in which a vulcanized rubber member as an adhesive sample was integrated was produced.

[0039]

[Table 1] (Measurement of adhesive strength)
Using the CS500 (Shimadzu Corporation), each rigid member and the screw portion of the iron member are attached to a jig having a female screw adapted to the screw portion formed on the rigid member and the iron member of the iron member, and the screw sample of the iron member is attached. After mounting, a tensile test was performed under the following conditions. Tensile measure: 20 mm / min Temperature: 23 ° C. Humidity: 65% RH (Example 1) A cavity for accommodating a composite member in which an iron member and a vulcanized rubber member are integrated in advance and a cavity for forming a rigid resin member Using a mold having the above, the composite member obtained in the above (1) is arranged in a predetermined cavity, and a rigid resin member is formed by injection-molding a fiber-reinforced thermoplastic resin in a molten state, An adhesion test sample was prepared. The fiber reinforced thermoplastic used was 3mm
Nylon-6,6 to which 50% by weight of glass fiber chop strands are kneaded and added. The injection molding conditions for the thermoplastic resin were a mold temperature of 140 ° C., a resin temperature of 300 ° C., and an injection pressure of 80 MPa.

At the time of injection molding, a vulcanizing adhesive containing chlorosulfonated polyethylene as a main component is applied to the surface of the rubber molded body to be bonded to the thermoplastic resin so as to have a dry film thickness of 15 μm, dried and vulcanized. An adhesive layer was formed. No preheating of the rubber molding was performed.

Example 2 As a vulcanized rubber adhesive layer, a vulcanized adhesive mainly composed of chlorosulfonated polyethylene was applied by brush coating so that the film thickness after drying was about 15 μm. An adhesion test sample was prepared in exactly the same manner as in Example 1 except that Si-69 was applied as a silane coupling agent in a neat state to the formed adhesive layer and dried.

Example 3 As a vulcanized rubber adhesive layer, Si-69 was added as a silane coupling agent to a vulcanized adhesive mainly composed of chlorosulfonated polyethylene at 25% by weight based on the solid content of the adhesive. The obtained adhesive solution was applied by brush coating so that the film thickness after drying was about 15 μm, and an adhesion test sample was prepared in the same manner as in Example 1 except that the adhesive solution was dried. (Comparative Example 1) Before placing the vulcanized rubber member in a mold,
An adhesion test sample was prepared under the same conditions as in Example 1 except that the sample was preheated at 0 ° C. for 30 minutes.

Comparative Example 2 An adhesion test sample was produced under the same conditions as in Example 2 except that the vulcanized rubber member was preheated at 120 ° C. for 30 minutes before being placed in the mold.

Table 2 shows the evaluation results. The adhesive strength was represented by an index with the adhesive strength of Example 1 being 100. From these results, it can be seen that the adhesive strength of the sample obtained by injection molding of the thermoplastic resin without preheating the vulcanized rubber member is excellent, and the vulcanized adhesive layer to which the silane coupling agent is added as the vulcanized adhesive. Or the sample obtained by applying the silane coupling agent to the vulcanized adhesive layer has a further excellent adhesive strength.

[0045]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of an anti-vibration rubber member of the present invention.

FIG. 2 is a longitudinal side view and a bottom view showing an example of a vibration-proof rubber member of the present invention.

FIG. 3 is a view showing an adhesion test sample for measuring an adhesion strength.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vibration-proof rubber member 3 1st rigid member 4 2nd rigid member 5 Vulcanized rubber member 13, 15 Vulcanized adhesive layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29K 105: 12 B29K 105: 12 621: 00 621: 00 F term (Reference) 3J048 AA01 BA19 DA01 EA07 EA13 EA15 3J059 AD06 BA42 BC06 BC14 BD01 BD05 BD06 EA03 EA06 GA02 4F206 AB25 AD05 AD34 AE07 AH17 JA07 JB12 JB28 JF01 JF02 JF05

Claims (6)

[Claims] 1. A method of manufacturing a vibration-proof rubber member comprising a first rigid member, a second rigid member, and a vulcanized rubber member provided between the first rigid member and the second rigid member. Wherein at least one of the first rigid member and the second rigid member is a rigid resin member made of a fiber reinforced thermoplastic resin containing 30 to 60 parts by weight of inorganic short fibers, and
A method for manufacturing a vibration-proof rubber member, comprising the step (3). (1) A vulcanized rubber member molding step of vulcanizing and molding the vulcanized rubber member in advance. (2) An adhesive layer forming step of providing a vulcanized adhesive layer containing chlorosulfonated polyethylene as a main component on an adhesive surface of the vulcanized rubber member with the fiber-reinforced thermoplastic resin. (3) disposing the surface-treated rubber member without preheating in the surface-treated rubber member accommodating cavity of a mold having a cavity for accommodating a surface-treated rubber member and a cavity for forming a rigid resin member; A resin injecting step of injecting a fiber reinforced thermoplastic resin into the member forming cavity in a molten state to form the rigid resin member. 2. The adhesive layer forming step includes: (2 ′) providing a vulcanized adhesive layer mainly composed of chlorosulfonated polyethylene on a surface of the vulcanized rubber member to be bonded to the fiber-reinforced thermoplastic resin. After that, the surface of the vulcanized adhesive layer is treated with a coupling agent, or a chlorosulfonated polyethylene is used as a main component on the bonding surface of the vulcanized rubber member with the fiber-reinforced thermoplastic resin, and a coupling agent is used. The method for producing a vibration-proof rubber member according to claim 1, which is an adhesive layer forming step of providing an added vulcanized adhesive layer. 3. The method according to claim 2, wherein the coupling agent is a silane coupling agent. 4. An anti-vibration rubber member manufactured by the manufacturing method according to claim 1. 5. The vulcanized rubber member is cylindrical, and has an outer surface bonded to an inner surface of the first rigid member and an inner surface bonded to an outer surface of the second rigid member. The anti-vibration rubber member according to claim 4, wherein 6. The vibration damping rubber member according to claim 5, wherein the rubber member has at least one cavity at a position opposite to the second rigid member.