WO2001027196A1

WO2001027196A1 - Rubber composition, composite material, and process for producing composite material

Info

Publication number: WO2001027196A1
Application number: PCT/JP2000/007042
Authority: WO
Inventors: Kunio Mori
Original assignee: Zeon Corporation
Priority date: 1999-10-14
Filing date: 2000-10-11
Publication date: 2001-04-19
Also published as: JP2001114942A

Abstract

A rubber composition comprising a rubber, a crosslinking agent, and a specific organonickel salt; a composite material obtained by directly bonding the rubber composition to a metallic material comprising either a metal having higher ionization tendency than nickel or an alloy of the metal while crosslinking the composition; and a process for producing a composite material which comprises heating the rubber composition kept in contact with a metallic material comprising either a metal having higher ionization tendency than nickel or an alloy of the metal to thereby directly bond the composition to the metallic material and crosslink the composition. Thus, a composite material excellent in interfacial adhesion to the metallic material can be obtained by the direct crosslinking/bonding method without the need of subjecting the metallic material to a surface treatment such as coating with an adhesive or plating.

Description

Description Rubber composition, composite material, and method for producing composite material

The present invention relates to a rubber composition having excellent adhesion to a metal material, a composite material of rubber and a metal material (adhesive body of rubber and a metal material), and a method for producing the composite neo. The composite material of the present invention can be applied to a wide range of fields as, for example, seismic isolation rubber, vibration damping rubber, packing, diaphragm, rubber roll, belt, and automobile tire. Background art

Various rubbers are often used as composites with metallic materials, fibers, inorganic compounds, and plastics. In particular, composite materials obtained by bonding rubber and metal materials are used in various products or parts such as seismic isolation rubber, automobile tires, belts, rubber mouths, etc., for electrical and electronic equipment, automobiles, aircraft, medical equipment, It is used in a wide range of other fields such as industrial materials. Conventionally, with respect to composites of rubber and metal materials, improvements in adhesion between the two have been attempted from the viewpoint of improving performance and functionalization.

Conventionally, as the bonding technology between rubber and metal materials, for example, the surface of metal materials such as ebony method, cyclized rubber method, phenolic resin method, halogenated rubber method, brass plating method, and electroless plating method Processing methods are known. However, none of these surface treatment methods was fully satisfactory.

The ebonite method is a method in which a rubber material is coated on a surface of a metal material, and a rubber compound is put on the sheet and heat-pressed. However, there is a problem that heat resistance and impact resistance are poor. The cyclized rubber method is a method in which a cyclized rubber solution is applied to the surface of a metal material, the solvent is dried, and then the rubber compound is pressed and vulcanized and bonded. The phenol resin method is a method in which a resol-type phenol resin solution is applied to the surface of a metal material, the solvent is dried, and a rubber compound is pressed and bonded by vulcanization. The halogenated rubber method is a method of applying a chlorinated rubber solution or a mixed solution of chlorinated rubber and isocyanate to the surface of a metal material, drying the solvent, and pressing and bonding the rubber compound by vulcanization.

According to such a cyclized rubber method or an adhesive method, various types of rubber and various types of metal materials can be adhered with a certain level of adhesive strength. In addition, there is a problem of low productivity. The brass plating method is a method in which a brass plating treatment is performed on the surface of a metal material, and an unvulcanized rubber compound containing an organic acid cobalt or sulfur is vulcanized and bonded. This brass plating method is applied to the bonding between steel cord and rubber in a steel radial tire, but there is a problem in the hot water resistance of the obtained composite material.

The electroless plating method is a method in which an electroless palladium-phosphorus alloy plating or an electroless nickel-copper-phosphorus alloy plating is applied to the surface of a metal material, and a rubber compound is pressed and vulcanized to the plating-treated surface.

Further, as a plating method, a method is known in which a zinc plating treatment is performed on the surface of a metal material, and a rubber compound containing cobalt naphthenate as an adhesion promoter is vulcanized and bonded. However, this method has a problem in that thermal decomposition of rubber is promoted by cobalt. The nickel plating method has excellent heat resistance and water resistance, has little rubber deterioration, and can be effectively vulcanized and bonded when combined with a rubber vulcanization method using triazine thiols.

Furthermore, these various plating methods have a problem that the plating process must be performed on the surface of the metal material, which is troublesome. Moreover, the plating process is mainly applied to metal materials made of iron, copper, brass, etc. There was a problem of being squeezed. For example, according to the nickel plating method, a composite material having excellent adhesiveness and physical properties can be obtained, but it is difficult to perform nickel plating on a metal material made of aluminum magnesium. Therefore, it is difficult to apply it. Disclosure of the invention

An object of the present invention is to provide a composite material having excellent adhesiveness at an interface with a metal material by a direct cross-linking (vulcanization) bonding method without applying a surface treatment such as an adhesive application and a plating process to the metal material. It is to provide a rubber composition which can be used.

Another object of the present invention is to provide an excellent adhesive property at the interface between rubber and a metal material by a direct cross-linking (vulcanization) bonding method without subjecting the metal material to surface treatment such as application of an adhesive and plating. An object of the present invention is to provide a composite material and a method for producing the same.

The present inventor has made intensive studies to overcome the problems of the prior art, and as a result, came to a rubber composition in which a crosslinking agent and a specific organic nickel salt are mixed with rubber. By heating the rubber composition of the present invention in contact with a metal material, the rubber and the metal material are simultaneously bonded at the same time as the rubber is crosslinked, and a composite material having excellent bonding strength (peel strength) at the interface is obtained. Wood can be given. The present inventor has presumed that when the rubber composition and the metal material are heated under contact, nickel plating due to the organic nickel salt is generated at the interface, whereby strong adhesiveness can be obtained. I have. However, the present invention is not limited by the bonding mechanism or the bonding theory of the characteristics.

According to the present invention, it is possible to achieve the cross-linking adhesion between a nickel-plated metal material and a rubber compound containing triazinediols by a nickel plating method without a nickel plating process. . In addition, the rubber composition of the present invention can be used for aluminum or nickel which is difficult to nickel-plate. It can be directly cross-linked and adhered to a metal material composed of magnesium or an alloy containing these. The rubber composition of the present invention can directly cross-link and adhere to a metal having a greater ionization tendency than nickel or a metal material comprising an alloy containing the metal. The present invention has been completed based on these findings.

According to the present invention, a rubber, a crosslinking agent, and

(1) Equation (I)

R! COO -N i 1〇C〇R ₂ (1),

(2) Equation (II)

R! O-N i-O R 2 (II),

(3) Formula (III)

i S 0 ₃ N i-OSO ₉ R (III),

(4) Equation (IV)

as well as

Equation (5)

(In each formula, and R ₂ are each independently a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, an aromatic hydrocarbon group, An alkyl-substituted aromatic hydrocarbon group or an alicyclic hydrocarbon group. The present invention provides a rubber composition containing at least one organic nickel salt selected from the group consisting of compounds represented by the following formula:

Further, according to the present invention, there is provided a composite material obtained by directly cross-linking and bonding a rubber composition containing the organic nickel salt and a metal material having an ionization tendency greater than nickel or an alloy containing the metal. Provided. Further, according to the present invention, the rubber composition containing the organic nickel salt and a metal material having a higher ionization tendency than nickel or a metal material made of an alloy containing the metal are heated in contact with each other. A method for producing a composite material which is directly crosslinked and adhered is provided. BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the rubber used in the present invention include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber, acrylonitrile-butadiene rubber (NBR), and styrene. Isoprene rubber, butadiene-isoprene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber (EPR), ethylene-propylene-gen rubber (EPDM), acrylic rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber And urethane rubber. These rubbers may be modified or modified. These rubbers can be used alone or as a blend of two or more.

As the cross-linking agent (vulcanizing agent), one suitable for the type of each rubber and the performance of the composite (adhesive) can be used. Specific examples of crosslinking agents include sulfur, triazine thiols, resin crosslinking agents, polyol crosslinking agents, peroxides, and combinations (mixtures) of two or more of these. Can be The cross-linking agent content can be appropriately determined according to the type of rubber and the performance of the composite material, but in most cases, 0.1 to 5 parts by weight of rubber, which is generally used, is used in 100 parts by weight of rubber. Preferred results can be obtained within the range.

For crosslinking of rubber, a crosslinking accelerator, a crosslinking aid, and the like can be added as necessary, in addition to the crosslinking agent. For example, sulfenamide-based crosslinking accelerators, thiuram-based crosslinking accelerators, thiazole-based crosslinking accelerators, amine-based crosslinking accelerators, polyfunctional monomers, etc., adjust the rubber crosslinking rate and use metal materials. It is effective in increasing the adhesive strength between and. The content of the crosslinking accelerator and the crosslinking aid can be appropriately determined according to the type of the rubber and the performance of the composite material. In many cases, the content is 0.1 to 10 parts by weight based on 100 parts by weight of the rubber. Good results can be obtained in the range of parts by weight.

Metal activators such as Zn〇, MgO, Ca〇, and Ca (OH) ₂ are used to adjust the vulcanization rate of rubber, improve the properties of vulcanized rubber, and improve adhesive strength. preferable. The metal activators can be used alone or as a mixture of two or more. The content of the metal activator can be appropriately determined according to the type of the rubber and the performance of the composite material. In many cases, the content is preferably in the range of 1 to 20 parts by weight relative to 100 parts by weight of the rubber. The result can be obtained.

In the present invention, a rubber is combined with a specific organic nickel salt in order to exhibit adhesiveness to a metal material and obtain a composite material of rubber and metal having good adhesive strength. As described above, by heating a nickel-plated metal material and a rubber compound containing triazine thiols by contact heating, the metal material composed of various metals and various rubbers are vulcanized and bonded without using an adhesive. can do. However, this nickel plating method needs to apply nickel plating to a metal material, and in addition to a metal material made of aluminum or magnesium, which has a high ionization tendency, in particular. It was difficult to apply them, and it was a problem to be solved. However, when a rubber composition comprising a rubber and a cross-linking agent and an organic nickel salt is heated by contact with a metal material containing a metal having a higher ionization tendency than nickel, the rubber composition does not require an adhesive and a plating treatment, and thus can be treated with a rubber. A composite material in which the metal material is firmly bonded can be obtained. In the cross-linking and bonding process, when the organic nickel salt in the rubber composition and the metal on the surface of the metal material are replaced, nickel plating occurs, and the rubber and the metal material are strongly bonded through the nickel plating. Presumed.

In the present invention, the rubber contains at least one organic nickel salt selected from the group consisting of compounds represented by the following formulas (I), (II), (III), (IV) and (V). Let it.

(1) Equation (I)

R! COO-N i -OCOR ₂ (1),

(2) Equation (II)

R! O-Ni-OR ₂ (11),

(3) Formula (III)

R, S O N i-O S 0 R (III)

(4) Equation (IV)

Equation (5) )

In these formulas (I) to (V), and R ₂ each independently represent a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, an aromatic hydrocarbon group, an alkyl group, It is a group-substituted aromatic hydrocarbon group or alicyclic hydrocarbon group. However, since these compounds are organic nickel salts, in formulas (I) to (III), and and R ₂ are not both hydrogen atoms.

R! And R ₂ include, for example, H, CH ₃ —, C ₂ H ₅ , C 3 H ₇ —, C ₄ H ₉ —, (CH ₃ ) 3 CCH ₂ , n-C ₇ H ₁₅ —, iso one _{_{C 7 H 15 -, n- C}} uH "-, iso- C nH 23 -, n- C 17 H 25 -, iso - C 17 H 25 -, iso- C 24 H 49 _, C 8 H 17 CH = CH C ₇ H _14- , CH ₃ [(CH ₃ ) ₂ C] ₂ C ₆ H ₄ ―, C ₈ H ₁₇ C ₆ H ₄ ―, C ₉ H ₁₉ CH = CH-, CH ₃ C ₆ H ₄ _{_{_{one, (CH 3) 3 CC 6}}} H 4 -, [(CH 3) 3 C] 2 C 6 H 3 -, n- C 8 H 17 C 6 H 4 _{_{one, (CH 3) 3 CC 6}} H 10 - And the like.

R 1 and R ₂ may be linear, but the branched one is more excellent in the expression of adhesive strength. Among these organic nickel salts, those represented by the formulas (I) and (II) are particularly preferred.

Specific examples of the organic nickel salt of the formula (I) include (iso—C ₇ H ₁₅ COO) 2 Ni.

Specific examples of the organic nickel salt of the formula (II) include the following formula (Ila)

_{_{CH 3 [(C) 3 C}} ] 2 C 6 H 4 0- Ni-OC 6 H 4 [C (CH 3) 3] 2 CH 3 (Ila) The compound represented by these is mentioned.

Specific examples of the organic nickel salt of the formula (III) include the following formula (Ilia)

_{_{_{_{C a H 17 C 6 H 4}}}} S0 3 - compound represented by _{_{_{Ni- OS0 2 C 6 H 4 C}}} 8 H 17 (Ilia) can be mentioned.

Specific examples of the organic nickel salt of the formula (IV) include the following formula (IVa)

CH ₃ COCH = (CH ₃ ) CO—Ni—OC (CH ₃ ) = CHCOCH ₃ (IVa)

Specific examples of the organic nickel salt of the formula (V) include the following formula (Va)

The compound represented by these is mentioned.

As a method of incorporating these organic nickel salts into the rubber, an organic nickel salt may be generated in situ, in addition to a method of adding the already synthesized organic nickel salt to the rubber. For example, when nickel oxide or nickel particles and an organic acid are added to rubber and kneaded and heated, an organic nickel salt is generated. Therefore, an embodiment in which an inorganic nickel compound or the like and an organic acid are added in combination also falls within the scope of the present invention. The content of the organic nickel salt cannot be unambiguously determined as the nickel content because it is related to the molecular weight and the diffusivity of the molecule, but usually 0.1 to 15 parts by weight with respect to 100 parts by weight of rubber. It is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. Each of the organic nickel salts can be used alone, but if desired, two or more can be used in combination. Use a combination of two or more organic nickel salts. Thus, a more favorable result can be obtained in terms of the balance between the adhesiveness and the crosslinkability.

The rubber composition of the present invention includes reinforcing agents, fillers, stabilizers, lubricants, softeners, crosslinking regulators, vulcanization retarders, processing aids, processing oils, and the like, which are generally used in the rubber technical field. Can be contained. Examples of the reinforcing agent include various grades of carbon black such as HAF and ISA, and silica. Examples of the filler include calcium carbonate, _c these various additives and the like talc, are used in amounts required in accordance with the respective purposes.

The rubber composition of the present invention can be prepared by melt-kneading a rubber, a crosslinking agent, an organic nickel salt, and if necessary, other additives. To suppress premature cross-linking, it is preferable to melt-knead rubber and a reinforcing agent, and then mix and knead a bridging agent, a cross-linking accelerator, and an organic nickel salt. After kneading, the rubber composition can be shaped into a desired shape. As the metal material used in the present invention, a metal material having a higher ionization tendency than nickel is preferably used. The ionization tendency means the tendency of a metal to become a cation when it comes into contact with a liquid, particularly water, and can be quantitatively evaluated by the standard electrode potential of the metal. The order of metal elements in which the ionization tendency with respect to water is arranged in the order of the size is called the ionization sequence, which is arranged in the order of Mg, Al, Zn, Cr, Fe (II), Ni, and the like. In the present invention, a metal material composed of a metal having a higher ionization tendency than nickel or an alloy containing the metal is used. Preferred materials include, for example, iron, chromium, brass (copper-zinc alloy), zinc, aluminum, aluminum alloy, and magnesium. The metal material can have a desired shape such as a plate shape, a linear shape, a roll shape, and a net shape. Before bonding, the metal material can be subjected to a pretreatment such as degreasing, washing with water, phosphate treatment, monochromic phosphate treatment, and chromate rinse. In the present invention, Although plating treatment of a metal material is not required, plating treatment may be performed if desired.

In order to directly cross-link and adhere the rubber composition and the metal material, the rubber composition and the metal material may be cross-linked by heating under contact. For example, if a rubber composition formed into a desired shape such as a sheet and a metal material are brought into contact with each other and heated and pressed, crosslinking and bonding occur simultaneously. The specific method of direct cross-linking can be appropriately selected according to the shape of the metal material, the viscosity of the rubber composition, the type of the intended composite material, and the like. The heating temperature and the heating time can also be appropriately set according to the type of the rubber, the type of the crosslinking agent, and the like. For example, in the case of a rubber composition containing a general-purpose rubber such as SBR, NR, NBR, EPDM, etc., a heating time of about 140 to 200 ° C and a heating time of about 5 to 60 minutes are sufficient. A composite material having a high adhesive strength can be obtained.

Composite materials of rubber and metal materials include seismic isolation rubber, vibration damping rubber, vibration isolating rubber, packing, diaphragms, gaskets, large rubber rolls, rubber rolls for copiers, conveyor belts, reinforcing belts, and freeway escalators. Examples include handrails, car tires, metal fiber reinforced hoses, etc., and can be used in many fields such as electrical products, electronic products, computer products, automotive 'bus' trucks and airplane parts. Example

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In Examples and Comparative Examples, “parts” indicates parts by weight. The method for measuring the peel strength (adhesive strength) is as follows.

After bonding the rubber compound sheet to the metal plate and directly cross-linking and bonding in a mold (thickness = 3 mm), take out the sample, cut a 1 Omm into the cross-linked rubber layer, and use a tensile tester (tensile Velocity: Peel strength using 5 mm Z min) (Unit = kNZm) was measured.

[Example 1]

In accordance with the formulation shown in Table 1, 70 parts of styrene-butadiene rubber (SBR), 30 parts of natural rubber (NR), 50 parts of HAF bonbon black, 1 part of stearic acid, and zinc oxide (Zn〇 5 parts were mixed in a kneader and kneaded with two rolls to prepare an SBRZNR blended rubber master batch. Next, using a small experimental roll, 3.5 parts of sulfur and 4 parts of nickel salt [(iso—C ₇ H ₁₅ CO〇) 2 Ni] were mixed with the SB RZNR blend rubber masterbatch, An adhesive rubber sheet (thickness = 2.2 mm) was prepared. As a metal material, an aluminum plate (30 X 50 X lmm) obtained by cutting a commercially available pure aluminum plate was used, degreased with acetone and dried before bonding.

An aluminum plate and a rubber sheet for bonding were bonded together, placed in a mold (thickness == 3 mm), and heated and pressed with 16 O: for 30 minutes to directly crosslink and bond. After bonding, the composite material (adhesive) was taken out, a 10 mm cut was made in the crosslinked rubber sheet, and the peel strength (adhesive strength) was measured using a tensile tester (tensile speed = 5 mm Zmin). Table 1 shows the results.

[Example 2]

Except that t-butylbenzothiazylsulfenamide (BBS) was added as a vulcanization accelerator in the proportions shown in Table 1 when preparing an adhesive rubber sheet using a small experimental roll. Then, an adhesive rubber sheet was produced in the same manner as in the examples. Next, the aluminum sheet and the rubber sheet were bonded together, put into a mold, and heated and pressed at 160 ° C. for 10 minutes to directly crosslink and bond. Table 1 shows the results.

[Example 3]

Table 1 shows the dibenzothiazyl disulfide (MBTS) used as a vulcanization accelerator when preparing rubber sheets for bonding using small rolls for experiments. A rubber sheet for bonding was produced in the same manner as in Example except that the rubber sheet was further added. Next, the aluminum plate and the rubber sheet were bonded together, placed in a mold, and heated and pressed at 160 ° C. for 10 minutes to directly crosslink and bond. Table 1 shows the results.

[Comparative Example 1]

The production was performed in the same manner as in Example 1 except that no nickel salt was added when producing the bonding rubber sheet. Table 1 shows the results.

[Comparative Example 2]

The same procedure as in Example 2 was carried out except that no nickel salt was added and that the heating and pressing time was changed to 30 minutes when producing the rubber sheet for bonding. Table 1 shows the results.

[Comparative Example 3]

The same procedure as in Example 3 was carried out except that no nickel salt was added and that the heating and pressing time was changed to 30 minutes when producing the rubber sheet for bonding. Table 1 shows the results.

Table 1: Direct cross-linking adhesion between aluminum plate and SB RZNR blend

As is clear from the results in Table 1, when the rubber sheet to which the nickel salt was not added was used (Comparative Examples 1 to 3), the rubber sheet did not adhere to the aluminum plate. In contrast, a vulcanizing agent in the rubber sheet _{_{(iso - C 7 H 15 COO}} ) 2 N if i coexist (Examples 1 3), high peel strength composite (adhesin) is obtained. In the case of Example 1, (iso— C ₇ H ₁₅ C OO) ₂ Ni also serves as a vulcanization accelerator. When t-butylbenzothiazylsulfenamide (BBS) and dibenzothiazyldisulfide (MBTS) are added as a vulcanization accelerator (Examples 2 and 3), the bonding speed is further increased, and The peel strength also increases.

[Example 4]

An SBRZNR blended rubber masterbatch was prepared in the same manner as in Example 1. Next, using a small experimental roll, 4.0 parts of sulfur and the following nickel salt (Ila)

CH ₃ [(CH ₃ ) ₃ C] ₂ C ₆₀ -Ni-OC ₆ H ₄ [C (CH ₃ ) ₃ ] ₂ CH ₃ (Ila) 0.5 part, and t-butylbenzothiazylsulfenami (BBS) 0.5 part was mixed with one batch of S BRZNR blended rubber master to prepare an adhesive rubber sheet (thickness = 2 mm). As a metal material, a zinc plate (30 X 50 X lmm) that was degreased with acetone, activated with an aqueous acetic acid solution, washed with water, and dried was used. The zinc plate and the rubber sheet for bonding were bonded together, and heated and pressed in a mold at 160 ° C. for 30 minutes to directly crosslink and bond to obtain a composite material (adhesive). Table 2 shows the results.

[Example 5]

Nickel salt (Ila) is replaced with the following nickel salt (Ilia)

_{_{_{_{C 8 H 17 C 6 H 4}}}} S0 3 - Ni - OS0 except that instead of _{_{_{_{2 C 6 H 4 C B H}}}} 17 (Ilia), was performed in the same manner as in Example 4. Table 2 shows the results.

[Example 6]

Nickel salt (Ila) is replaced with the following nickel salt (IVa)

The same operation as in Example 4 was performed, except that CH ₃ COCH— (CH ₃ ) CO—Ni—OC (CH ₃ ) —CHCOCH ₃ (IVa) was used instead. Table 2 shows the results. [Example 73

Nickel salt (Ila) is replaced with the following nickel salt (Va)

The procedure was performed in the same manner as in Example 4 except that Table 2 shows the results.

[Comparative Example 4]

The same operation as in Example 4 was performed except that no nickel salt (Ila) was used. Table 2 shows the results.

Table 2: Direct cross-linking between zinc plate and SBR No NR blend

As is clear from the results in Table 2, when various nickel salts are present in the rubber (Examples 4 to 7), a composite material having good peel strength can be obtained. On the other hand, when the nickel salt is not present in the rubber (Comparative Example 4), the zinc plate and the rubber sheet do not adhere.

[Example 8]

According to the formulation shown in Table 3, 100 parts of chlorine-based acrylic rubber (AR), 50 parts of HAF carbon black and 1 part of stearic acid were mixed in a kneader and kneaded with two rolls to prepare one batch of AR rubber master. Next, using a laboratory size roll, triazine trithiol 0.5 parts, benzothiazole zinc salt (BZ) 1. 0 parts, and nickel salts [(iso- C ₇ H ₁₅ C_〇_〇) 2 N i] Four parts were mixed with an AR rubber masterbatch to produce an adhesive rubber sheet (thickness = 2.2 mm). As the metal material, a commercially available aluminum plate (30 × 50 × 1 mm) obtained by cutting a pure aluminum plate was degreased with acetone and then dried. The aluminum sheet and the rubber sheet for bonding were bonded together, placed in a mold (thickness = 3 mm), heated and pressed at 160 ° C for 30 minutes, and directly cross-linked to obtain a composite material. Table 3 shows the results.

[Example 9]

An NBR rubber masterbatch was prepared in the same manner as in Example 8, except that the chlorinated acryl rubber was changed to acrylonitrile butadiene rubber (NBR; acrylonitrile content = 31%). Next, using a laboratory size opening one Le, triazine trithiol 1.5 parts of bis one t - butyl per O key Consequences isopropyl benzene 5 parts, and nickel salts [(iso- C ₇ H ₁₅ C_〇_〇) _[ 2Ni] 4 parts were mixed in a batch of NBR rubber mass to prepare an adhesive rubber sheet (thickness = 2.2 mm). Thereafter, a composite material was produced in the same manner as in Example 8. Table 3 shows the results.

[Example 10]

An EPDM rubber masterbatch was prepared in the same manner as in Example 8, except that the chlorine-based acrylic rubber was replaced by ethylene-propylene-gen rubber (EPDM; gen = ethylidene norporene). Next, using a laboratory size roll, triazine trithiol 1.5 parts of 2, 5-dimethyl Chiruji t- to Buchiruperuokishi relaxin 5 parts, and nickel salts [(iso _ C ₇ H ₁₅ C_〇_〇) 2 N i] 4 parts EPDM rubber masterbatch To prepare an adhesive rubber sheet (thickness = 2.2 mm). Thereafter, a composite material was produced in the same manner as in Example 8. Table 3 shows the results.

[Comparative Example 5]

The same procedure as in Example 8 was carried out except that no nickel salt was added when producing the rubber sheet for bonding. Table 3 shows the results.

[Comparative Example 6]

The same procedure as in Example 9 was carried out except that no nickel salt was added when producing the rubber sheet for bonding. Table 3 shows the results.

[Comparative Example 7]

The production was performed in the same manner as in Example 10 except that no nickel salt was added when producing the bonding rubber sheet. Table 3 shows the results.

Table 3: Influence of rubber type and crosslinking system on adhesion to aluminum plate

Each formulation shown in Comparative Examples 5 to 7 in Table 3 is a formulation that adheres to the nickel plating treated surface in the nickel plating method. However, as can be seen in Comparative Examples 5-7, these formulations did not Does not adhere at all. On the other hand, in each of the formulations of Examples 8 to 10, since the nickel salt is contained, it can be seen that the aluminum plate and various rubber sheets can be directly cross-linked and adhered.

[Example 11]

In the same manner as in Example 2, an SBRZNR blended rubber master batch and an adhesive rubber sheet were prepared. As the metal material, a soft iron plate (30 × 50 × I mm) obtained by degreasing with acetone and then drying was used. The soft iron plate and the bonding rubber sheet were bonded together, placed in a mold (thickness = 3 mm), and heated and pressed at 160 ° C for 30 minutes to directly crosslink and bond. Table 4 shows the results.

[Example 12]

Example 11 was repeated except that the soft iron plate was replaced by a brass plate (30 X 5 O X l mm) which was degreased with acetone and dried. Table 4 shows the results.

[Example 13]

Example 11 was repeated except that the soft iron plate was replaced with a magnesium plate (30 X 5 O X l mm) which was degreased with acetone and dried. Table 4 shows the results.

[Comparative Example 8]

The production was performed in the same manner as in Example 11 except that no nickel salt was added when producing the rubber sheet for bonding. Table 4 shows the results.

[Comparative Example 9]

The production was performed in the same manner as in Example 12 except that no nickel salt was added when producing the bonding rubber sheet. Table 4 shows the results.

[Comparative Example 10]

The production was performed in the same manner as in Example 13 except that no nickel salt was added when producing the bonding rubber sheet. Table 4 shows the results. Table 4: Direct cross-linking of metal materials and SBR / NR blends

The vulcanizing agent and _{_{(iso _ C 7 H 15 COO}} ) 2 N if i and was used Gomushi one you want to coexist (Example 1 1-1 3), iron, brass plate, and good in magnetic Shiumu plate It shows excellent adhesiveness. On the other hand, when a rubber sheet containing no nickel salt is used (Comparative Examples 8 to 10), no adhesion is made to these metal plates.

Claims

INDUSTRIAL APPLICABILITY According to the present invention, by using a rubber composition containing an organic nickel salt in an uncrosslinked rubber containing a crosslinking agent, a metal material comprising a metal having a higher ionization tendency than Nigel Cross-linking between rubber and rubber is possible. Conventionally, in order to directly cross-link and bond a metal material and a rubber, a surface treatment of the metal material is performed, but according to the manufacturing method of the present invention, In addition, plating and bonding can be performed substantially simultaneously, and there is a dramatic improvement over the prior art in this regard. In particular, the use of aluminum, magnesium, and alloys of these metals, which have a higher ionization tendency than nickel, is also significant in terms of supplying methods and materials for achieving the 21st century's challenges of recycling and energy saving. is there. INDUSTRIAL APPLICABILITY The present invention can be applied to many types of composites of rubber and metal materials, and these composites can be inexpensive products having features of recycling and energy saving. The scope of the claims

1. rubber, crosslinker, and

(1) Equation (I)

R! COO-N i -OCOR ₂ (1),

(2) Equation (Π)

R! O-Ni-OR ₂ (11),

(3) Formula (III)

RJSO 3-Ni-OSO 2 R ₂ (III)

(4) Equation (IV)

as well as

Equation (5)

(In each formula, ェ and R ₂ are each independently a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, an aromatic hydrocarbon group, an alkyl-substituted aromatic hydrocarbon. A rubber composition comprising at least one organic nickel salt selected from the group consisting of compounds represented by the formula:

2. Rubber is natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, styrene-isoprene rubber, butadiene-isoprene rubber, butylene rubber, halogenated butyl rubber, ethylene-propylene rubber, ethylene 2. The rubber composition according to claim 1, wherein the rubber composition is selected from propylene-one-gen rubber, acrylic rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber, urethane rubber, and a mixture thereof.

3. The rubber composition according to claim 1, wherein the crosslinking agent is selected from sulfur, triazinethiols, resin crosslinking agents, polyol crosslinking agents, peroxides, and mixtures thereof.

4. The rubber composition according to claim 1, wherein the content of the crosslinking agent is 0.1 to 5 parts by weight based on 100 parts by weight of the rubber.

5. The rubber composition according to claim 1, further comprising a metal activator selected from ZnO, MgO, CaO, Ca (OH) ₂ , and a mixture thereof.

6. The rubber composition according to claim 5, wherein the content of the metal activator is 1 to 20 parts by weight based on 100 parts by weight of the rubber.

In 7. formula (I) to the compound represented by (V), and R _{_2, H, CH 3 -, C} 2 H 5 -, C 3 H 7 -, C 4 H 9 -, (CH 3) 3 CCH 2 _{_{one, n - C 7 H 15 -}} , iso- C 7 H 15 -, n - C j jH 23 -, iso- C 11 H 23 _> n- C 17 H 25 -, iso- C 17 H 25 _{_{-, iso - C 24 H 49}} -, C 8 H 17 CH = CHC 7 H 14 -, CH 3 [(CH 3) 2 C] 2 C 6 H 4 _{_{_{one, C 8 H 17 C 6 H}}} 4 one, C ₉ H ₁₉ CH = CH—, C H 3 C ₆ H 4 (CH 3) 3 CC ₆ H-, [(CH ₃ ) 3 C] ₂

Selected from C _R 6 H ¹丄 3 n -C ₈ H ₁₇ C 6 H 1 and (CH ₃ ) 3 CC ₆ H ₁₀ [wherein in formulas (I) to (III), any one of R ₂ One is not H. ] The rubber composition according to claim 1.

Organic nickel salts of 8. formula _{_{(I), (iso _ C 7 H 15}} C OO) according to claim 1 rubber composition wherein the ₂ N i.

9. The organic nickel salt of the formula (II) is

_{_{_{CH 3 [(CH 3) 3}}} C] 2 C 6 H 4 0 -Ni- OC 6 H 4 [C (CH 3) 3] 2 CH 3 rubber composition of claim 1 wherein the is a compound represented by (Ila) object,

10 0. The organic nickel salt of formula (III) is

_{_{_{_{C 8 H 17 C 6 H 4}}}} S0 3 - Ni-OS0 2 C e H 4 C 8 H 17 The rubber composition according to claim 1, wherein the compound represented by (Ilia), and organic nickel salts of formula (IV) , The formula (IVa)

CH ₃ COCH = (CH ₃ ) CO-Ni-OC (CH ₃ ) = CHCOCH ₃ (IVa) is a compound represented by the rubber composition according to claim 1,

2. The organic nickel salt of the formula (V) is converted to the formula (Va)

2. The rubber composition according to claim 1, which is a compound represented by the formula:

1 3. The rubber composition according to claim 1, wherein the content of the organic nickel salt is from 0.1 to 15 parts by weight based on 100 parts by weight of the rubber.

1 4. Rubber, crosslinker, and

(1) Equation (I)

R! COO-N i -OCOR ₂ (1),

(2) Equation (II)

R! O-Ni-OR ₂ (11),

(3) Formula (III)

R! SO 3-Ni-OS 0 ₂ R 2 (III)

(4) Equation (IV)

as well as

Equation (5)

(In each formula, and R ₂ are each independently a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, an aromatic hydrocarbon group, an alkyl-substituted aromatic hydrocarbon group. Or an alicyclic hydrocarbon group.) A rubber composition (A) containing at least one kind of organic nickel salt selected from the group consisting of the compounds represented by), and having a greater ionization tendency than nickel. A composite material obtained by directly cross-linking and bonding a metal or a metal material (B) made of an alloy containing the metal. 15. The composite material according to claim 14, wherein the metal having a higher ionization tendency than nickel or an alloy containing the metal is selected from iron, chromium, zinc, aluminum, magnesium, and these alloys.

16. The composite material according to claim 15, wherein the alloy is brass (copper-zinc alloy) or an aluminum alloy.

1 7. Rubber, crosslinker, and

(1) Equation (I)

R! C OO -N i-0 C 0 R ₂ (1),

(2) Equation (Π)

R! O-Ni-OR ₂ (11),

(3) Formula (III)

R, S 0 ₃ -N i-OS 0 ₂ R ₂ (III), (4) Equation (IV)

as well as

Equation (5)

(In each formula, and R ₂ are each independently a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, an aromatic hydrocarbon group, an alkyl-substituted aromatic hydrocarbon group, Or an alicyclic hydrocarbon group.) A rubber composition (A) containing at least one organic nickel salt selected from the group consisting of compounds represented by the following formulas: and a metal or a metal having a higher ionization tendency than nickel. A method for producing a composite material in which a metal material (B) made of an alloy containing the metal is heated in contact with and directly cross-linked and adhered.

18. The production method according to claim 17, wherein the rubber composition (A) and the metal material (B) are heated in contact with each other at a heating temperature of 140 to 200 ° C for 5 to 60 minutes.

19. The method according to claim 17, wherein the metal material (B) is selected from iron, chromium, zinc, aluminum, magnesium, and alloys thereof.