Adhesion of polyester to rubber using an adhesive containing added metal compounds

Abstract

A shaped polyester article having a rubber latex-polyepoxide-polyisocyanate-phenol-formaldehyde adhesive coating is obtained by the addition of compounds containing at least one of the following metals: sodium, potassium, rubidium, cesium, strontium, silver, cadmium, barium, cerium, uranium, titanium, vanadium, chromium, tin, antimony, manganese, iron, cobalt, nickel, copper, zinc, lead, bismuth, calcium and zirconium to the adhesive prior to the deposit of the adhesive coating on the polyester. The use of said metals in said adhesive composition allows the use of less adhesive to achieve the same degree of adhesion as when an adhesive containing no metal-containing compound is used.

We claim: 
     
       1. In a shaped polyester article bearing from 2 to about 30% by weight of an adhesive coating composition comprising the reaction products of: a first component (I) comprising I. a. a polyepoxide having an average of at least two epoxy groups in each molecule, a melting point below about 150° C., an average molecular weight below about 3,000 and an epoxide equivalent below about 2,500 and   B. an aromatic polyisocyanate from the class consisting of Ar(NCO) n  [Ar(NCO) n  ] m , and Ar(NHCOX) n  ; wherein Ar is an organic residue containing at least one aromatic nucleus, X is a radical, selected from the group consisting of aryloxy, arylthio, iminoxy and lactam-N-yl, and m and n are whole numbers of at least 2; the weight ratio of (A)/(B) being within the range of from about 0.01 to about 5.0 and the % by weight being 0.2 to 5.0; in combination, with   Ii. .[.the residue amounting to.]. .Iadd.a second component (II), of from about .Iaddend. 1.8 to 25% by weight of a .[.rubber latex containing the reaction product of a phenol.]. .Iadd.mixture of the dried reaction products of a phenolicformaldehyde resin, a rubber latex .Iaddend.and formaldehyde, said rubber latex being selected from the group consisting of natural rubber, SBR and butadiene-vinylpyridine-styrene rubber;   the improvement comprising having added to said .[.coating composition.]. .Iadd.first component I while in admixture with a liquid carrier and .Iaddend.prior to deposit on said polyester article, .Iadd.a .Iaddend.sufficient amount of a metal-containing compound in the range between 0.00001 and 0.010 moles per 1,000 grams of said .[.coating composition.]. .Iadd.first component I in its liquid carrier .Iaddend.to result in an adhesive bond which has at least a 5% improvement in appearance rating using the hot strip adhesion test, said improvement being compared with a rubber-polyester article control that contains no metal containing compound in said adhesive coating composition, said metal being selected from the group consisting of sodium, potassium rubidium, cesium, strontium, silver, cadmium, barium, cerium, uranium, titanium, vanadium, chromium, tin, antimony, maganese, iron, cobalt, nickel, copper, zinc, lead, bismuth, calcium and zirconium whereby less adhesive is required to achieve the same degree of adhesion as when an adhesive containing no metal-containing compound is used.     
     
     
       2. The adhesive coating composition of claim 1 wherein A is a polyepoxide formed by the reaction of epichlorhydrin with glycerol. 
     
     
       3. The adhesive coating composition of claim 1 wherein B is phenol blocked meta phenylene diisocyanate. 
     
     
       4. The adhesive coating composition of claim 1, wherein B is phenol blocked p,p'-diphenylmethane diisocyanate. 
     
     
       5. The adhesion coating of claim 1 wherein B is the dimer of p,p'-diphenylmethane diisocyanate. 
     
     
       6. The adhesion coating of claim 1 wherein B the dimer of toluene diisocyanate. 
     
     
       7. The adhesive coating composition of claim 1 which contains 0.00010 to 0.0040 mole of a cadmium compound per 1000 grams of .[.adhesive coating composition.]. .Iadd.component I in said liquid carrier.Iaddend.. 
     
     
       8. The adhesive coating composition of claim 1 which contains 0.00002 to 0.00189 mole of a copper compound per 1000 grams of .[.adhesive coating composition.]. .Iadd.Component I in said liquid carrier.Iaddend.. 
     
     
       9. The adhesive coating composition of claim 1 which contains 0.00046 to 0.004 mole of a silver compound per 1000 grams of .[.adhesive coating composition.]. .Iadd.Component I in said liquid carrier.Iaddend.. 
     
     
       10. The adhesive coating composition of claim 1 which contains 0.00002 to 0.00185 mole of zinc compound per 1000 grams of .[.adhesive coating composition.]. .Iadd.Component I in said liquid carrier.Iaddend.. 
     
     
       11. The adhesive coating composition of claim 1 which contains 0.00005 to 0.002 mole of a manganese compound per 1000 grams of .[.adhesive coating composition.]. .Iadd.component I in said liquid carrier.Iaddend.. 
     
     
       12. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium nitrate. 
     
     
       13. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium acetylacetonate. 
     
     
       14. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium chloride. 
     
     
       15. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium stearate. 
     
     
       16. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium acetate. 
     
     
       17. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium sulfate. 
     
     
       18. The adhesive coating composition of claim 7 wherein the cadmium compound is cadmium carbonate. 
     
     
       19. The adhesive coating composition of claim 8 wherein the copper compound is cupric nitrate. 
     
     
       20. The adhesive coating composition of claim 8 wherein the copper compound is cupric acetylacetonate. 
     
     
       21. The adhesive coating composition of claim 10 wherein the zinc compound is zinc acetate. 
     
     
       22. The adhesive coating composition of claim 10 wherein the zinc compound is zinc acetylacetonate. 
     
     
       23. The adhesive coating composition of claim 10 wherein the zinc compound is zinc stearate. 
     
     
       24. The adhesive coating composition of claim 10 wherein the zinc compound is zinc oxide. 
     
     
       25. The adhesive coating composition of claim 10 wherein the zinc compound is zinc chloride. 
     
     
       26. The adhesive coating composition of claim 10 wherein the zinc compound is zinc sulfate. 
     
     
       27. The adhesive coating composition of claim 10 wherein the zinc compound is zinc carbonate. 
     
     
       28. A shaped article of manufacture comprising a natural or synthetic elastomer which is reinforced in its interior with at least one layer of said shaped polyester article defined in claim 1. 
     
     
       29. The shaped article of manufacture defined in claim 28 wherein said shaped polyester article is a fabric. 
     
     
       30. The shaped article of manufacture defined in claim 29 wherein said elastomer is natural rubber. 
     
     
       31. The shaped article of manufacture defined in claim 29 wherein said elastomer is synthetic and is selected from the group consisting of conjugated diolefin homopolymers, copolymers of conjugated dienes with monoethylenically unsaturated monomers or EPDM rubbers. 
     
     
       32. The article of manufacture defined in claim 31 wherein the polyester in said fabric has a melting point of 175° C. and above and has ester linkages which are intralinear. .Iadd. 33. The adhesive coating composition of claim 1 wherein said phenolicformaldehyde resin in second component II is resorcinol-formaldehyde resin. .Iaddend.