Granted Patent B2

US 6,969,737 · App. 10/435,212 · Granted Nov 29, 2005

Abstract

Claims (113)

1. A rubber composition comprising rubber selected from the group consisting of natural rubber, synthetic rubber, and a combination thereof; and an adhesion promoter comprising a solid carrier that contains (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 R 1 is a C 3 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; R 2 is a C 3 -C 24 saturated fatty avid residue, or an unsaturated fatty acid residue having 1 to 6 carbon-to-carbon double bonds;

wherein n=3-24, and R 3 and R 4 , same or different, are a C 6 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds;

wherein R 5 and R 7 , same or different, are a C 3 -C 24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;

R 6 and R 8 , same or different, are C 3 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and

R 10 and R 11 , same or different, are a C 3 -C 24 , saturated hydrocarbon chain, straight chain or branched; or an unsaturated C 3 -C 24 , hydrocarbon chain, straight chain or branched, having 1 to 6, carbon-to-carbon double bonds;

wherein R 12 , R 14 and R 18 , same or different, are a C 3 -C 24 , hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;

R 13 , R 15 and R 19 , same or different, are a C 3 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and

R 16 , R 17 and R 20 , same or different, are a C 3 -C 24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C 3 -C 24 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 R 1 is a C 3 -C 18 ailcyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and R 2 is a C 8 -C 18 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 3 carbon-to-carbon double bonds;

wherein n=6-18, and R 3 and R 4 , same or different, are a C 6 -C 18 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds;

wherein R 5 and R 7 , are a C 6 -C 24 hydrocarbon chain, straight chain or branched; either saturated or having 1 to 3 carbon-to-carbon double bonds;

R 6 and R 8 , same or different, are a C 3 -C 18 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and

R 10 and R 11 , same or different, are a C 3 -C 18 , 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 R 12 , R 14 and R 18 , same or different, are a C 8 -C 18 , hydrocarbon chain, straight chain or branched, either saturated or having 1 to 3 carbon-to-carbon double bonds;

R 13 , R 15 and R 19 , same or different, are a C 6 -C 18 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and

R 16 , R 17 and R 20 , same or different, are a C 6 -C 18 saturated hydrocarbon chain, straight chain or branched; or an unsaturated C 6 -C 18 hydrocarbon chain, straigbt 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, acetoguanarnine, benzoguanamine, cyclohexylguanamine and glycoluril, which contain vinyl terminated radicals, 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 carbanioylmethyl 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 —CH 2 —R 1 , and any remaining R are H, and at least 2 R 1 are radicals selected from

CH 2 ═C(R 2 )—C(O)—O—,

CH 2 ═C(R 2 )—C(O)-Z,

CH 2 ═C(R 2 )—C(O)—NH —, and

CH 2 ═C(R 2 )—CH 2 —O—,

wherein R 2 is hydrogen or C 1 -C 18 alkyl, and Z is a radical selected from

—O—CH 2 —CH 2 —O—,

—O—CH 2 —CH(CH 3 )—O—,

—O—CH 2 —CH 2 —CH 2 O—, and

—O—CH(C 2 H 5 )—O—, and

any remaining R 1 radicals are selected from

—O—R 3 ,

—NH—C(O)—OR 4 , and

—NH—C(O)—R 4 , and

wherein R 3 is hydrogen or R 4 , and R 4 is a C 1 -C 18 alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or aromatic radical, and in the oligomers, P is 2 to about 10, and L is methylene or the radical

—CH 2 —O—CH 2 —.

9. A rubber composition in accordance with claim 8 , wherein on average at least one R 1 in each monomer or in each oligomenzed unit of the adhesive resin is:

—NH—C(O)—OR 4

wherein R 4 is as defined in claim 8 .

10. A rubber composition in accordance with claim 8 , wherein the adhesive resin is a compound of the formula

wherein P, L and R are as defined in claim 8 .

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

—CH 2 —NH—C(O)—OR 4

wherein R 4 is a C 1 -C 18 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 from

CH 2 ═C(CH 3 )—C(O)O—C 3 H 6 —O—CH 2 —

and

CH 2 ═CH 2 —C(O)O—C 2 H 4 —O—CH 2 —

and at least one R radical is selected from

CH 2 —NH—C(O)—O—CH 3

and

CH 2 —NH—C(O)—O—C 3 H 7 .

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, derivatives of 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 ailcylated 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)(CH 2 OR 1 ), aryl having 6 to 10 carbon atoms, alkyl having 1 to 20 carbon atoms or an acetyl group,

each R is independently hydrogen or —CH 2 OR 1 , and

each R 1 is independently hydrogen or an alkyl group having 1 to 12 carbon atoms,

provided that at least one R is hydrogen or —CH 2 OH and at least one R 1 is selected from the alkyl group; and

wherein the vulcanizable rubber composition is substantially free of methylene acceptor coreactants.

19. The rubber composition in accordance with claim 18 , wherein at least one R group is hydrogen.

20. The rubber composition in accordance with claim 19 , wherein at least one R 1 group 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 a derivative of melamine, benzoguanamine, cyclohexylguanamine, or acetoguanamine, or an oligomer thereof.

22. The rubber composition in accordance with claim 20 , wherein Z is —N(R)(CH 2 OR 1 ).

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 C 6 -C 24 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 C 36 dimer acid and a C 3 -C 18 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 C 3 -C 24 alcohol:

31. A rubber composition in accordance with claim 1 , wherein the ester comprises the following dimer acid reacted with a C 3 -C 24 alcohol:

32. A rubber composition in accordance with claim 1 , wherein the ester comprises the following dimer acid reacted with a C 3 -C 24 alcohol:

33. A rubber composition in accordance with claim 1 , wherein the ester is the reaction product of a C 3 -C 24 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 C 3 -C 24 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. A method of increasing the adhesion of a rubber composition to a polymer, glass, or metal substrate, said rubber composition inchzding a natural or synthetic rubber, a rubber vulcanizing agent, 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 solid carrier containing an ester having formula I, II, III, IV, or mixtures thereof:

wherein R 1 is a C 3 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; R 2 is a C 3 -C 24 saturated fatty acid residue, or an unsaturated fatty acid residue having 1 to 6 carbon-to-carbon double bonds;

wherein n=3-24 and R 3 and R 4 , same or different, are a C 6 -C 24 alkyl radical, straight chain or branched;

wherein R 5 and R 7 , same or different, are a C 3 -C 24 hydro carbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;

R 6 and R 8 , same or different, are a C 3 -C 24 alkyl radical, straight chain or branched; and

R 10 and R 11 , same or different, are a C 3 -C 24 , saturated hydrocarbon chain, straight chain or branched; or an unsaturated C 3 -C 24 , hydrocarbon chain, straight chain or branched, having 1 to 6 carbon-to-carbon double bonds;

wherein R 12 , R 14 and R 18 , same or different, are a C 3 -C 24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;

R 13 , R 15 and R 19 , same or different, are C 3 -C 24 alkyl radical, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and

R 16 , R 17 and R 20 , same or different, are C 3 -C 24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C 3 -C 24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds.

40. A method in accordance with claim 39 , wherein the substrate is a plurality of cords.

41. A method in accordance with claim 39 , wherein the substrate is a polymeric sheet or fabric.

42. A method in accordance with claim 39 , wherein the substrate is metal flat stock material.

43. 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 .

44. The rubber composition in accordance with claim 1 , wherein the R 2 , R 5 , R 7 , R 12 , R 14 are fatty acid residues derived from animal or vegetable fatty acids.

45. The rubber composition of claim 44 , 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.

46. The rubber composition of claim 45 , wherein the fatty acid residues are selected from the group consisting of hexanoic; optanoic; 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.

47. The rubber composition of claim 1 , wherein the carrier is calcium silicate.

48. The rubber composition of claim 47 , wherein the carrier is synthetic calcium silicate.

49. The rubber composition of claim 47 , wherein the carrier is calcium silicate powder.

50. The method of claim 39 , wherein the carrier is calcium silicate.

51. The method of claim 50 , wherein the carrier is synthetic calcium silicate.

52. The method of claim 50 , wherein the carrier is calcium silicate powder.

Assignments (10)