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

Patent metadata

Field	Value
Publication number	US-9365700-B2
Application number	US-201414450799-A
Country	US
Kind code	B2
Filing date	Aug 4, 2014
Priority date	Dec 31, 2007
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

Amino alkoxy-modified silsesquioxanes (amino AMS), and/or amino co-AMS compounds that also comprise a mercaptosilane or a blocked mercaptosilane, are excellent adhesives for coating plated or unplated metal wire for adherence of the wire to a rubber stock. The amino AMS and/or the amino/mercaptan co-AMS adhesives can be used with all types of rubber and there is no requirement for the use of special adhesive additives to the rubber vulcanizates, such as, but not limited to, cobalt, resins and high sulfur levels. In particular, the use of amino AMS and/or amino/mercaptan co-AMS compounds as adhesives for bonding wire to rubber also improves the adherence performance of the reinforcements to obtain sufficient bonding that is resistant to degradation over the course of time, especially resistance to thermal aging and/or thermo-oxidizing aging, in particular corrosion in the presence of water.

First claim

It is claimed:

1. A method comprising:
coating a metal with an adhesive composition comprising an 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 a weak acid-neutralized solid or aqueous solution thereof, wherein the AMS liberates about 0.05% to about 10% by weight alcohol based on the weight of the AMS when the product is treated by substantially total acid hydrolysis, thereby forming a coated metal;
embedding the coated metal in a rubber composition; and
vulcanizing the rubber composition.

2. A composition comprising:
a coated metal comprising metal coated with adhesive composition, the coated metal embedded in a vulcanizable rubber composition;
the adhesive composition comprising an 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 a weak acid-neutralized solid or aqueous solution thereof, wherein the AMS liberates about 0.05% to about 10% by weight alcohol based on the weight of the AMS when the product is treated by substantially total acid hydrolysis.

3. The method of claim 1 , wherein the adhesive composition is in a solution and neutralized by a weak acid.

4. The method of claim 1 , wherein the rubber composition comprises 0 to 0.9 of adhesion promoting metallic salts.

5. The method of claim 1 , wherein the rubber composition is formed into a tire structural component selected from the group consisting of: a body ply, a bead, a sidewall insert, a chafer, a sub-tread, sidewall, and an apex.

6. The method of claim 1 , wherein the metal comprises a wire cord selected from the group consisting of an unplated steel cord, a brass plated steel cord, a zinc plated steel cord, a bronze plated steel cord, a plated steel cord at least a portion of which is bright steel, and combinations thereof.

7. The method of claim 1 , wherein the vulcanized rubber composition has improved adhesion to the steel after humidity aging compared with a vulcanized rubber composition not containing the AMS.

8. The method of claim 1 , wherein the rubber composition is substantially free of additives and complexes that promote adhesion to the steel.

9. The method of claim 1 , wherein the metal is exclusive of brass.

10. The method of claim 1 , wherein the metal is a coated wire, the coating consisting essentially of zinc and the AMS is coated over the coated wire.

11. The method of claim 1 , wherein the rubber composition comprises 8 phr or less of silica filler.

12. The method of claim 1 , wherein the amine is NH 2 .

13. The method of claim 1 , wherein the rubber is selected from the group consisting of: natural rubber, synthetic polyisoprene, polybutadiene, copolymers of conjugated diene monomers with at least one monoolefin monomer, poly(styrene-butadiene), and mixtures thereof.

14. The method of claim 1 , wherein the metal is coated by dipping the metal in a solution comprising the adhesive composition for 30 seconds to 5 minutes and subsequently drying for over twenty minutes prior to embedding in the rubber composition.

15. The composition of claim 2 , wherein the vulcanizable rubber composition with the coated metal embedded therein is a tire structural component selected from the group consisting of: a body ply, a bead, a sidewall insert, a chafer, a sub-tread, sidewall, and an apex.

16. The composition of claim 2 , wherein the metal comprises a wire cord selected from the group consisting of an unplated steel cord, a brass plated steel cord, a zinc plated steel cord, a bronze plated steel cord, a plated steel cord at least a portion of which is bright steel, and combinations thereof.

17. The composition of claim 2 , wherein the metal is exclusive of brass.

18. The composition of claim 2 , wherein the metal is a coated wire, the coating consisting essentially of zinc and the AMS coating is over the zinc coating.

19. The composition of claim 2 , wherein the rubber composition comprises 8 phr or less of silica filler.

20. The composition of claim 2 , wherein the rubber is selected from the group consisting of: natural rubber, synthetic polyisoprene, polybutadiene, copolymers of conjugated diene monomers with at least one monoolefin monomer, poly(styrene-butadiene), and mixtures thereof.

Assignees

• Bridgestone Corp

Inventors

• Hergenrother William L
• Tomaszewski Walter
• Hilton Ashley
• Hayes Michael
• Pawlow James H
• Hogan Terrence E

Classifications

• C09D183/08 Primary

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen · CPC title

• B29C66/71

  characterised by the composition of the plastics material of the parts to be joined (welding bar compositions B29C65/125) · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C09J183/08

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen · CPC title

• C08G77/28

  sulfur-containing groups · CPC title