Compagnie Generale Des Etablissements Michelin

Michelin Recherche Et Technique S.a.

Compagnie Generale Des Establissements Michelin

Marco Ribezzo

Milan Fedurco

Antonio Delfino

Alain Faugeras

A laminate comprising a first layer and a second layer directly covering the first layer, the first layer being a layer of a silicone rubber composition comprising a micrometric silicone powder and a mixture of crosslinkable organopolysiloxanes, the second layer being a layer of a silicone rubber composition comprising a hydrophobic silica and a mixture of crosslinkable organopolysiloxanes, is provided. The first layer and the second layer are crosslinked. The laminate, in particular when it is used as a coating for the outer surface of an expandable bladder for a tire curing mold, makes it possible to eliminate molding defects on the inner liner of the tire.

Laminate based on silicone rubber compositions

A metallic or metallized reinforcer has at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide whose repeating units include at least one unit corresponding to formula (I) or (II): in which the two oxazine rings are connected together via a central aromatic group, the benzene ring of which bears one, two, three or four groups of formula &#x2014;S&#x2014;R in which 'x' is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P. Such a reinforcement can be used for the reinforcement of a rubber article, in particular a motor vehicle tire.

Metal or metal-plated reinforcement with sulfur polybenzoxazine-coated surface

A polybenzoxazine sulfide has repeating units including at least one unit corresponding to formula (I) or (II): in which the two oxazine rings are connected together via a central aromatic group, the benzene ring of which bears one, two, three or four groups of formula &#x2014;S&#x2014;R in which 'x' is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P. Such a polybenzoxazine can be used as an adhesive layer on metal, in particular for the adhesive bonding of a metallic substrate, in particular made of carbon steel, to rubber.

Sulfurized polybenzoxazine that can be used for coating metal and for the bonding of same to rubber

A metal or metallized reinforcer, at least the surface of which is at least partially metallic, comprises at least a metallic part coated with a polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formulae (I) or (II): in which Zand Z, which are identical or different, represent an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P. Such a reinforcement can be used for the reinforcement of a rubber article, in particular a motor vehicle tire.

Metal or metallized reinforcement with polybenzoxazine-coated surface

Polybenzoxazine comprises repeat units which comprise at least one unit corresponding to the formulae (I) or (II): in which Zand Z, which are identical or different, represent an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P. Such a polybenzoxazine may be used as a metal-adhesive layer, in particular for the adhesive bonding of a metal substrate, in particular made of carbon steel, to a rubber.

Polybenzoxazine that can be used for coating metal and for the bonding of same to rubber

At least a metallic part of a metal or metallized reinforcer, at least the surface of which is at least partially metallic, is coated with a polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formulae (I) or (II): in which Zrepresents an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P; Xand X, which are identical or different, represent O or S; Arand Ar, which are identical or different, represent a substituted or unsubstituted phenylene group; and Zrepresents O or (S), the symbol 'n' representing an integer equal to 1 or greater than 1. Such a reinforcement can be used for the reinforcement of a rubber article, in particular a motor vehicle tyre.

Metallic or metallized reinforcement, 1HE surface of which is coated with a polybenzoxazine

A sulfurized benzoxazine compound, which is usable for the synthesis of a polybenzoxazin, corresponds to formula (A): in which: each benzene nucleus of the two oxazine rings bears at least one radical denoted as 'G'; the two oxazine rings are connected together via a central aromatic group, the benzene ring of which bears one, two, three or four groups of formula &#x2014;S&#x2014;R in which 'x' is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P; and the at least two radicals G, which may be identical or different, are chosen from various groups.

Sulfurized benzoxazine for use in the synthesis of a polybenzoxazine

A halogenated benzoxazine compound, which can be used in particular as monomer in the synthesis of polybenzoxazine, corresponds to the formula (the symbol Hal representing at least one halogen): in which: each benzene nucleus bears at least one halogen; Rand R, which are identical or different, represent hydrogen or an alkyl comprising from 1 to 8 carbon atoms; 'x' and 'x', which are identical or different, are integers equal to or greater than 1; &#x201c;x&#x201d; is an integer equal to or greater than 1; and X is a heteroatom chosen from O and S.

Halogenated benzoxazine for use in the synthesis of polybenzoxazine

A halogenated benzoxazine compound, which can be used in particular as monomer in the synthesis of polybenzoxazine, corresponds to the formula: in which: each benzene nucleus of the two oxazine rings bears at least one halogen (represented by the symbol Hal), in particular bromine, chlorine or fluorine; and Zand Z, which are identical or different, represent an aliphatic, at least divalent, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S, N and P.

A borated benzoxazine compound, which can be used in particular as monomer in the synthesis of polybenzoxazine, corresponds to the formula: in which: Z represents an at least divalent, aliphatic, cycloaliphatic or aromatic, bonding group comprising at least one carbon atom and optionally at least one heteroatom chosen from O, S and P; and R, R, Rand R, which are identical or different, represent hydrogen or an alkyl comprising from 1 to 12 carbon atoms, it being possible for Rand R, on the one hand, and Rand R, on the other hand, optionally to form a heterocycle with the two oxygen atoms and the boron atom to which they are respectively bonded.

Borated benzoxazine for use in the synthesis of polybenzoxazine

The repeat units of a polybenzoxazine comprise at least one unit corresponding to the formulae (I) or (II): in which Zrepresents an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P; Xand X, which are identical or different, represent O or S; Arand Ar, which are identical or different, represent a substituted or unsubstituted phenylene group; and Zrepresents O or (S), the symbol 'n' representing an integer equal to 1 or greater than 1. Such a polybenzoxazine can be used as metal-adhesive layer, in particular for the adhesive bonding of a metal substrate, in particular made of carbon steel, to a rubber.

Polybenzoxazine that can be used for coating metal and bonding of same to rubber

A polymer has urethane or thiourethane units, which can be used, in particular, as an adhesion primer for the adhesive bonding of metal or glass to rubber. The polymer comprises base units comprising at least a sub-unit of formula XCO&#x2014;NH&#x2014;, in which Xrespectively represents O or S, and additional units comprising at least a secondary alcohol function and a thioether function in the &#x3b1; position relative to the alcohol function. The polymer can be used as an adhesion primer for the adhesive bonding of a substrate, for example glass or metal, to an unsaturated rubber, or as a corrosion-resistant protective coating for a metal substrate. A metal reinforcer, such as wire, cord, film or plate, can be coated with the polymer.

Polymer with urethane or thiourethane units for use, in particular, as an adhesion primer for bonding metal to rubber

A polyurea comprises at least urea base units of formula &#x2014;NH&#x2014;CO&#x2014;NH&#x2014; and additional units. The additional units comprise at least, on the one hand, a secondary alcohol functional group and, on the other hand, an ether, thioether or secondary amine functional group in the alpha position with respect to the secondary alcohol functional group. Such a polymer can be used as an adhesion primer for the adhesive bonding of a substrate, for example, glass or metal, to an unsaturated rubber or as corrosion-resistant protective coating for a metal substrate. Metal reinforcers, such as thread, cord, film or plate, coated can also be coated with such a polymer.

Polyurea that is particularly useful as an adhesion primer for adhering metal to rubber

A sulphur-comprising polyaromatic polyamine compound can be used as a monomer or prepolymer, when n is different from zero, in the synthesis of polyurea. The compound corresponds to the formula (I):HN&#x2014;Ar&#x2014;NH&#x2014;CH&#x2014;CH(OH)&#x2014;(CH)&#x2014;O&#x2014;Z&#x2014;O&#x2014;(CH)&#x2014;CH(OH)&#x2014;CH&#x2014;[X]&#x2014;HN&#x2014;Ar&#x2014;NHin which X represents the string:&#x2014;HN&#x2014;Ar&#x2014;NH&#x2014;(CH)&#x2014;CH(OH)&#x2014;(CH)&#x2014;O&#x2014;Z&#x2014;O&#x2014;(CH)&#x2014;CH(OH)&#x2014;(CH)&#x2014;and in which n represents an integer equal to zero or different from zero; m, which are identical or different, represent an integer within a range from 1 to 10; Zand Z, which are identical or different, represent a divalent bonding group comprising from 1 to 30 carbon atoms; and Ar, Arand Ar, which are identical or different, each represent a phenylene group, at least one of these phenylene groups bearing one, two, three or four groups of formula &#x2014;S&#x2014;R in which 'x' is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon group which can comprise a heteroatom and which comprises from 1 to 10 carbon atoms.

Growing community of inventors

Clermont-Ferrand, France

Marco Ribezzo