Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber

A rubber composite comprising steel embedded in a vulcanizable rubber stock, wherein the steel comprises a coating of an adhesive that comprises a solution of an amino alkoxy-modified silsesquioxane (AMS) that comprises one or more compounds selected from the group consisting of an amino-AMS, an amino/mercaptan co-AMS, an amino/blocked mercaptan co-AMS, and mixtures thereof, and having the formula

• wherein w, x, y and z represent mole fractions, z does not equal zero, at least one of w, x or y must also be present, and w+x+y+z=1.00;
• wherein at least one of R1, R2, R3 and R4 must be present and selected from the group consisting of R6Z, wherein Z is selected from the group consisting of NH2, HNR7 and NR72;
• and the remaining R1, R2, R3 or R4 are the same or different and selected from the group consisting of (i) H or an alkyl groups having one to about 20 carbon atoms, (ii) cycloalkyl groups having 3 to about 20 carbon atoms, (iii) alkylaryl groups having 7 to about 20 carbon atoms, (iv) R6X, wherein X is selected from the group consisting of Cl, Br, SH, SaR7, NR72, OR7, CO2H, SCOW, CO2R7, OH, olefins, epoxides, amino groups, vinyl groups, acrylates and methacrylates, wherein a=1 to about 8, and (v) R6YR8X,
• wherein Y is selected from the group consisting of O, S, NH and NR7;
• wherein R6 and R8 are selected from the group consisting of alkylene groups having one to about 20 carbon atoms, cycloalkylene groups having 3 to about 20 carbon atoms, and a single bond;
• and R5 and R7 are selected from the group consisting of alkyl groups having one to about 20 carbon atoms, cycloalkyl groups having 3 to about 20 carbon atoms, and alkylaryl groups having 7 to about 20 carbon atoms;
• wherein the amino AMS liberates about 0.05% to about 10% by weight alcohol when treated by substantially total acid hydrolysis.

A structural component for a pneumatic tire comprising a vulcanized rubber composite comprising a steel wire cord and having improved metal adhesion and metal adhesion retention properties, wherein the improvement comprises an adhesive coating on the steel wire cord, wherein the adhesive comprises an amino alkoxy-modified silsesquioxane (AMS) selected from the group consisting of an amino AMS, an amino/mercaptan co-AMS, an amino/blocked mercaptan co-AMS, and mixtures thereof, and having the formula

• wherein w, x, y and z represent mole fractions, z does not equal zero, at least one of w, x or y must also be present, and w+x+y+z=1.00;
• wherein at least one of R1, R2, R3 and R4 must be present and selected from the group consisting of R6Z, wherein Z is selected from the group consisting of NH2, HNR7 and NR72;
• and the remaining R1, R2, R3 or R4 are the same or different and selected from the group consisting of (i) H or an alkyl groups having one to about 20 carbon atoms, (ii) cycloalkyl groups having 3 to about 20 carbon atoms, (iii) alkylaryl groups having 7 to about 20 carbon atoms, (iv) R6X, wherein X is selected from the group consisting of Cl, Br, SH, SaR7, NR72, OR7, CO2H, SCOW, CO2R7, OH, olefins, epoxides, amino groups, vinyl groups, acrylates and methacrylates, wherein a=1 to about 8, and (v) R6YR8X, wherein Y is selected from the group consisting of O, S, NH and NR7;
• wherein R6 and R8 are selected from the group consisting of alkylene groups having one to about 20 carbon atoms, cycloalkylene groups having 3 to about 20 carbon atoms, and a single bond;
• and R5 and R7 are selected from the group consisting of alkyl groups having one to about 20 carbon atoms, cycloalkyl groups having 3 to about 20 carbon atoms, and alkylaryl groups having 7 to about 20 carbon atoms;
• wherein the amino AMS liberates about 0.05% to about 10% by weight alcohol when treated by substantially total acid hydrolysis.

A pneumatic tire comprising a structural component that comprises a vulcanized rubber composite comprising a steel wire cord and having improved metal adhesion and metal adhesion retention properties, wherein the improvement comprises an adhesive coating on the steel wire cord, wherein the adhesive comprises an amino alkoxy-modified silsesquioxane (AMS) selected from the group consisting of an amino AMS, an amino/mercaptan co-AMS, an amino/blocked mercaptan co-AMS, and mixtures thereof, and having the formula

• wherein w, x, y and z represent mole fractions, z does not equal zero, at least one of w, x or y must also be present, and w+x+y+z=1.00;
• wherein at least one of R1, R2, R3 and R4 must be present and selected from the group consisting of R6Z, wherein Z is selected from the group consisting of NH2, HNR7 and NR72;
• and the remaining R1, R2, R3 or R4 are the same or different and selected from the group consisting of (i) H or an alkyl groups having one to about 20 carbon atoms, (ii) cycloalkyl groups having 3 to about 20 carbon atoms, (iii) alkylaryl groups having 7 to about 20 carbon atoms, (iv) R6X, wherein X is selected from the group consisting of Cl, Br, SH, SaR7, NR72, OR7, CO2H, SCOW, CO2R7, OH, olefins, epoxides, amino groups, vinyl groups, acrylates and methacrylates, wherein a=1 to about 8, and (v) R6YR8X, wherein Y is selected from the group consisting of O, S, NH and NR7;
• wherein R6 and R8 are selected from the group consisting of alkylene groups having one to about 20 carbon atoms, cycloalkylene groups having 3 to about 20 carbon atoms, and a single bond;
• and R5 and R7 are selected from the group consisting of alkyl groups having one to about 20 carbon atoms, cycloalkyl groups having 3 to about 20 carbon atoms, and alkylaryl groups having 7 to about 20 carbon atoms;
• wherein the amino AMS liberates about 0.05% to about 10% by weight alcohol when treated by substantially total acid hydrolysis.