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A rubber composition including a natural or synthetic rubber, and an adhesive resin capable of unexpected adhesion to metal, polymer and glass substrates, particularly cords in radical tires, hoses, conveyor belts, transmission belts, and the like by the addition of a liquid composition containing l

A rubber composition including a natural or synthetic rubber, and an adhesive resin capable of unexpected adhesion to metal, polymer and glass substrates, particularly cords in radical tires, hoses, conveyor belts, transmission belts, and the like by the addition of a liquid composition containing long chain esters, including mono, di- and trimesters.

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1. A rubber composition comprising rubber selected from the group consisting of natural rubber, synthetic rubber, and a combination thereof; and a liquid adhesion promoter selected from the group consisting of a solution and a water-based emulsion containing (1) an adhesive resin in an amount of abo

1. A rubber composition comprising rubber selected from the group consisting of natural rubber, synthetic rubber, and a combination thereof; and a liquid adhesion promoter selected from the group consisting of a solution and a water-based emulsion containing (1) an adhesive resin in an amount of about 0.1% to about 15% by weight, based on the weight of rubber in the composition; and (2) an ester having formula I, II, III, IV or a combination of any two or more of said esters in an amount of about 0.1% to about 15% by weight, based on the weight of rubber in the composition: wherein R1 is a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; R2 is a C3-C24 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 6 carbon-to-carbon double bonds; wherein n=3-24, and R3 and R4, same or different, are a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; wherein R5 and R7, same or different, are a C3-C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R6 and R8, same or different, are C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R10 and R11, same or different, are a C3-C24, saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3-C24, hydrocarbon chain, straight chain or branched, having 1 to 6, carbon-to-carbon double bonds; wherein R12, R14 and R18, same or different, are a C3-C24, hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R13, R15 and R19, same or different, are a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R16, R17 and R20, same or different, are a C3-C24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C3-C24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds. 2. A rubber composition in accordance with claim 1, wherein the ester is selected from the group consisting of formula I, II, III, IV, and a combination of any two or more of said esters: wherein R1 is a C3-C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R2 is a C8-C18 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 3 carbon-to-carbon double bonds; wherein n=6-18, and R3 and R4, same or different, are a C3-C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; wherein R5 and R7, are a C6-C24 hydrocarbon chain, straight chain or branched; either saturated or having 1 to 3 carbon-to-carbon double bonds;R6 and R8, same or different, are a C3-C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R10 and R11, same or different, are a C3-C18, saturated hydrocarbon chain, straight chain or branched; or an unsaturated hydrocarbon chain, straight chain or branched, containing 1 to 3 carbon-to-carbon double bonds; wherein R12, R14 and R18, same or different, are a C8-C18, hydrocarbon chain, straight chain or branched, either saturated or having 1 to 3 carbon-to-carbon double bonds;R13, R15 and R19, same or different, are a C6-C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R16, R17 and R20, same or different, are a C6-C18 saturated hydrocarbon chain, straight chain or branched; or an unsaturated C6-C18 hydrocarbon-chain, straight chain or branched, containing 1 to 3 carbon-to-carbon double bonds. 3. The rubber composition of claim 1, wherein the adhesive resin is a condensation product of a methylene acceptor and a methylene donor.4. The rubber composition in accordance with claim 3, wherein the adhesive resin is selected from the group consisting of phenol-formaldehyde, melamine-formaldehyde; naphthol-formaldehyde; polyepoxide; a reaction product of triallyl cyanurate, resorcinol, and formaldehyde; a reaction product of p-chlorophenol, resorcinol, and formaldehyde; a copolymer of styrene, butadiene, and 2-vinylpyridine; and mixtures thereof.5. The rubber composition in accordance with claim 4, wherein the phenol-formaldehyde resin is resorcinol-formaldehyde.6. The rubber composition in accordance with claim 1, wherein the adhesive resin is a monomer or oligomer selected from the group consisting of melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril, which contained vinyl terminated rascals, on average, at two or more positions on the monomer or on each unit of the oligomer, the rubber composition being free of resorcinol.7. The rubber composition in accordance with claim 6, wherein at least one of the adhesive resins has been further substituted on average at one or more positions with a radical which comprises carbamoylmethyl or amidomethyl.8. A rubber composition in accordance with claim 6, wherein the adhesive resin is selected from compounds of the formula: and positional isomers thereof,wherein, in each monomer and in each polymerized unit of the oligomers, Y is selected from methyl, phenyl and cyclohexyl, and, on average, at least two R are ?CH2?R1, and any remaining R are H, and at least 2 R1 are radicals selected from CH2?C(R2)?C(O)?O?, CH2?C(R2)?C(O)?Z, ?CH2?C(R2)?C(O)?NH?, andCH2?C(R2)?CH2?O?, wherein R2 is hydrogen or C1-C18 alkyl, and Z is a radical selected from?O?CH2?CH2?O?, ?O?CH2?CH(CH3)?O?, ?O?CH2?CH2?CH2O?, and ?O?CH(C2H5)?O?, and any remaining R1 radicals are selected from?O?R3, ?NH?C(O)?OR4, and ?NH?C(O)?R4, and wherein R3 is hydrogen or R4, and R4 is a C1-C18 alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical, and in the oligomers, P is 2 to about 10, and L is methylene or the radical?CH2?O?CH2?. 9. A rubber composition in accordance with claim 8, wherein on average at least one R1 in each monomer or in each oligomerized unit of the adhesive resin is:?NH?C(O)?OR4 wherein R4 is as defined in claim 8.10. A rubber composition in accordance with claim 9, wherein the adhesive resin is a compound of the formula wherein P is 2 to about 10, L is methylene or the radical ?CH2?O?CH2?, and R is as follows:at least two R are ?CH2?R1, and any remaining R are H, and at least 2 R1 are radicals selected from CH2?C(R2)?C(O)?O?, CH2?C(R2)?C(O)?Z, CH2?C(R2)?C(O)?NH?, and CH2?C(R2)?CH2?O?, wherein R2 is hydrogen or C1-C18 alkyl, and Z is a radical selected from?O?CH2?CH2?O?, ?O?CH2?CH(CH3)?O?, ?O?CH2?CH2?CH2O?, ?O?CH(C2H5)?O?, and any remaining R1 radicals are selected from ?O?R3, ?NH?C(O)?OR4, and ?NH?C(O)?OR4, and wherein R3 is hydrogen or R4, and R4 is a C1-C18 alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical.11. A rubber composition in accordance with claim 10, wherein in the adhesive resin formulas, on average at least one R radical in each monomer or in each oligomerized unit is?CH2?NH?C(O)?OR4 wherein R4 is a C1-C18 alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical.12. A rubber composition in accordance with claim 10, wherein on average at least two R radicals are selected fromCH2?C(CH3)?C(O)O?C3H6?O?CH2?andCH2?CH2?C(O)O?C2H4?O?CH2?and at least one R radical is selected fromCH2?NH?C(O)?O?CH3andCH2?NH?C(O)?O?C3H7. 13. A rubber composition in accordance with claim 8, further comprising an additional additive selected from hydroxymethylated and alkoxymethylated, alkoxy having 1-5 carbon atoms, melamine, acetoguanamine, benzoguanamine, cyclohexylguanamine and glycoluril and their oligomers.14. The composition in accordance with claim 6, wherein the adhesive resin is melamine or an oligomer of melamine.15. The composition in accordance with claim 6, wherein the adhesive resin is acetoguanamine or an oligomer of acetoguanamine.16. The composition in accordance with claim 6, wherein the adhesive resin is benzoguanamine or an oligomer of benzoguanamine.17. The composition in accordance with claim 6, wherein the adhesive resin is cyclohexylguanamine or an oligomer of cyclohexylguanamine.18. A rubber composition in accordance with claim 1, wherein the adhesive resin is a self-condensing alkylated triazine resin selected from the group consisting of (i), (ii), and (iii):(i) a self-condensing alkylated triazine resin having at least one of imino or methylol functionality and represented by formula (I) (ii) an oligomer of (i), or (iii) a mixture of (i) and (ii), wherein Z is ?N(R)(CH2OR1), aryl having 6 to 10 carbon atoms, alkyl having 1 to 20 carbon atoms or an acetyl group, each R is independently hydrogen or ?CH2OR1, and each R1 is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that at least one R is hydrogen or ?CH2OH and at least one R1 is selected from the alkyl group; and wherein the rubber composition is substantially free of methylene acceptor coreactants. 19. The rubber composition in accordance with claim 18, wherein at least one R group of the alkylated triazine resin is hydrogen.20. The rubber composition in accordance with claim 19, wherein at least one R1 group of the alkylated triazine resin is a lower alkyl group having 1 to 6 carbon atoms.21. The rubber composition in accordance with claim 20, wherein the adhesive resin is melamine, benzoguanamine, cyclohexylguanamine, or acetoguanamine, or an oligomer thereof.22. The rubber composition in accordance with claim 20, wherein Z is ?N(R)(CH2OR1).23. The rubber composition in accordance with claim 4, wherein the phenol-formaldehyde resin is resorcinol-formaldehyde; and the melamine-formaldehyde resin is N-(substituted oxymethyl) melamine-formaldehyde.24. A rubber composition in accordance with claim 1, wherein the ester has the formula II and comprises a saturated diester formed by the reaction of sebacic acid and a C6-C24 alcohol, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds.25. A rubber composition in accordance with claim 24, wherein the alcohol is 2-ethylhexyl alcohol, and the ester has the following formula: 26. A rubber composition in accordance with claim 1, wherein the ester is an unsaturated diester formed by the reaction of a C36 dimer acid and a C3-C18 alcohol, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds.27. A rubber composition in accordance with claim 26, wherein the alcohol is 2-ethylhexyl alcohol.28. A rubber composition in accordance with claim 26, wherein the alcohol is tridecyl alcohol.29. A rubber composition in accordance with claim 26, wherein the alcohol is oleyl alcohol.30. A rubber composition in accordance with claim 1, wherein the ester comprises the following dimer acid reacted with a C3-C24 alcohol: 31. A rubber composition in accordance with claim 1, wherein the ester comprises the following dimer acid reacted with a C3-C24 alcohol: 32. A rubber composition in accordance with claim 1, wherein the ester comprises the following dimer acid reacted with a C3-C24 alcohol: 33. A rubber composition in accordance with claim 1, wherein the ester is the reaction product of a C3-C24 alcohol with a tricarboxylic acid, having the following formula: 34. A rubber composition in accordance with claim 1, wherein the ester is a combination of compounds of formula I, II, III, and IV.35. A rubber composition in accordance with claim 34, wherein the ester is a reaction product of a C3-C24 alcohol straight chain or branched, saturated, or unsaturated having 1 to 3 carbon-to-carbon double bonds, with a dimer acid.36. A rubber composition in accordance with claim 35, wherein the alcohol is 2-ethylhexyl alcohol.37. A rubber composition in accordance with claim 35, wherein the alcohol is a tridecyl alcohol.38. A rubber composition in accordance with claim 35, wherein the alcohol is an oleyl alcohol.39. The rubber composition in accordance with claim 1, wherein the R2, R5, R7, R12, R14 are fatty acid residues derived from animal or vegetable fatty acids.40. The rubber composition of claim 39, wherein the fatty acids are selected from the group consisting of butter; lard; tallow; grease; herring; menhaden; pilchard; sardine; babassu; castor; coconut; corn; cottonseed; jojoba; linseed; oiticia; olive; palm; palm kernel; peanut; rapeseed; safflower; soya; sunflower; tall; tung; and mixtures thereof.41. The rubber composition of claim 40, wherein the fatty acid residues are selected from the group consisting of hexanoic; octanoic; decanoic; dodecanoic; 9-dodecenoic; tetradecanoic; 9-tetradecenoic; hexadecanoic; 9-hexadecenoic; octadecanoic; 9-octadecenoic; 9-octadecenoic, 12-hydroxy; 9, 12-octadecadienoic; 9, 12, 15-octadecatrienoic; 9, 11, 13-octadecatrienoic; 9, 11, 13-octadecatrienoic, 4-oxo; octadecatetrenoic; eicosanoic; 11-eicosenoic; eicosadienoic; eicosatrienoic; 5, 8, 11, 14-eicosatetraenoic; eicosapentaenoic; docosanoic; 13-docosenoic; docosatetraenoic; 4, 8, 12, 15, 19-docosapentaenoic; docosahexaenoic; tetracosenoic; and 4, 8, 12, 15, 18, 21-tetracosahexaenoic.42. A method of increasing the adhesion of a rubber composition to a substrate, said rubber composition including a natural or synthetic rubber, and an adhesive resin, comprising adding to said rubber composition, in an amount of about 0.1% to 15% by weight, based on the weight of the rubber, a liquid ester additive of formula I, II, III, IV, or mixtures thereof: wherein R1 is a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; R2 is a C3-C24 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 6 carbon-to-carbon double bonds; wherein n=3-24 and R3 and R4, same or different, are a C3-C24 alkyl radical, straight chain or branched; wherein R5 and R7, same or different, are a C3-C24 hydro carbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R6 and R7, same or different, are a C3-C24 alkyl radical, straight chain or branched; and R10 and R11, same or different, are a C3-C24, saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3-C24, hydrocarbon chain, straight chain or branched, having 1 to 6 carbon-to-carbon double bonds; wherein R12, R14 and R18, same or different, are a C3-C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R13, R15 and R19, same or different, are C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R16, R17 and R20, same or different, are C3-C24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C3-C24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds. 43. A method in accordance with claim 42, wherein the substrate is a plurality of cords.44. A method in accordance with claim 42, wherein the substrate is a polymeric sheet or fabric.45. A method in accordance with claim 42, wherein the substrate is flat metal stock material.46. A method of increasing the adhesion of a rubber composition to a substrate comprising an expedient selected from the group consisting of (1) applying a liquid adhesion promoter comprising an adhesive resin component and an ester component to the substrate prior to contacting the substrate with the rubber composition; (2) contacting the substrate separately with a solvent solution or water-based emulsion containing the ester component of the liquid adhesion promoter, and contacting the substrate separately with a solvent solution or water-based emulsion containing the adhesive resin component of the liquid adhesion promoter prior to contacting the substrate with the rubber composition; (3) applying the adhesive resin component of the liquid adhesion promoter to the substrate prior to contacting the adhesive resin-applied substrate with the rubber composition containing a solvent solution or water-based emulsion containing the ester component of the liquid adhesion promoter; (4) applying the ester component of the liquid adhesion promoter to the substrate prior to contacting the ester-applied substrate with the rubber composition containing a solvent solution or water-based emulsion containing the adhesive resin component of the liquid adhesion promoter; wherein the ester component of the adhesion promoter is selected from the group consisting of formulas I, II, III, IV, and a combination of any two or more: wherein R1 is a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; R2 is a C3-C24 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 6 carbon-to-carbon double bonds; wherein n=3-24, and R3 and R4, same or different, are a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; wherein R5 and R7, same or different, are a C3-C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R6 and R8, same or different, are C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R10 and R11, same or different, are a C3-C24, saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3-C24, hydrocarbon chain, straight chain or branched, having 1 to 6, carbon-to-carbon double bonds; wherein R12, R14 and R18, same or different, are a C3-C24, hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;R13, R15 and R19, same or different, are a C3-C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R16, R17 and R20, same or different, are a C3-C24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C3-C24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds. 47. A method in accordance with claim 46, wherein the amount of the adhesive resin component contained in the rubber composition or applied to the substrate is about 0.1% to about 15% by weight, based on the weight of rubber in the composition, and the amount of ester component contained in the rubber composition or applied to the substrate is about 0.1% to about 15% by weight, based on the weight of rubber in the composition.48. The method of claim 47, wherein the rubber composition contains a vulcanizing agent.49. A cord-reinforced article of manufacture comprising a plurality of cords selected from polymeric cords, metal cords, glass cords, and a combination thereof, adhered to the rubber composition of claim 1.