JPH03236952A - Compounding process for rubber - Google Patents

Abstract

PURPOSE:To manufacture a rubber composition of superior bonding property at high temperature and high humidity without adding organic cobalt salt and upgrade the processing properties at the time of higher drawing in the case of compounding with a fine cord or the like by bonding and compounding a base and the rubber composition by means of a specified copper alloy film formed on the surface of base. CONSTITUTION:Copper alloy containing aluminum, copper alloy containing aluminum and zinc or copper alloy containing aluminum and nickel is used for a metallic film formed on the surface of a base. It is preferable to contain 5 - 40atom% aluminum, particularly 10 - 30atom%, 0 - 25% of zinc, particularly 5 - 15atom%, and 0 - 30atom% of nickel, particularly 5 - 25atom%, and copper for the balance. In addition, the total of aluminum and zinc or the total of aluminum and nickel should preferably is 40atom% or less. If ratio is out of the above range, sometimes enough bonding force with a rubber composition without being blended with organic cobalt salt may not be produced. As the copper alloy film is flexible, a rubber bonded composite material with a metal cord of the like is provided with processing properties such as wire drawing.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides adhesive composites between a base material and a rubber composition using a copper alloy thin film formed on the surface of the base material, thereby improving adhesion especially under high temperature and high humidity environments. The present invention relates to a rubber compounding method that provides a rubber adhesive compound with excellent durability.

[Prior art and problems to be solved by the invention] Rubber-based composite materials are used in a wide range of fields such as tires, conveyor belts, belts, anti-vibration rubber, hoses and other automobile parts, industrial goods, electronic parts, and sporting goods. In particular, rubber-based composite materials with metal base materials have important industrial fields of use, such as tires, anti-vibration rubber, and belts.

Conventionally, such rubber-based composite materials have been produced by applying an adhesive to a base material to adhere the rubber composition, or after applying plus (copper-zinc alloy) plating or zinc plating to the base material using a wet plating method. Methods such as vulcanization bonding of rubber compositions have been adopted.

Among these methods, methods using adhesives generally have a coating film that is several to several dozen thick, hard and brittle, so this does not pose a problem if the base material is strong and does not deform, such as anti-vibration rubber. In the case of thin cords where the base material is significantly deformed,
There is a problem in that the adhesive part is damaged and cannot be used for such purposes.

On the other hand, in the case of plus or zinc plating, it is soft and flexible, but in order to obtain stable and productive adhesion, it is necessary to use a rubber composition containing organic cobalt salt, which is an adhesion promoter. There is a disadvantage of not being able to do so.

In addition, in the case of tire cords, plastic-plated cords are used because in addition to excellent initial adhesion performance, a fastening material with excellent corrosion resistance and heat resistance is required, but car tires have harsh running conditions and high temperatures. There is a problem in that the adhesive strength of the adhesive surface decreases in a high humidity environment.

Furthermore, zinc plus plating by the electrolytic method conventionally practiced industrially generates waste liquid, and disposal of the waste liquid becomes a problem.

In response to this, the present inventors previously proposed bonding a base material and a rubber composition via a zinc, copper, cobalt or cobalt alloy plating film using a tri-plating method (Japanese Patent Laid-Open No. 62-8731 -1 Publication, Publication No. 62-246278).

However, although the rubber adhesive composite proposed by these proposals provided excellent adhesive performance and solved the problem of waste liquid, in the case of zinc-plus, rubber compositions containing the above-mentioned organic cobalt salts were used. Furthermore, there is also room for improvement in the decrease in adhesive strength under the above-mentioned high temperature and high humidity environment. On the other hand, in the case of cobalt or cobalt alloy plating,
Cobalt is expensive and has a cost disadvantage,
Cobalt or cobalt alloy plating is hard and has poor toughness, so when it is applied to a base material such as a thin cord, it is difficult to draw, and since Cobal 1 is a ferromagnetic material, Magne I-ron sputtering is difficult. The film forming method has problems such as limitations in film forming speed and target thickness.

The present invention has been made in view of the above circumstances, and is a method for bonding and composing a base material and a rubber composition via a metal thin film. Goss 1 adhesive composite that adheres to rubber, and the resulting rubber adhesive composite has excellent adhesive durability in high temperature and high humidity environments, and when combined with a thin coat, etc., has excellent processability during wire drawing. The purpose of the present invention is to provide a method for compounding rubber that provides the following properties.

[Means and effects for solving the problem] The present inventors,
In order to achieve the above objectives, we have conducted extensive research and found that the base material is a copper alloy thin film selected from copper alloys containing aluminum, copper alloys containing aluminum and tin, and copper alloys containing aluminum and nickel. When formed on the surface, the base material and the rubber composition are strongly bonded and composited without using an adhesion promoter such as organic cobalt salt, and furthermore, the adhesive property does not deteriorate significantly under high temperature and high humidity conditions. It has been discovered that the copper alloy thin film is soft and has good workability during wire drawing even when combined with a thin cord etc., and has made the present invention. This is what we have come to.

Therefore, the present invention provides an adhesive composite of a rubber composition and a substrate on which a thin film of a copper alloy selected from copper alloys containing aluminum, copper alloys containing aluminum and tin, and copper alloys containing aluminum and nickel is formed on the surface. A method of compounding rubber is provided.

The present invention will be explained in more detail below.

In the rubber composite method of the present invention, the type of target base material is not particularly limited, and the method is applicable to metals, ceramics, plastics, FRP, etc.

In this case, the types of metal base materials include, for example, mineral steel, stainless steel, titanium, titanium alloy, aluminum,
Examples include, but are not limited to, aluminum alloy, copper, copper alloy, zinc, zinc alloy, amorphous alloy, and the like. Also, ceramics, plastics, F
Various RPs can be selected depending on the purpose.

The shape and size of this base material are appropriately selected depending on the purpose, but examples include steel wire, steel cord, steel tire cord, steel cable, steel strand, steel cord, steel plate, steel filament, etc. (generally referred to as steel cord), metal plates, metal fittings, plastic plates, FRP plates, etc. are used.

The rubber composite method of the present invention combines these base materials with a rubber composition, and the resulting rubber composite has good adhesion between the base material and rubber, especially under high temperature and high humidity environments. Because of its stable properties and excellent workability during stretching, it can be used, for example, in tires, power transmission belts, conveyor belts, hoses, etc. Rubber-based composite materials that use fibrous metal as a core material, vibration-proof rubber, and seismic isolation Various rubber products such as rubber materials, Go11 crawlers, rubber screens, rubber rolls, and OA
It can be widely applied to manufacturing parts.

Before forming the copper alloy thin film described below on the base material described above, the surface of the base material may be cleaned using a wet method such as solvent cleaning, ultrasonic cleaning, acid or alkali cleaning, or plasma cleaning (bombardment) performed in a vacuum. , perform pre-treatment using methods such as dry cleaning such as the reverse sputtering method,
It is desirable to improve the adhesion between the copper alloy thin film and the base material.

In the present invention, the metal thin film formed on the surface of the base material is made of a copper alloy containing aluminum, a copper alloy containing aluminum and tin, or a copper alloy containing aluminum and nickel.

Here, the composition of the above alloy includes 5 to 5 aluminum rams.
40 atom%, especially 10 to 30 atom%, tin 0 to 25 atom%, especially 5 to 15 atom%, nickel ○ to 30 atom%
It is particularly preferable that the total amount of aluminum and tin or the total amount of aluminum and nickel be 40 at% or less, with the remainder being copper.

Outside the above range, sufficient adhesive strength may not be produced with rubber compositions that do not contain organic cobalt salts.

These thin copper alloy plating films can be formed on a base material and alloyed at the same time using a dry plating method using an alloy target. It is also possible to form an aluminum and tin plating film or an aluminum and nickel plating film separately or as an alloy on a copper base material or copper plating, and then alloy it by thermal diffusion.

The thickness of the copper alloy thin film can be appropriately selected depending on the purpose, but usually 10A-1OOpxl is preferable from the viewpoint of thin film productivity, and 50λ to 1/in is particularly preferable.

Note that aluminum is an electrochemically base substance and has a low standard electrode potential.For this reason, electroplating using an aqueous electrolyte is generally not possible, but electroplating is possible when a special organic solvent is used; The same applies to alloy systems. Therefore, in order to easily form copper alloy plating containing aluminum, it is preferable to employ a dry plating method.

Therefore, as a method for forming a copper alloy thin film, it is preferable to adopt a dry plating method entirely or partially, for example, vacuum evaporation, ion bubbling, etc., since wet plating of aluminum is difficult. This can be carried out by employing a rating method, a DC and high frequency magnetron sputtering method, a two-pole sputtering method, a high frequency sputtering method, an arc discharge sputtering method, an electron cyclotron resonance (ECR) plasma method, and the like. Among these dry plating methods, ion blating method, DC and high frequency magnetron sputtering method, bipolar sputtering method, and high frequency sputtering method are suitable.

Next, as a rubber component in a rubber composition for obtaining a composite material of a base material and rubber, natural rubber (NR) and synthetic rubber having a carbon-carbon double bond in the structural formula may be used alone or in a blend of two or more. You can use the one you made. The above synthetic rubber includes polyisoprene rubber (IR), which is a homopolymer of conjugated diene compounds such as isoprene, butadiene, and chloroprene.
, polybutadiene rubber (BR), polychloroprene rubber, etc., are copolymers of the above conjugated diene compounds and vinyl compounds such as styrene, acrylonitrile, vinylpyridine, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, etc. Styrene butadiene copolymer rubber (SBR), vinylpyridine butadiene styrene copolymer rubber, acrylonitrile butadiene copolymer rubber,
Copolymerization of olefins such as ethylene, propylene, and imbutylene with diene compounds, such as butadiene acrylate copolymer rubber, butadiene methacrylate copolymer rubber, methyl acrylate butadiene copolymer rubber, methyl methacrylate butadiene copolymer rubber, etc. 9-10 [for example, isobutylene isoprene copolymer rubber (IIR
)), copolymers of olefins and non-conjugated dienes (EP
DM) (e.g. ethylene-propylene-cyclopentadiene terpolymer, ethylene-propylene-5-ethylidene-2-norbornene terpolymer, ethylene-propylene-1,4-hexadiene terpolymer), cyclo Included are polyalkenamers obtained by ring-opening polymerization of olefins (e.g., polypentenamers), rubbers obtained by ring-opening polymerization of oxirane rings (e.g., polyepichlorohydrin rubber that can be sulfur-cured), polypropylene oxide rubbers, etc. Halogenated compounds of the various rubbers mentioned above, such as chlorinated isobutylene isoprene copolymer rubber ((1-II
R), brominated isobutylene isoprene copolymer rubber (Br
-IIR) etc. are also included. Furthermore, ring-opened polymers of norbornene may also be used. Furthermore, 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.

In addition to the above rubber components, according to the purpose and use, fillers such as carbon black, silica, calcium carbonate, calcium sulfate, clay, and mica, softeners such as mineral oil and vegetable oil, crosslinkers such as sulfur, etc. A rubber composition can be prepared by adding a vulcanization accelerator, a vulcanization accelerator, a vulcanization accelerating aid such as zinc white, and stearic acid.

In the present invention, an organic cobalt salt or the like which is a vulcanization adhesion promoter between the copper alloy thin film and rubber is not normally required, but may be added depending on the case.

The combination of the above rubber composition and the copper alloy thin film on the surface of the base material is as follows:
This can be carried out by heat-pressing a rubber composition onto one unit of the copper alloy thin film and vulcanizing it.

Here, as the vulcanization method, in addition to sulfur vulcanization, organic sulfur vulcanization using an organic sulfur compound such as dithiomorpholine or thiuram vulcanization is employed, and vulcanization can be carried out according to a conventional method.

Among these, a method using sulfur vulcanization is particularly preferred. In this case, the amount of sulfur or sulfur in the organic sulfur compound can be 0.5 to 7 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight of the rubber content.

〔Effect of the invention〕

As explained above, the rubber composite method of the present invention is based on a copper alloy thin film selected from a copper alloy containing aluminum, a copper alloy containing aluminum and tin, and a copper alloy containing aluminum 11 and nickel. By compounding the material and rubber, it is possible to make a compound with a rubber composition that does not use organic cobalt salts, and the resulting rubber adhesive compound has excellent adhesive durability, especially at high temperatures and high humidity. Moreover, since the copper alloy thin film is soft, the rubber adhesive composite with metal cord etc. has excellent processability such as wire drawing.

EXAMPLES Hereinafter, examples and comparative examples will be shown to further specifically illustrate the present invention, but the present invention is not limited to the following examples.

[Example, comparative example]

Steel cord with brass plating as base material (diameter: 0
．． 18 nm, twisted structure: 3+9), and the surface of this steel cord was exposed to a high frequency of 13.56 Mt (z, power 100
Argon plasma treatment was performed with W for 3 minutes.

A thin film having the alloy composition shown in Table 2 was formed to a thickness of about 50 OA by DC magnetron sputtering using a Cu-AQ alloy target on the steel cord subjected to the above treatment. Here, the sputtering conditions were Ar gas pressure of 5 mnTorr, power of 0.5A x 400V, and 30
Seconds. Note that the alloy composition was determined by measuring an alloy thin film formed on a glass substrate using an optical emission spectrometry method.

Next, the above cord was bonded to an unvulcanized rubber composition having the composition shown in Table 1, and then vulcanized and bonded at 145° C. for 40 minutes.

13 14 Table 1 N-phenyl-N1-isopropyl-P-phenylenediamine N-oxydiethy1non-2-benzothiazole sulfamide ability was evaluated.

Soryo Tsujibari R (%): % rubber adhesion area of the cord part after peeling test (rubber cohesive failure rate) F/R (%): Peeling area % of the interface between the rubber layer and alloy thin film after peeling test ( Fracture rate of cord and rubber interface) Note that the Cu-Zn alloy of the comparative example was bonded using a rubber composition in which an organic cobalt salt (cobalt naphthenate) was added to the rubber composition shown in Table 1.

The results are also listed in Table 2.

The vulcanized adhesive sample obtained in this way was subjected to an 18o peel test using a tensile tester at a tensile rate of 50 nwn/mj, n, and the adhesive force was measured. According to the results of adhesion in Table 2, Cu-AQ, Cu-AQ-8n and Cu-A
It is observed that both Q-N i alloy thin film systems provide good adhesion performance using rubber compositions that do not contain organic cobalt salts.

Next, for each sample of Examples 2, 3, 6, 7, 9゜10 and comparative example in Table 2, high temperature of 80 ° C. and 95% RH,
Leave it in a high humidity atmosphere to achieve the above adhesive strength and adhesive performance.
1. Oral changes in the atmosphere were measured.

The results are shown in Table 3.

7 8 From the results in Table 3, Cu-Aff, Cu-Al2Sn
It is recognized that both the alloy thin films of Cu-AQ-Nj and Cu-AQ-Nj provide composite materials with superior adhesive durability under high temperature and high humidity conditions than the Cu-Zn alloy thin film of the comparative example.

In addition, for a sample in which a thin alloy film with a thickness of about 4 prn was formed on a substrate (plus plate) by sputtering method, the Vickers hardness (Hv) was measured using a microhardness meter at a load of 0.5 kgf.
The processability of the product, including its softness and wire drawability, was evaluated by measuring . In this case, if the Vickers hardness value is large, processing is difficult, and if the value is small, processing is easy. The results are shown in Table 4.

As shown in Table 4, although Cu-Zn is soft and has excellent workability, it has poor durability under high temperature and high humidity as described above, while Go is hard and has poor workability. On the other hand, C
u-A Q, Cu-AQ-8n and Cu-A n-N
i alloy is slightly harder than Cu-Zn, but CO
It is recognized that it is softer and has both workability and durability.

Claims (1)

[Claims] 1. Adhesively composite a rubber composition with a base material on which a thin film of a copper alloy selected from copper alloys containing aluminum, copper alloys containing aluminum and tin, and copper alloys containing aluminum and nickel is formed on the surface. A method for compounding rubber, which is characterized by: