Bonding rubber to metal

Claim 2

The process for bonding rubber to a ferrous metal substrate which comprises depositing a layer of copper from a copper salt solution on said ferrous metal substrate by electroless deposition or electrodeposition, wherein when electroless deposition is used the copper salt solution is free of cupric halide, applying an adhesive thereover, said adhesive consisting essentially of an interpolymer of about 50 to about 99% by weight of a conjugated diene, about 1-45% by weight of a heterocyclic base and 0 to about 40% by weight of at least one additional copolymerizable monomer, thereafter contacting said adhesive with the rubber to be bonded and bonding by heat and pressure, said copper layer being deposited in an amount falling within the range of from about 0.1 to about 9.5 g/m 2 and sufficient to provide a bond strength between the copper coated substrate and the rubber of 40 Kg/2 cm to 90 Kg/2 cm according to the H-Test as defined in the above specification.

Claim 3

The process according to claim 1 wherein said layer of copper is deposited by electrodeposition.

Claim 4

The process according to claim 1 wherein said copper layer is deposited by electroless deposition.

Claim 5

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric sulfate solution in an amount of 0.09 to 4.4 g/m 2 .

Claim 6

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cupric nitrate solution in an amount of 0.5 to 9.5 g/m 2 .

Claim 7

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from cupric formate solution in an amount of 0.5 to 1.3 g/m 2 .

Claim 8

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cupric phosphate solution in an amount of 0.9 to 3.7 g/m 2 .

Claim 9

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric cyanide solution in an amount of 0.3 to 1.9 g/m 2 .

Claim 10

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cupric sulfate solution in an amount of 0.2 to 1.1 g/m 2 .

Claim 11

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric carbonate solution in an amount of 0.1 to 1.5 g/m 2 .

Claim 12

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cupric perchlorate solution in an amount of 0.02 to 1.5 g/m 2 .

Claim 13

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric hydroxide solution in an amount of 0.3 to 3.7 g/m 2 .

Claim 14

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric oxalate solution in an amount of 0.09 to 8.2 g/m 2 .

Claim 15

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric acetate solution in an amount of 0.09 to 3.7 g/m 2 .

Claim 16

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cupric pyrophosphate solution in an amount of 0.1 to 1.6 g/m 2 .

Claim 17

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cuprous bromide solution in an amount of 0.1 to 3.5 g/m 2 .

Claim 18

The process according to claim 1 wherein the layer of copper is deposited by electroless deposition from a cuprous chloride solution in an amount of 0.09 to 1.7 g/m 2 .

Claim 19

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cuprous iodide solution in an amount of 0.3 to 6.4 g/m 2 .

Claim 20

The process according to claim 1 wherein the layer of copper is deposited by electrodeposition from a cuprous cyanide solution in an amount of 0.1 to 1.1 g/m 2 .

Claim 21

The process of claim 1 wherein said conjugated diene is a hydrocarbon containing 4 to 8 carbon atoms, a halogen-substituted hydrocarbon containing 4 to 8 carbon atoms or a lower alkoxy-substituted hydrocarbon containing 4 to 8 carbon atoms.

Claim 22

A process according to claim 1 wherein said heterocyclic nitrogen base has the formula ##STR3## wherein R is selected from the group consisting of hydrogen, alkyl, vinyl, alpha-methylvinyl, alkoxy, halo, hydroxy, cyano, aryloxy, aryl, halo-alkyl, hydroxy alkyl, alkoxyalkyl, cyano-alkyl, halo aryl, alkoxy aryl, hydroxy aryl, cyano aryl, and alkyl aryl, one of said R's having the formula CH 2 ═C < and the total number of carbon atoms in each R substituent being not greater than 15.

Claim 23

A process according to claim 1 wherein said heterocyclic nitrogen base is selected from the group consisting of 2-vinyl pyridine; 2-vinyl-5-ethylpyridine; 2-methyl-5-vinylpyridine; 4-vinyl pyridine; 2,3,4-trimethyl-5-vinylpyridine; 3,4,5,6 tetramethyl-2-vinylpyridine; 3-ethyl-5-vinylpyridine; 2,6-diethyl-4-vinylpyridine; 2-isopropyl-4-nonyl-5-vinylpyridine; 2-methyl-5-undecyl-3-vinylpyridine; 2-decyl-5-(alpha-methylvinyl)pyridine; 2-vinyl-3-methyl-5-ethyl-pyridine; 2-methoxy-4-chloro-6-vinyl-pyridine; 3-vinyl-5-ethoxypyridine; 2-vinyl-4,5-dibromopyridine; 2-vinyl-4-chloro-5-bromopyridine; 2(alpha-methylvinyl)-4-hydroxy-6-cyanopyridine; 2-vinyl-4-phenoxy-5-methylpyridine; 2-cyano-5-(alpha-methylvinyl)pyridine; 3-vinyl-5-phenyl pyridine; 2-(paramethylphenyl)-3-vinyl-4-methylpyridine; 3-vinyl-5-(hydroxyphenyl)-pyridine; 2-vinylquinoline; 2-vinyl-4-ethylquinoline; 3-vinyl-6,7-din-propyl quinoline; 2-methyl-4-nonyl-6-vinylquinoline; 4(alpha-methylvinyl)-8-dodecyl quinoline; 3-vinylisoquinoline; 1,6-dimethyl-3-vinylisoquinoline; 2-vinyl-4-benzylquinoline; 3-vinyl-5-chloroethylquinoline; 3-vinyl-5,6-dichloroisoquinoline; 2vinyl-6-ethoxy-7-methylquinoline and 3-vinyl-6-hydroxymethylisoquinoline.

Claim 24

A process according to claim 1 wherein said rubber is selected from the group consisting of natural rubber, polybutadiene, polyisoprene, copolymers of butadiene with styrene, copolymers of butadiene with acrylonitrile, and polychloroprene.

Claim 25

A process according to claim 1 wherein said interpolymer is a copolymer of butadiene and 2-vinyl pyridine.

Claim 26

A process according to claim 1 wherein said additional monomer is an organic compound containing at least one polymerizable ethylenic group.

Claim 27

A process according to claim 1 wherein said additional monomer is selected from the group consisting of styrene, 3-phenyl-3-butene-1-ol, p-chlorostyrene, p-methoxystyrene, alpha-methyl styrene, vinyl naphthalene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl ethacrylate, acrylonitrile, methacrylonitrile, methacrylamide, methyl isopropyl ketone, methyl vinyl ketone, methyl vinyl ether, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl furane, vinyl carbazole, and vinyl acetylene.

Claim 28

A process according to claim 1 wherein said interpolymer is a terpolymer of styrene, butadiene and 2-vinyl pyridine.

Claim 29

A process according to claim 1 wherein said interpolymer is a terpolymer of 2-vinyl pyridine, isoprene and styrene.

Claim 30

A process according to claim 1 wherein said interpolymer is a terpolymer of 4-vinyl pyridine, butadiene and styrene.

Claim 31

A process according to claim 1 wherein said interpolymer is a terpolymer of 2-methyl-5-vinyl pyridine, butadiene and styrene.