Bridgestone Corporation

The Firestone Tire & Rubber Company

Ashley S Hilton

William L Hergenrother

Terrence Eugene Hogan

James Herman Pawlow

William M Cole

Walter Tomaszewski

Michael W Hayes

Chenchy Jeffrey Lin

James Oziomek

David F Lawson

Roderic Paul Quirk

John R Schreffler

Thomas A Antkowiak

Amy M Randall

Mark L Stayer

Sheel Agarwal

Zhong-Ren Chen

Mark S Prichard

An adhesive includes a polymeric latex, a penetrant selected from the group consisting of: terpenes, polylimonene, limonene, carvone, &#x3b1;-pinene, citral, dipentene, 1,8-cineole, eucalyptol, citronellol, geraniol, citronellene, terpinen-4-ol, borneol, camphor, guayule resin, and combinations thereof; and a reinforcing filler. The adhesive has a solids content of 35-65% and a pH of 9 to 12. Articles of manufacture, such as tires and air springs incorporate the adhesive to join rubber interfaces. A method of making the adhesive is also is provided.

Water-based adhesives

Alkoxy-modified silsesquioxane compounds are described. The alkoxy-modified silsesquioxane compounds contain an alkoxysilane group that participates in an alkoxysilane-silica reaction as a silica dispersing agent in rubber, with the release of zero to about 0.1% by weight of the rubber of volatile organic compounds (VOC), especially alcohol, during compounding and further processing. Further described are methods for making alkoxy-modified silsesquioxanes, methods for making vulcanizable rubber compounds containing alkoxy-modified silsesquioxanes, vulcanizable rubber compounds containing alkoxy-modified silsesquioxanes, and pneumatic tires comprising a component that contains alkoxy-modified silsesquioxanes.

Compounding silica-reinforced rubber with low volatile organic compound (VOC) emission

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.

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

A method is presented for making alkoxy-modified silsesquioxanes (AMS) or co-alkoxy-modified silsesquioxanes (co-AMS,) comprising the steps of (a) combining as a reaction mixture (i) water, (ii) an acid-stable solvent for the water, (iii) a solid strong cationic hydrolysis and condensation catalyst, and (iv) a trialkoxysilane compound, (b) allowing the reaction mixture to react for about 0.5 hours to about 200 hours to form the alkoxy-modified silsesquioxanes; and (c) recovering the alkoxy-modified silsesquioxanes from the reaction mixture. The use of solid strong cationic catalysts in this reaction system is advantageous because they remain as solids throughout the reaction, allowing simplified separation of the solid catalyst from the soluble AMS or co-AMS products, resulting in total or near total recovery of the AMS or co-AMS products, the products being free of, or substantially free of residual acid catalyst, as well as virtual total recovery of the catalyst for recycling. The improved AMS and co-AMS compounds, vulcanizable rubber compounds containing them, and a pneumatic tire having a component made from the vulcanized rubber compounds are also presented.

Method for making alkoxy-modified silsesquioxanes

An amino alkoxy-modified silsesquioxane (AMS) comprising one or more compounds selected from the group consisting of an amino AMS, an amino/mercaptan co-AMS, an amino/blocked mercaptan co-AMS, mixtures thereof, and a weak acid-neutralized solid or aqueous solution thereof, and a method of making the amino AMS, are presented. The compounds are useful in compounding, processing, cure and storage of silica-reinforced rubbers because they contain low levels of volatile organic compounds (VOC).

Amino alkoxy-modified silsesquioxanes and method of preparation

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. Vulcanized rubber compositions that contain an amino AMS and/or amino/mercaptan co-AMS compound also have improved adhesion to embedded uncoated steel after humidity aging compared with vulcanized rubber compositions not containing the amino alkoxy-modified silsesquioxane.

A method is presented for making an amino alkoxy-modified silsesquioxane (amino AMS) comprising 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 of these. The use of solid strong cationic catalysts in this reaction system is advantageous because the catalyst remains as a solid throughout the reaction, allowing simplified separation of the solid catalyst from the soluble amino AMS or amino co-AMS products, resulting in total or near total recovery of the amino AMS or amino co-AMS products, as well as virtual total recovery of the catalyst for recycling. The use of the solid strong cationic catalysts is advantageous because it results in amino AMS products that are free of, or substantially free of, residual acid catalyst.

Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes

The present invention provides silica-filled, vulcanized elastomeric compounds comprising an elastomer mixed with at least a silica filler, a processing aid, and a curing agent, and processes for the preparation of the same. Generally, the present invention provides processing aids which effectively reduce or replace the amount (i.e., about 10 percent by weight based upon the silica filler) of the processing aid bis&lsqb;3-triethyoxysilyl)propyl&rsqb;tetrasulfide (&ldquo;Si69&rdquo;) used in the production of silica-filled rubber stocks. These new processing aids include alkyl alkoxysilanes, fatty acid esters of hydrogenated and non-hydrogenated sugars and the polyoxyethylene derivatives thereof, and combinations thereof, with or without various non-reinforcing fillers such as mineral fillers. The processing aids do not hinder the physical properties of the compounds and have been found to be excellent substitutes for Si69. The processing aids may be supported on the silica filler or any of the other fillers employed in the composition for improved handling, safety and performance. Processes for the preparation of the silica filled vulcanizable elastomers are provided as well as pneumatic tires employing tread stock comprising the novel vulcanizable elastomers.

Processability of silica-filled rubber stocks

Sulfur-vulcanizable elastomeric compounds and pneumatic tire components having improved tensile mechanical and dynamic viscoelastic properties are produced by compounding polymers with silica at a temperature of 165&deg; C. to about 200&deg; C., in the presence of a silica dispersing agent, and a very small amount (e.g., about 0.01% to about 1% by weight, based on the weight of the silica) of a bis(trialkoxysilylorgano) tetrasulfide silica coupling agent.

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Massillon, OH, United States of America

Ashley S Hilton