JP4577140B2 - Rubber metal laminate - Google Patents

Description

  The present invention relates to a rubber metal laminate. More specifically, the present invention relates to a rubber metal laminate excellent in wear resistance and heat resistance.

In a portion where the temperature change is large, such as an engine gasket portion, fretting occurs between the joint surfaces of the engine and the gasket due to the temperature change. Due to this fretting, a large shear stress is generated in the gasket, and the rubber layer peels off or wears due to the friction between the rubber and the metal. As a result, the rubber layer is peeled off from the metal.

Carbon black is generally added for the purpose of improving the friction resistance and wear resistance of rubber, but it is difficult to prevent the rubber layer from being worn or peeled off in the above-mentioned applications.

In addition, a method of applying a resin coating agent such as polytetrafluoroethylene (PTFE) or polyethylene resin on the surface of the rubber layer to reduce the friction coefficient and reducing rubber wear is also performed. However, there is a problem that the rubber wears instantaneously due to peeling or wear of the coating agent, and it is desired to improve the friction resistance and wear characteristics of the rubber layer itself.

Here, in the rubber metal laminate, in order to improve the wearability, it is necessary to improve the adhesion with the metal in addition to the wearability of the rubber layer itself. That is, if the adhesion is poor, even if the rubber does not wear during friction and wear, the rubber layer will peel off, and even if the adhesion is excellent, if the abrasion resistance of the rubber is poor The rubber layer will be worn out.

In Patent Document 1, a primer layer composed of a phenol resin and an NBR compound and a vulcanized rubber layer formed from the NBR compound are sequentially laminated on one side or both sides of a metal plate to form a primer layer and a vulcanized rubber layer. As an NBR compound to be used, a rubber laminated metal plate using NBR and a rubber compound containing 20% by weight or more of a white filler, carbon black, zinc oxide and an organic peroxide has been proposed. However, although such a rubber laminated metal plate is excellent in adhesiveness, the rubber layer itself does not have satisfactory wear resistance.
JP-A-6-335990

  On the other hand, in order to form a composite of metal and rubber that requires resistance to water or long life coolant (LLC), stainless steel is often used as the metal, but vulcanized adhesive directly on stainless steel When rubber is applied and vulcanized and bonded to rubber, the resulting rubber-stainless steel composite has poor water resistance and LLC resistance. When these immersion tests are performed, adhesion peeling occurs. As a countermeasure, as a pretreatment for applying a vulcanized adhesive, a coating type chromate treatment is performed on stainless steel to improve resistance to water and LLC. However, the coating-type chromate treatment is not preferable from the viewpoint of environmental measures because it contains Cr ions.

Further, in Patent Document 2, in a laminated metal gasket material plate in which a rubber layer is provided on a metal plate via an adhesive layer, a silica-alumina condensate is formed between the surface of the metal plate and the adhesive layer. A metal gasket material plate on which a primer layer is formed has been proposed. However, even with such a metal gasket material plate, although the adhesiveness and the abrasion resistance of the primer layer are good, the primer layer is hard, and when the rubber is thermally deteriorated, the adhesiveness is poor and the primer layer may break.
JP 2003-028307 A

Object of the present invention to enhance the adhesion of the rubber layer after wear or thermal degradation of the rubber layer due to fretting of the rubber-metal laminate, rubber-metal laminate which allows allowed to prevent peeling and cracking of the rubber layer It is to provide.

  An object of the present invention is to provide a rubber metal laminate in which an adhesive layer and a rubber layer are sequentially laminated on one side or both sides of a metal plate, wherein the rubber layer has 3 to 100 white carbons per 100 parts by weight of nitrile rubber. This is achieved by a nitrile rubber metal laminate formed of a vulcanized product of a nitrile rubber composition containing 10 parts by weight of aluminum oxide and 10 to 200 parts by weight of aluminum oxide having an average particle size of 0.1 to 10 μm.

A vulcanizate obtained from a nitrile rubber composition containing white carbon and aluminum oxide having an average particle size of 0.1 to 10 μm almost loses mechanical strength (normal physical properties) as in the case of adding carbon black to nitrile rubber. On the other hand, there is an excellent effect of improving the wear resistance and not lowering the adhesiveness of the rubber layer after heat deterioration.

  Furthermore, as the filler, white carbon that enables low friction and improved adhesion to the adhesive is selected, and aluminum oxide is added to white carbon, which is inferior to carbon black that is generally used in terms of wear resistance. By adding, it is possible to improve the wear resistance without lowering the adhesion, and the rubber metal laminate with improved adhesion between the rubber layer and the adhesive layer and the wear resistance of the rubber layer itself Can be given.

Nitrile rubber layer As the nitrile rubber (NBR), acrylonitrile having a bound acrylonitrile content of 18 to 48%, preferably 31 to 42%, and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 30 to 85, preferably 40 to 70 -Butadiene copolymer rubber is used, and a commercially available product can be used as it is. If the amount of bound acrylonitrile is less than this, the adhesion between the rubber layer and the adhesive layer becomes poor, while if the amount of bound acrylonitrile is larger than this, the cold resistance is impaired. On the other hand, if the Mooney viscosity is smaller than this, the friction and wear properties are poor, while if the Mooney viscosity is larger than this, the kneading processability is impaired. To this NBR, white carbon, aluminum oxide, vulcanizing agent, vulcanization accelerator, anti-aging agent and the like are added, and the nitrile rubber composition used for forming the rubber layer of the rubber metal laminate of the present invention is obtained. Prepared.

White carbon (reinforcing silica) includes dry-type white carbon produced by thermal decomposition of halogenated silicon or organosilicon compounds, heat reduction of silica sand, and air oxidation of vaporized SiO. A wet method white carbon produced by a thermal decomposition method of sodium acid, etc., and amorphous silica can be used, and commercially available products such as Nipsil LP, a Japanese silica industrial product, are used as they are. Further, those having a specific surface area of about 30 to 200 m ² / g, preferably about 30 to 100 m ² / g are generally used. White carbon is less in wear resistance than commonly used carbon black due to its price, handleability, and wear resistance, but improves the adhesion between the rubber layer and the adhesive layer. Make it possible.

  These white carbons are used in a ratio of about 3 to 100 parts by weight, preferably about 10 to 80 parts by weight per 100 parts by weight of NBR. If the blending ratio is less than this, the desired adhesiveness cannot be obtained, so that the rubber layer is peeled off during friction and wear. On the other hand, if it is used at a higher ratio, the rubber hardness becomes very high and the rubber elasticity is lost.

  As the aluminum oxide, those having an average particle diameter (measured by a laser diffraction method) of 0.1 to 10 μm, preferably 0.5 to 5 μm are used. When the average particle size is larger than this, the rubber portion is worn by the aluminum oxide particles, and the wear resistance is lowered. Here, the aluminum oxide is used at a ratio of about 10 to 200 parts by weight, preferably about 60 to 150 parts by weight per 100 parts by weight of NBR. If the proportion of aluminum oxide used is less than this, the effect of improving the wear resistance aimed at by the present invention cannot be obtained. On the other hand, if it is used in a proportion higher than this, kneadability and normal physical properties are deteriorated. Become. Also, the greater the amount of aluminum oxide, the better the wear resistance.

  In the nitrile rubber composition, in addition to the above essential components, other than polyfunctional unsaturated compounds such as triallyl (iso) cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, activated calcium carbonate, etc. Reinforcing agent, fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, palmitic acid, paraffin wax, acid acceptors such as zinc oxide, magnesium oxide, hydrotalcite, anti-aging agent Various compounding agents generally used in the rubber industry, such as plasticizers such as dioctyl sebacate (DOS), are appropriately added and used.

  The nitrile rubber composition comprising the above ingredients can be vulcanized by any vulcanization system such as sulfur vulcanization or peroxide vulcanization, either alone or in combination. Sulfur is preferred. As the vulcanization accelerator, processing aid, acid acceptor, anti-aging agent, etc., general commercially available products can be used according to the vulcanization system used.

  The composition is prepared by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll, and the vulcanization is performed by an injection molding machine, a compression molding machine, a vulcanizing press, and an oven vulcanization. Secondary vulcanization is generally performed by heating at about 160 to 250 ° C. for about 0.5 to 30 minutes, and further heating at about 150 to 250 ° C. for about 30 seconds to 10 hours as necessary. Done.

  Further, when the nitrile rubber composition is applied by dissolving in a solvent, the nitrile composition is prepared by dissolving and dispersing the nitrile composition in the solvent without kneading or kneading only a part of the raw materials. A dispersion solution is prepared.

  The vulcanized product of the above nitrile rubber composition is laminated as a nitrile rubber layer through an adhesive layer, preferably a primer layer and an adhesive layer formed on a metal plate.

As the metal plate , a stainless steel plate, a mild steel plate, a galvanized steel plate, a SPCC steel plate, a copper plate, a magnesium plate, an aluminum plate, an aluminum die cast plate, or the like is used. These are generally used in a degreased state, and the surface of the metal is roughened by shot blasting, scotch bride, hairline, dull finishing or the like as necessary. The plate thickness is generally about 0.1 to 1 mm.

  A primer layer is preferably formed on these metal plates. Although the primer layer is not an indispensable requirement for improving the wear resistance of the rubber layer which is the object of the present invention, it can be expected that the heat resistance and water resistance required for rubber adhesion of the rubber metal laminate are greatly improved. In particular, when a rubber metal laminate is used as a sealing material, it is desirable to form it.

Primer layer As the primer layer, zinc phosphate film, iron phosphate film, vanadium, zirconium, titanium, molybdenum, tungsten, manganese, zinc, cerium compounds or oxides thereof such as silane, phenol, epoxy, A commercially available chemical solution or a known technique such as an organic coating such as urethane can be used as it is, but preferably a primer layer containing an organometallic compound having at least one chelate ring and an alkoxy group, A primer layer in which a metal oxide or silica is added to this, more preferably a primer layer in which a hydrolysis condensation product of an amino group-containing alkoxysilane and a vinyl group-containing alkoxysilane is added to these primer layer forming components. This hydrolysis-condensation product can be used alone.

R：CH₃、C₂H₅、n-C₃H₇ 、i-C₃H₇、n-C₄H₉、i-C₄H₉などの低級アルキ
ル基
n：1〜4の整数
で表されるキレート環およびアルコキシ基から構成される有機チタン化合物が用いられる。 Examples of organometallic compounds include ethylacetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), aluminum-mono-acetylacetonate-bis (ethylacetoacetate), aluminum tris (acetylacetate) and other organoaluminum compounds, Organic titanium compounds such as propoxytitanium bis (ethyl acetoacetate), 1,3-propanedioxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (acetylacetonate), titanium tetra (acetylacetonate), di-n-butoxyzirconium And organic zirconium compounds such as bis (acetylacetonate) and di-n-butoxyzirconium bis (ethylacetoacetate).

R: Lower alkyl such as CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , iC ₃ H ₇ , nC ₄ H ₉ , iC ₄ H ₉
Le group
n: An organic titanium compound composed of a chelate ring represented by an integer of 1 to 4 and an alkoxy group is used.

  As the metal oxide added to the primer layer in the same manner as silica, alumina, titanium oxide, manganese oxide, zinc oxide, magnesium oxide, zirconium oxide, or the like is used. The metal oxide is used in a weight ratio of 0.9 or less, preferably 0.45 or less with respect to the organometallic compound. If the amount of the metal oxide is used more than this, mixing of the metal oxide in the primer component becomes difficult, which is not preferable.

  Examples of amino group-containing alkoxysilanes that form hydrolytic condensation products include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropyltrimethoxysilane, and the like. Used. As the vinyl group-containing alkoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, or the like is used. These alkoxysilanes can be hydrolyzed by mixing amino group-containing alkoxysilanes and water, adjusting the pH to the acidic side, and then maintaining the temperature at 40 to 60 ° C. and adding vinyl group-containing alkoxysilanes while stirring. Simultaneously with the reaction, a hydrolytic condensate is produced by a polycondensation reaction. Here, the vinyl group-containing alkoxysilane is mixed in an amount of 25 to 400 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the amino group-containing alkoxysilane. The obtained hydrolysis condensate is used in a weight ratio of 3 or less, preferably 1.5 or less, with respect to the organometallic compound. When the amount of the hydrolyzed condensate is larger than this, the compatibility with the adhesive is deteriorated and the adhesiveness is lowered.

  The primer composed of the above components is prepared as a solution of an organic solvent, for example, alcohols such as methanol, ethanol and isopropyl alcohol, and ketones such as acetone and methyl ethyl ketone, so that the solid content concentration is about 0.2 to 5% by weight. Prepared. Such organic solvent solution can be mixed with 20% by weight or less of water as long as the liquid stability is maintained.

The obtained primer solution is applied on a metal plate by spraying, dipping, brush, roll coater, etc., with a basis weight of about 50 to 200 mg / m ² , dried at room temperature or hot air, A primer layer is formed by baking at about 100 to 250 ° C. for about 0.5 to 20 minutes.

Adhesive layer As the adhesive, commercially available adhesives such as silane, phenol, epoxy, and urethane can be used as they are, but preferably novolak type phenol resins and resol type phenol resins are used. An adhesive consisting of two types of phenolic resin and unvulcanized NBR can be used.

  The novolac type phenolic resin includes phenol, p-cresol, m-cresol, p-tert-butylphenol, etc., 2 or 3 substitutable nuclear hydrogen atoms in the o-position and / or p-position with respect to the phenolic hydroxyl group. A resin having a melting point of 80 to 150 ° C., preferably m-cresol and formaldehyde, obtained by a condensation reaction of phenols having a salt or a mixture thereof with formaldehyde in the presence of an acid catalyst such as oxalic acid, hydrochloric acid, maleic acid, etc. Those having a melting point of 120 ° C. or higher produced from

  Resol-type phenolic resins include phenol, p-cresol, m-cresol, p-tert-butylphenol, etc., 2 or 3 substitutable nuclear hydrogen atoms in the o-position and / or p-position with respect to the phenolic hydroxyl group What is obtained by subjecting phenols having a hydrogen atom or a mixture thereof and formaldehyde to a condensation reaction in the presence of an alkali catalyst such as ammonia, an alkali metal hydroxide, or magnesium hydroxide is used.

  Uncured NBR includes commercially available very high nitrile content (nitrile content 43% or more), high nitrile content (36-42%), medium-high nitrile content (31-35%), medium nitrile content ( Various NBRs having a nitrile content of 25-30% and a low nitrile content (24% or less) can be used as they are, but those having a medium-high nitrile content are preferably used.

  Adhesives containing these components are dissolved in organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, or a mixed solvent thereof and used as a liquid. .

  Each of the above components forming a preferred adhesive is 10 to 1000 parts by weight of a resol type phenol resin, preferably 60 to 400 parts by weight and 30 to 3000 parts by weight of unvulcanized NBR, with respect to 100 parts by weight of a novolak type phenol resin. Preferably, it is used at a ratio of 60 to 900 parts by weight. Each of these components is prepared as a vulcanized adhesive by adding an organic solvent, mixing and stirring so that the total concentration of the components is about 3 to 10%. When the resol type phenol resin is used more than this, the adhesiveness of the high nitrile rubber material is lowered. On the other hand, when it is less than this, the adhesiveness with the metal surface is lowered, which is not preferable. Moreover, when unvulcanized NBR is used more than this, the adhesiveness with a metal surface will fall, and a viscosity rise will be large, and it will interfere with application | coating operation | work. On the other hand, if the amount is less than this, the compatibility with the nitrile rubber to be bonded is lowered, resulting in poor adhesion. Preparation of an adhesive using each of these components is performed by dissolving a predetermined amount of each component in an organic solvent, mixing, and stirring.

  Formation of the adhesive layer on the metal plate is preferably performed by applying the adhesive on the metal plate on which the primer layer is formed and air-drying at room temperature, and then at about 100 to 250 ° C. for about 5 to 30. It is performed by drying for about a minute.

  The adhesive layer can have not only a single layer structure but also a multilayer structure. For example, a phenolic adhesive layer containing an organometallic compound is formed immediately above the primer layer, and a phenolic adhesive layer containing the nitrile rubber composition is further provided thereon to apply the adhesive in multiple stages. And a rubber layer formed thereon. By adopting such a configuration, it is possible to further strengthen the adhesion between the primer layer and the rubber layer, although the application process of the adhesive layer increases.

  For the purpose of preventing the adhesion of rubber, a coating agent such as resin or graphite can be applied on the rubber layer.

  Next, the present invention will be described with reference to examples.

Example 1
A primer composed of 2.5 parts by weight of titanium tetra (acetylacetonate), 0.5 parts by weight of silica (SiO ₂ ) and 97 parts by weight of methanol is applied to the surface of a 0.2 mm thick stainless steel plate (Nisshin Steel SUS301) that has been degreased with alkali. Then, a primer layer was formed, and an adhesive having the following composition was formed on the entire surface of the primer layer with a thickness of one side of about 0.2 μm.
400 parts by weight of cresol-modified novolac phenolic resin
(Dai Nippon Ink Chemical Products KA-1053L solid content 40%)
Resol type phenolic resin 211 〃
(Dainippon Ink and Chemicals AF-2639 solid content 60%)
Unvulcanized NBR (JSR product N-237) 99 〃
Methyl ethyl ketone 2965 〃
Toluene 2965 〃

On the formed adhesive layer, a nitrile rubber composition obtained by kneading the following components using a kneader and an open roll, toluene: methyl ethyl ketone = 9: so that the solid content concentration is 25% by weight. A solution dissolved in one mixed solvent was applied to a thickness of 20 μm and vulcanized at 230 ° C. for 3 minutes.
Nitrile rubber (JSR product N235S; nitrile content 36%) 100 parts by weight White carbon (Nippon Silica product nip seal LP) 20 部
Aluminum oxide (Nippon Light Metal Products A32: average particle size 1μm) 120 〃
Zinc oxide 5 〃
Stearic acid 1.5 〃
FEF carbon black 40 〃
Anti-aging agent (Nocrac 224, a new chemical product from Ouchi) 2 〃
Sulfur 2 〃
Vulcanization accelerator (Ouchi Emerging Chemicals Noxeller TT) 2〃
Vulcanization accelerator (Ouchi Emerging Chemicals Noxeller CZ) 2 〃

  The formed vulcanized rubber surface is coated with a toluene dispersion of polyethylene resin to which a polybutadiene resin binder has been added for the purpose of preventing its sticking, and subjected to heat treatment by air heating at 200 ° C. for 5 minutes to a thickness of 5 μm. An anti-adhesion layer was formed.

Example 2
In Example 1, the same amount of ZrO ₂ was used instead of the primer component SiO ₂ .

Example 3
In Example 1, the same amount of di-n-butoxyzirconium bis (ethylacetoacetate) was used in place of titanium tetra (acetylacetonate) which is a primer component.

Example 4
In Example 1, di n-butoxyzirconium bis (ethyl acetoacetate) was used in place of the primer component titanium tetra (acetylacetonate), and ZrO ₂ was used in the same amount in place of SiO ₂ .

Example 5
In Example 1, a nitrile rubber composition having an aluminum oxide content changed to 40 parts by weight and a carbon black content changed to 80 parts by weight was used.

Example 6
In Example 1, a nitrile rubber composition having a white carbon amount changed to 60 parts by weight and a carbon black amount changed to 5 parts by weight was used.

Example 7
In Example 1, a nitrile rubber composition having a white carbon content of 60 parts by weight, an aluminum oxide content of 40 parts by weight, and a carbon black content of 80 parts by weight was used.

Example 8
In Example 1, as a nitrile rubber composition, 2.5 parts by weight of 1,3-bis-tert-butylperoxyisopropylbenzene was used instead of sulfur, and the vulcanization accelerator was (N-isopropyl-N′-phenyl-p-phenylene). Diamine) Triallyl isocyanurate was used in a modified form of 2 parts by weight, and further vulcanization was carried out by changing to press vulcanization at 180 ° C. for 6 minutes.

Example 9
In Example 1, an adhesive having the following composition was used.
400 parts by weight of cresol-modified novolac phenolic resin
(KA-1053L 40% solid content)
Resol type phenolic resin (AF-2639 solid content 60%) 975 〃
Unvulcanized NBR (N-237) 306 〃
Methyl ethyl ketone 9360 〃
Toluene 9360 〃

Example 10
In Example 1, an adhesive having the following composition was used.
400 parts by weight of cresol-modified novolac phenolic resin
(KA-1053L 40% solid content)
Resol type phenolic resin (AF-2639 solid content 60%) 65 〃
Unvulcanized NBR (N-237) 60 〃
Methyl ethyl ketone 1748 〃
Toluene 1748 〃

Example 11
In Example 1, when the primer layer was formed, a primer composed of 1.5 parts by weight of titanium tetra (acetylacetonate), 0.5 parts by weight of ZrO _2, 1 part by weight of alkoxysilane hydrolysis condensate and 97 parts by weight of methanol was used. In addition, the alkoxysilane hydrolysis-condensation product used here was manufactured as follows.

  A flask equipped with a stirrer, a heating jacket and a dropping funnel is charged with 40 parts by weight of γ-aminopropyltriethoxysilane and 20 parts by weight of water, and prepared by adding acetic acid so that the pH is 4-5, and for several minutes. Stir. While further stirring, 40 parts by weight of vinyltriethoxysilane was gradually added dropwise using a dropping funnel. After completion of dropping, the mixture was heated to reflux at a temperature of about 60 ° C. for 5 hours and cooled to room temperature to obtain an alkoxysilane hydrolyzed condensate.

Example 12
In Example 1, when forming the primer layer, a primer comprising 1.5 parts by weight of di-n-butoxyzirconium bis (ethylacetoacetate), 0.5 parts by weight of ZrO _2, 1 part by weight of the above alkoxysilane hydrolysis condensate and 97 parts by weight of methanol Was used.

Example 13
In Example 1, when the primer layer was formed, a primer composed of 1.5 parts by weight of titanium tetra (acetylacetonate), 1 part by weight of the above alkoxysilane hydrolysis condensate and 97.5 parts by weight of methanol was used.

Example 14
In Example 1, a primer composed of 1 part by weight of the alkoxysilane hydrolysis condensate and 99 parts by weight of methanol was used for forming the primer layer.

Example 15
In Example 1, the primer layer was not formed.

Example 16
In Example 1, a silane-based adhesive (Lord Far East product Chemlock AP-133) was used in forming the primer layer.

Example 17
In Example 1, a zirconium-based surface treatment agent (Nippon Parkerizing Product Palcoat 3762) was used in forming the primer layer.

Reference Example In Example 1, a primer layer was formed with a Japanese Parkerizing product chromate treatment agent.

Comparative Example 1
In Example 1, no adhesive was used.

Comparative Example 2
In Example 1, a nitrile rubber composition in which the same amount of calcium carbonate was used instead of aluminum oxide was used.

Comparative Example 3
In Example 1, a nitrile rubber composition in which white carbon and aluminum oxide were not used and the amount of FEF carbon black was changed to 120 parts by weight was used.

Comparative Example 4
In Example 1, the following composition was used as the nitrile rubber composition, and the vulcanization was performed by changing to press vulcanization at 180 ° C. for 6 minutes.
Nitrile rubber (N235S; nitrile content 36%) 100 parts by weight
SRF carbon black 80 〃
Calcium silicate 40 〃
Calcium carbonate 40 〃
White carbon (Nippon Silica product nip seal LP) 20 〃
Zinc oxide 5 〃
Stearic acid 2 〃
Anti-aging agent (Nocrac 224, a new chemical product from Ouchi) 2 〃
(N-isopropyl-N'-phenyl-p-phenylenediamine)
Triallyl isocyanurate 2 〃
1,3-bis-tert-butylperoxyisopropylbenzene 2.5 〃

About the obtained rubber | gum laminated metal plate, the test of each following item was done.
Friction / wear test: According to JIS K7125 and P8147, using a surface testing machine (manufactured by Shinto Kagaku), using a 10 mm diameter hard chrome plated steel ball friction element as the mating material, moving speed 400 mm / min, reciprocating motion Evaluate by reciprocating test under conditions of moving width 30mm, room temperature, load 2kg, and measure the number of times until the rubber is worn and the adhesive layer is exposed. Air heating test: Air heating under the condition of 165 ° C for 100 hours Later, a cross-cut test was conducted in accordance with JIS K5600, and the degree of rubber peeling after rubber cure deterioration was 5 for rubber remaining 100%, 4 for 95% to less than 100%, 85% for 95% Less than 3, less than 65% and less than 85% is rated as 2, and less than 65% as 1. Water resistance test: In a pressure vessel, immersed in water at 150 ° C for 100 hours, according to JIS K5600 A cross-cut test is performed and the degree of rubber peeling is evaluated according to the same standard as the air heating test.

The results obtained in the above Examples, Reference Examples and Comparative Examples are shown in the following table.
table
Example Friction / wear test (times) Air heating test Water resistance test
Example 1 2200 5 5
〃 2 2200 4 5
３ 3 2200 5 5
４ 4 2200 5 4
５ 5 1200 4 5
６ 6 2100 4 5
７ 7 1500 4 5
８ 8 2300 5 5
９ 9 2200 4 5
〃 10 2200 5 4
〃 11 2200 5 4
〃 12 2200 5 5
〃 13 2200 4 2
〃 14 2200 5 1
〃 15 1500 1 1
〃 16 2200 4 1
〃 17 2200 1 5

Reference example 2200 5 5

Comparative Example 1 300 1 1
〃 2 700 2 5
900 3 900 1 5
４ 4 600 3 5

The rubber metal laminate according to the present invention is suitably used as a vulcanized rubber metal laminate that forms a sealing material such as an oil seal, packing, or gasket that requires wear resistance.

Claims (7)

  In a rubber metal laminate in which an adhesive layer and a rubber layer are sequentially laminated on one side or both sides of a metal plate, the rubber layer is 3 to 100 parts by weight of white carbon and an average particle size of 0.1 with respect to 100 parts by weight of nitrile rubber. A nitrile rubber metal laminate formed of a vulcanized product of a nitrile rubber composition containing 10 to 200 parts by weight of aluminum oxide of -10 μm.   The nitrile rubber metal laminate according to claim 1, wherein a primer layer is formed between the metal plate and the adhesive layer.   The nitrile rubber metal laminate according to claim 2, wherein the primer layer is formed of an organic metal compound having at least one chelate ring and an alkoxy group.   The nitrile rubber metal laminate according to claim 2, wherein the primer layer is formed of an organic metal compound having at least one chelate ring and an alkoxy group and a metal oxide or silica.   The nitrile rubber metal laminate according to claim 2, 3 or 4, wherein the primer layer comprises a hydrolysis condensation product of an amino group-containing alkoxysilane and a vinyl group-containing alkoxysilane.   The nitrile rubber metal laminate according to claim 1, wherein the adhesive layer is a phenol-based adhesive layer containing NBR. NBR contained in the phenol-based adhesive layer contains 3 to 100 parts by weight of white carbon and 10 to 200 parts by weight of aluminum oxide having an average particle size of 0.1 to 10 μm with respect to 100 parts by weight of nitrile rubber. The nitrile rubber metal laminate according to claim 6 which is a composition.