# US 10,864,774 B2 · Rubber composite reinforced by at least one steel reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,864,774 B2 - Document ID: US10864774B2 - Status: Granted - Kind: B2 - Application number: 15/117,036 - Filed: 2015-02-05 - Published: 2017-06-15 - Granted: 2020-12-15 - Earliest claimed: 2014-02-06 - Assignees: Compagnie Generale Des Etablissements Michelin - Applicants: Compagnie Generale Des Etablissements Michelin; Michelin Recherche et Technique S.A. - Inventors: Clément Michoud; David Doisneau - Web page: https://patentgrep.com/patent/US10864774B2 ## CPC - B60C 9/0007: {Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal} - B32B 7/12: using interposed adhesives or interposed materials with bonding properties - B32B 15/06: of {natural rubber or synthetic} rubber - C08J 5/12: Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives - B32B 2255/06: on metal layer - B32B 2255/26: Polymeric coating - B32B 2405/00: Adhesive articles, e.g. adhesive tapes - B32B 2605/08: Cars - B60C 2009/0014: {Surface treatments of steel cords} - B60C 2009/0021: {Coating rubbers for steel cords} - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract The rubber composite comprises a steel reinforcing element coated with an adhesive layer coating at least a portion of the reinforcing element. The adhesive layer comprises an adhesive composition comprising at least one phenol/aldehyde resin based on at least: one aromatic aldehyde and one polyphenol comprising one or more aromatic nucleus/nuclei. The coated steel reinforcing element is embedded in a rubber matrix based on a rubber composition comprising a crosslinking system comprising a content of molecular sulphur ranging from 1 to 5 phr. ## Claims ### Claim 1 A rubber composite reinforced with at least one steel reinforcing element coated at least in part with an adhesive layer, the reinforced rubber composite comprising a rubber matrix in which the coated steel reinforcing element is embedded, wherein the adhesive layer comprises an adhesive composition comprising at least one phenol/aldehyde resin based on at least: one aromatic aldehyde bearing at least one aldehyde functional group and comprising at least one aromatic nucleus; and one polyphenol comprising one or more aromatic nucleus/nuclei, wherein, if there is only one aromatic nucleus, the one aromatic nucleus bears two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another, the remainder of the aromatic nucleus being unsubstituted, and wherein, if there is more than one aromatic nuclei, at least two of them each bear two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another and the two positions ortho to at least one of these hydroxyl functional groups are unsubstituted, wherein the rubber matrix is based on a rubber composition comprising a crosslinking system comprising a content of molecular sulphur ranging from 1 to 5 phr, wherein the coated steel reinforcing element comprises one or more threadlike reinforcing elements, each comprising a steel core, and wherein the adhesive layer directly coats a layer of a metal coating directly coating at least a portion of the steel core of the or each threadlike reinforcing element such that no other layer or coating is interposed between the adhesive layer and the metal coating and no other layer or coating is interposed between the metal coating and the steel core. ### Claim 2 (depends on 1) The rubber composite according to claim 1, wherein the content of molecular sulphur of the crosslinking system of the rubber composition ranges from 1 to 4 phr. ### Claim 3 (depends on 2) The rubber composite according to claim 2, wherein the content of molecular sulphur of the crosslinking system of the rubber composition ranges from 1 to 3 phr. ### Claim 4 (depends on 3) The rubber composite according to claim 3, wherein the content of molecular sulphur of the crosslinking system of the rubber composition ranges from 1 to 2.5 phr. ### Claim 5 (depends on 1) The rubber composite according to claim 1, wherein the content of molecular sulphur of the crosslinking system of the rubber composition ranges from 1.5 to 5 phr. ### Claim 6 (depends on 5) The rubber composite according to claim 5, wherein the content of molecular sulphur of the crosslinking system of the rubber composition ranges from 2 to 5 phr. ### Claim 7 (depends on 1) The rubber composite according to claim 1, wherein the rubber composition comprises at least one diene elastomer. ### Claim 8 (depends on 7) The rubber composite according to claim 7, wherein the at least one diene elastomer is selected from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene/styrene copolymers, isoprene/butadiene copolymers, isoprene/styrene copolymers, butadiene/styrene/isoprene copolymers and mixtures thereof. ### Claim 9 (depends on 1) The rubber composite according to claim 1, wherein the metal of the layer of the metal coating directly coating at least a portion of the steel core of the or each threadlike reinforcing element is selected from the group consisting of zinc, copper, tin and alloys thereof. ### Claim 10 (depends on 1) The rubber composite according to claim 1, wherein the aromatic aldehyde bears at least two aldehyde functional groups. ### Claim 11 (depends on 1) The rubber composite according to claim 1, wherein the at least one aromatic nucleus of the aromatic aldehyde bears two aldehyde functional groups. ### Claim 12 (depends on 10) The rubber composite according to claim 10, wherein the aromatic aldehyde is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde and mixtures thereof. ### Claim 13 (depends on 1) The rubber composite according to claim 1, wherein the aromatic aldehyde is of general formula (A): in which X comprises N, S or O, and R represents —H or —CHO. ### Claim 14 (depends on 13) The rubber composite according to claim 13, wherein the aromatic aldehyde is selected from the group consisting of furfuraldehyde, 2,5-furandicarboxaldehyde and mixtures thereof. ### Claim 15 (depends on 1) The rubber composite according to claim 1, wherein the polyphenol is selected from the group consisting of phloroglucinol, 2,2′,4,4′-tetrahydroxydiphenyl sulphide and mixtures thereof. ### Claim 16 (depends on 1) The rubber composite according to claim 1, wherein the adhesive composition comprises an unsaturated elastomer latex. ### Claim 17 (depends on 16) The rubber composite according to claim 16, wherein the unsaturated elastomer of the latex is a diene elastomer. ### Claim 18 (depends on 17) The rubber composite according to claim 17, wherein the diene elastomer is selected from the group consisting of polybutadienes, butadiene copolymers, polyisoprenes, isoprene copolymers, vinylpyridine/styrene/butadiene terpolymers and mixtures thereof. ### Claim 19 A process for the manufacture of a rubber composite comprising the steps of: coating at least a portion of a steel reinforcing element with an adhesive layer; and embedding the steel reinforcing element in a rubber matrix based on a rubber composition, wherein the adhesive layer comprises an adhesive composition comprising at least one phenol/aldehyde resin based on at least: one aromatic aldehyde bearing at least one aldehyde functional group and comprising at least one aromatic nucleus; and one polyphenol comprising one or more aromatic nucleus/nuclei, wherein, if there is only one aromatic nucleus, the one aromatic nucleus bears two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another, the remainder of the aromatic nucleus being unsubstituted, and wherein, if there is more than one aromatic nuclei, at least two of them each bear two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another and the two positions ortho to at least one of these hydroxyl functional groups is unsubstituted, wherein the rubber composition comprises a crosslinking system comprising a content of molecular sulphur ranging from 1 to 5 phr, wherein the coated steel reinforcing element comprises one or more threadlike reinforcing elements, each comprising a steel core, and wherein the adhesive layer directly coats a layer of a metal coating directly coating at least a portion of the steel core of the or each threadlike reinforcing element such that no other layer or coating is interposed between the adhesive layer and the metal coating and no other layer or coating is interposed between the metal coating and the steel core. ### Claim 20 (depends on 1) A tire comprising at least one rubber composite according to claim 1. ### Claim 21 A rubber composite reinforced with at least one steel reinforcing element coated at least in part with an adhesive layer, the reinforced rubber composite comprising a rubber matrix in which the coated steel reinforcing element is embedded, wherein the adhesive layer comprises an adhesive composition comprising at least one phenol/aldehyde resin based on at least: one aromatic aldehyde bearing at least one aldehyde functional group and comprising at least one aromatic nucleus; and one polyphenol comprising one or more aromatic nucleus/nuclei, wherein, if there is only one aromatic nucleus, the one aromatic nucleus bears two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another, the remainder of the aromatic nucleus being unsubstituted, and wherein, if there is more than one aromatic nuclei, at least two of them each bear two or three hydroxyl functional groups in the meta position with respect to each other or with respect to one another and the two positions ortho to at least one of these hydroxyl functional groups are unsubstituted, wherein the rubber matrix is based on a rubber composition comprising a crosslinking system comprising a content of molecular sulphur ranging from 1 to 5 phr, wherein the coated steel reinforcing element comprises one or more threadlike reinforcing elements, each comprising a steel core, and wherein the adhesive layer directly coats at least a portion of the steel core of the or each threadlike reinforcing element such that no other layer or coating is interposed between the adhesive layer and the steel core.