JPH0580500B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a rubber-based composite material that can produce a composite by bonding a plastic substrate and a rubber composition to each other with good adhesiveness. Problems to be solved by conventional techniques and inventions Composite materials have recently been used in various fields because they are far superior to single materials in terms of functionality, reliability, durability, and other characteristics, as well as cost. It is attracting attention, and the development of new composite materials by combining various materials is active. Composite materials are classified into blend type and laminated type depending on their composite form, but among these, laminated type composite materials have been particularly actively developed because they can impart unique properties such as anisotropy. Composite materials are used not only in automobile parts such as tires and bumpers, but also in many fields such as electrical and electronic parts and sporting goods.The development of new composite materials is highly anticipated, especially in the field of materials based on plastics. Rubber-based composite materials are one of the materials that are currently attracting attention in connection with new materials such as engineering plastics. Whether or not the above laminated composite material can be manufactured depends on whether or not the base and the coating can be bonded.
Particularly when a rubber composition is used as a coating, bonding properties are poor, and bonding techniques for imparting and improving adhesion are a major challenge for laminated composite materials, especially rubber-based composite materials. Conventionally, methods for manufacturing composite materials suitable for laminated composite materials of a plastic substrate and a rubber composition include forming a fine rough surface on at least one surface of the substrate or coating, or chemical treatment. There is a method of adhering the rubber composition by applying an adhesive after treatment, or a method in which the rubber composition is vulcanized (crosslinked) in advance, the surface is treated with chemicals, flames, low-temperature plasma, or corona, and then melted or solvent is applied. A method has been adopted in which a plastic material melted in water is bonded in contact with the surface. However, this method of combining a substrate and a rubber composition with an adhesive using a rough surface or without roughening the surface of the substrate reduces workability due to stickiness and stickiness of the adhesive, and In addition to damaging the appearance and causing errors in dimensional accuracy due to solidified adhesive, when using plastic materials as a base material, the adhesive that can be used to bond and manufacture composite materials may be special. Not only is it limited, but it also has drawbacks such as the bondable substrate is limited to only a few types of materials such as nylon and ABS resin. Furthermore, the method of vulcanizing a rubber composition in advance, treating the surface, and then melting or melting the plastic to adhere it is a complicated process, as it requires vulcanization molding of the rubber in advance. However, there is a problem in that it is quite difficult to obtain a composite material with high dimensional accuracy. The present invention was made in view of the above circumstances, and it is an object of the present invention to provide a method for compounding a rubber composition with good adhesion without using an adhesive or wet plating on a plastic substrate. . Means and Effects for Solving the Problems In order to achieve the above object, the present inventors used various plastic materials as the base, and as a result of conducting intensive studies on the bonding method between the base and the rubber composition, they found that dry plating Metal thin films of zinc, copper, cobalt, and their alloys obtained by this method become strong when a rubber composition is vulcanized and pressed at a temperature similar to that heated during normal vulcanization. A rubber-based composite material with good adhesion is obtained by adhesion, and zinc, copper, and cobalt can be easily deposited as a thin film on the substrate by dry plating method, and the metal thin film thus obtained can be coated as described above. It was discovered that a rubber composition can be bonded with good adhesiveness, and the present invention was completed. Accordingly, the present invention provides a method for producing a rubber composite material formed by bonding a plastic substrate and a rubber composition, in which a thin metal film selected from zinc, copper, cobalt, and alloys thereof is deposited on the surface of the substrate by a dry plating method. The present invention provides a method for producing a rubber-based composite material, in which a rubber composition containing an organic cobalt salt is formed on the metal thin film, and then a rubber composition containing an organic cobalt salt is heat-pressed and vulcanized and bonded. The present invention will be explained in more detail below. The method for manufacturing a rubber-based composite material according to the present invention involves bonding a base and a rubber composition to form a composite, but a wider variety of plastic materials than conventional ones can be used as the base. For example, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyester such as polyoxybenzoyl, polyamide such as 6-nylon, 6,6-nylon and aromatic polyamide, polyacetal, polyphenylene oxide, polyether ether ketone, Polyethers such as polyphenylene sulfide, polysulfones such as polysulfone, polyethersulfone,
Polyimides such as polyimide, polyetherimide, polyamideimide, polybismaleimide, thermoplastic resins such as polycarbonate, formaldehyde resins such as phenolic resins and melamine resins,
Allyl resins such as diallyl phthalate, epoxy resins, silicone resins, thermosetting resins such as polyurethane, unsaturated polyester resins and vinyl ester resins often used in FRP may be used alone or in combination of two or more. Furthermore, these plastic materials include, for example, glass fiber, carbon fiber,
Composite plastics, such as those mixed with boron fibers, silicone carbide, or high-stiffness organic fibers such as Kevlar as reinforcing materials, may also be used.
Furthermore, carbon black, calcium carbonate, clay, coloring agents, ultraviolet absorbers, anti-aging agents, etc. may be mixed with these. Further, there are no restrictions on the shape or size of the substrate, and a substrate of an appropriate material, shape, and size can be selected and used depending on the purpose. In the present invention, when a rubber composition is composited onto the above-mentioned substrate, a thin metal film selected from zinc, copper, cobalt, and alloys thereof is first formed on the surface of the substrate by a dry plating method. To form a thin metal film, select the chamber capacity and fixing jig of the dry plating device depending on the size and shape of the substrate, and use vacuum evaporation method or ion plating method depending on the material of the substrate, desired film thickness, thin film properties, etc. Various dry plating methods such as , sputtering method, etc. can be adopted, and operating conditions such as the ultimate vacuum of the dry plating device, whether or not gas such as argon or oxygen is injected, substrate temperature, annealing, etc.
Furthermore, evaporation methods such as resistance heating of the evaporation source in vacuum evaporation method, ion plating method, induction heating, and electron beam heating, high frequency plasma in ion plating method, DC voltage application, cluster beam, hot cathode method, etc. Various sputtering methods such as DC magnetron, bipolar direct current, and high frequency sputtering methods can be selected and employed. In addition, as a method for obtaining an alloy thin film by the dry plating method according to the present invention, a plurality of vapor deposition sources that can be heated independently are installed in a dry plating apparatus, and a plurality of vapor deposition sources are simultaneously heated according to the heating conditions of each vapor deposition source according to the alloy composition. Methods include flying different metals. Furthermore, in order to obtain the metal thin film according to the present invention, an optical measurement system consisting of a spectral filter, a monitor glass, etc. for optical film thickness control such as the λ/4 control method is installed in the dry plating device,
There is no problem in making various modifications to the dry plating device in order to automate the operation.In fact, by such installation and modification, the film thickness can be easily controlled during thin film formation, and the manufacturing quality can be stabilized. More preferable for the purpose. The metal thin film obtained by the above method contains zinc,
It must be made of a metal material selected from copper, cobalt, and their alloys; however, if these alloy materials contain any of the metals zinc, copper, or cobalt, any of these metals may be used. There is no particular limit to the thickness of the metal thin film obtained by the rubber composition and the above method during vulcanization, but from 10 Å to
A thickness of 100 .mu.m is preferable from the viewpoint of the main productivity of the thin film, and a thickness of 10 .ANG. to 1 .mu.m is particularly preferable from the viewpoint of forming a thin film that does not affect the properties of the composite. Next, the method for producing a rubber-based composite material of the present invention is to produce a rubber-based composite material by heat-pressing and vulcanizing a rubber composition onto the metal thin film obtained by the above method. Here, as the rubber component in the rubber composition used in the present invention, natural rubber (NR) and synthetic rubber having a carbon-carbon double bond in the structural formula can be used alone or in a blend of two or more. . The above synthetic rubbers include polyisoprene rubber (IR), which is a homopolymer of conjugated diene compounds such as isoprene, butadiene, and chloroprene, polybutadiene rubber (BR), and polychloroprene rubber, and the above conjugated diene compounds and styrene, acrylonitrile, and vinylpyridine. , styrene-butadiene copolymer rubber (SBR), which is a copolymer with vinyl compounds such as acrylic acid, methacrylic acid, alkyl acrylates, and alkyl methacrylates, vinylpyridine-butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic acid Copolymers of diene compounds and olefins such as ethylene, propylene, and isobutylene, such as butadiene copolymer rubber, methacrylic acid butadiene copolymer rubber, methyl acrylate butadiene copolymer rubber, methyl methacrylate butadiene copolymer rubber, etc. polymerized rubber (IIR)], copolymers of olefins and non-conjugated dienes (EPDM) [e.g. ethylene, propylene, cyclopentadiene terpolymer, ethylene propylene-5-ethylidene-2-norbornene terpolymer] , ethylene propylene-1,4-hexadiene terpolymer], polyalkenamers obtained by ring-opening polymerization of cycloolefins [e.g. polypentenamer], rubbers obtained by ring-opening polymerization of oxirane rings [e.g. Possible polyepichlorohydrin rubber], polypropylene oxide rubber, etc. Also included are halides of the various rubbers mentioned above, such as chlorinated isobutylene isoprene copolymer rubber (Cl-IIR) and brominated isobutylene isoprene copolymer rubber (Br-IIR).
Furthermore, ring-opened polymers of norbornene can also be used. Further, as a blended rubber, a saturated elastic material such as epichlorohydrin rubber, polypropylene oxide rubber, or chlorosulfonated polyethylene may be blended with the above-mentioned rubber. Furthermore, the rubber composition used in the present invention may be filled with carbon black, silica, calcium carbonate, calcium sulfate, clay, diatomaceous earth, mica, etc. according to the purpose and use of the rubber composite to be manufactured, according to a conventional method. softeners such as mineral oil, vegetable oil, synthetic plasticizers, and vulcanization accelerators such as stearic acid,
Antiaging agents, crosslinking agents, etc. can be added. The rubber composition and the metal thin film are bonded together by vulcanization bonding by heat-pressing the rubber composition onto the metal thin film as described above. In addition to sulfur vulcanization, which is the most common and most important vulcanization method, vulcanization with organic sulfur compounds, such as dithiodimorpholine,
Examples include methods such as thiuram vulcanization. In addition, the heating and compression bonding operations performed in the method for producing a rubber-based composite material of the present invention are carried out at a temperature and pressure that does not damage the original shape of the substrate and the rubber composition. and the rubber composition, supplying the activation thermal energy necessary to form an adhesive force between zinc or copper and the vulcanized rubber composition, and furthermore, supplying the activation thermal energy necessary to vulcanize the rubber composition. This is carried out for the purpose of supplying activation thermal energy, and the appropriate temperature and pressure for this purpose are appropriately selected depending on the type of substrate and rubber composition, and the range thereof is not limited. Effects of the Invention As explained above, a metal thin film selected from zinc, copper, cobalt, and alloys thereof is deposited and formed on the surface of a plastic substrate by dry plating, and then a rubber composition is heat-pressed onto the metal thin film. Since the adhesive is vulcanized, it is possible to composite a wide variety of plastic substrates and rubber compositions with excellent bonding properties, and there is no need to use adhesives or wet plating methods. Various problems associated with its use have been solved, and a rubber-based composite material with excellent durability has been obtained, and a material that has been difficult to composite with conventional rubber compositions as a base material.
Any shape or size can be used. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. [Example 1] As the substrate material, polyarylate (manufactured by Unitika Co., Ltd., trade name: U Polymer), polyamide (6,6-
Nylon), polyether (manufactured by Engineering Plastics Co., Ltd.: trade name: Noryl), polysulfone (manufactured by Nissan Chemical Co., Ltd.: trade name: PES), polycarbonate cut into 25 mm width x 60 mm length x 2 mm thickness, and the surface degreased with a solvent. These substrates were placed in a vacuum evaporator using a vacuum evaporator, and the vacuum inside the chamber was brought to below 10 ^-5 Torr, and then a small amount of Ar gas was flowed into the chamber to adjust the vacuum to 5 × 10 ^-3 Torr. rear,
The surface of the test piece was cleaned for 5 minutes using RF glow discharge using an RF high frequency power source. After cleaning,
The RF glow discharge was stopped, and a metal thin film of the type and thickness shown in Table 2 was formed on the surface of the substrate by a resistance heating method. The film thickness was measured using a Talystep manufactured by Taylor Hobson. After laminating an unvulcanized rubber composition of the type shown in Table 1 below on the metal thin film on the surface of the substrate obtained by the vacuum evaporation method, the rubber composition was pressurized at a temperature of 145°C for 40 minutes. It was attached with sulfur.

[Table] The composite material obtained by vulcanization adhesion of the above rubber composition was subjected to a 90° peel test using a tensile tester at a tensile speed of 50 mm/min to evaluate adhesiveness. The above adhesive evaluation results are shown in Table 2.

[Example 2]

A rubber-based composite material was prepared in the same manner as in Example 1, except that the metal thin films of the types shown in Tables 3 and 4 were formed by the following sputtering method and ion plating method, respectively, instead of the vacuum evaporation method in Example 1. was manufactured, and the adhesion of the obtained rubber-based composite material was evaluated. Sputtering method Using a magnetron sputtering device, place the substrate in the substrate holder inside the device, and spread the inside of the chamber at 10 ^-5
After setting the vacuum to less than Torr, a trace amount of
After adjusting the degree of vacuum to 0.1 Torr by flowing Ar gas, the surface of the substrate was cleaned for 5 minutes using a high frequency glow discharge of 13.56 MHz. After cleaning, the high frequency glow discharge was stopped, a DC voltage of -600 V was applied to the metal sample target, and sputtering was performed with Ar plasma at a target current of 0.5 A to form a metal thin film on the surface of the substrate. Ion plating method The substrate was placed in an ion plating device, Ar plasma was generated using a high frequency power source according to a conventional method, and the metal sample was evaporated in that state by resistance heating to form a metal thin film on the surface of the substrate. The above results are also listed in Tables 3 and 4.

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[Table] From the results in Tables 3 and 4, even if the sputtering method or ion plating method is used instead of the vacuum evaporation method in Example 1, the manufacturing method still satisfies the scope of the present invention. In this case, regardless of the type of dry plating method, as in Example 1, even if a plastic material such as polyarylate, polyamide, polyether, polysulfone, or polycarbonate is used as the substrate, the metal thin film layer cannot be formed. It was shown that a rubber-based composite material with excellent adhesiveness independent of thickness could be obtained, further confirming the effects of the present invention.

Claims (1)

[Scope of Claims] 1. A method for manufacturing a rubber-based composite material formed by bonding a plastic substrate and a rubber composition, in which zinc, zinc,
A rubber-based composite material characterized in that a metal thin film selected from copper, cobalt, and alloys thereof is adhered and formed, and then a rubber composition containing an organic cobalt salt is heat-pressed and vulcanized onto the metal thin film. manufacturing method. 2. The method according to claim 1, wherein the vulcanization is sulfur vulcanization or organic sulfur vulcanization.