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    • 专利摘要:
    The reinforcing steel member comprises: - one or more wire reinforcing elements each comprising a steel core; a layer of a coating of a copper-tin alloy coating at least a portion of the steel core of the or each wire reinforcing element; and an adhesive layer coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element. The adhesive layer comprises an adhesive composition comprising at least one phenol-aldehyde resin based on at least: - an aromatic aldehyde and - a polyphenol having one or more aromatic ring (s).
    公开号:FR3017071A1
    申请号:FR1450903
    申请日:2014-02-06
    公开日:2015-08-07
    发明作者:Clement Michoud；David Doisneau
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The field of the present invention is that of metal reinforcing elements and adhesive compositions or "glues" intended to adhere such metal reinforcing elements to unsaturated rubber matrices such as those commonly used in articles or products. semi-finished rubber.
    [0002] The present invention more particularly relates to steel reinforcing elements coated with adhesive layers based on a phenol-aldehyde resin, in particular to coated steel reinforcing elements capable of reinforcing tire structures. 1 () Pneumatic steel reinforcing elements comprising one or more steel wire reinforcing elements, for example steel wires, are known from the state of the art. It is known to adhere these steel son to rubber compositions through the use of adhesives known under the name "RFL" (for resorcinol-formaldehyde), as for example in EP2006341. These RFL glues are well known to include a thermosetting phenolic resin obtained by condensing resorcinol with formaldehyde and one or more diene rubber latex in aqueous solution. The RFL glues of EP2006341 ensure good adhesion of the coated steel wire (s) to rubber matrices without the latter being surface-treated, i.e., in the absence of a layer of metal coating, for example a layer of brass. However, the RFL glue requires the use of a halogenated polymer and a metal oxide. In addition, this RFL adhesive requires the use of a rubber matrix comprising an acrylic rubber composition and thus does not allow satisfactory adhesion with any rubber matrix. Also known from the state of the art are steel reinforcing elements for tires coated with a layer of brass. During the baking of the tire, an adhesive interface is formed comprising zinc oxide and zinc sulphide resulting from the reaction between the zinc of the brass layer and the rubber composition. However, a dezinsification of the brass layer is observed over time and thus a loss of adhesion which is obviously not desirable. Thus, the designers of rubber articles, especially tire manufacturers, have the aim today of finding new simple adhesive systems which can satisfactorily adhere the metal reinforcing elements to the rubber matrices without the need for them. they are necessarily based on an acrylic rubber composition or that the glue must be used in combination with a halogenated polymer and a metal oxide and to ensure that the adhesion between the metal reinforcing elements and the rubber is perennial. P10-3282_EN - 2 - During their research, the Applicants have discovered an adhesive composition that makes it possible to meet the above objective. Thus, a first object of the invention relates to a coated steel reinforcing element comprising: - one or more wire reinforcing elements each comprising a steel core; a layer of a coating of a copper-tin alloy coating at least a portion of the steel core of the or each wire reinforcing element; and an adhesive layer coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element, the adhesive layer comprising an adhesive composition comprising at least one phenol-aldehyde resin based on least: an aromatic aldehyde bearing at least one aldehyde function, comprising at least one aromatic ring; a polyphenol comprising one or more aromatic ring (s), it being understood that: in the case of a single aromatic ring, the latter is carrying two or three hydroxyl functions in the meta position with respect to the other or each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that both Ortho positions of at least one of these hydroxyl functions are unsubstituted.
    [0003] The invention also relates to a method of manufacturing a coated steel reinforcing element comprising: - one or more wire reinforcing elements each comprising a steel core; a layer of a coating of a copper-tin alloy coating at least a portion of the steel core of the or each wire reinforcing element; and an adhesive layer coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element. The method according to the invention comprises a step of coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element with the adhesive layer comprising an adhesive composition as described above. .
    [0004] Furthermore, the invention relates to the use, for the adhesion of a steel reinforcing element to a rubber matrix, of an adhesive composition forming an adhesive layer coating at least a portion of a layer of a a copper-tin alloy coating coating at least a portion of each steel core with one or more wire reinforcing elements, the adhesive composition being as described above. The invention also relates to a rubber composite reinforced with at least one reinforcing element of coated steel as described above comprising a rubber matrix in which the reinforcement element is embedded in coated steel.
    [0005] Another object of the invention is a tire comprising at least one rubber composite as described above. The invention therefore relates to any composite (article or semi-finished product) of rubber, in particular any tire, before or after firing (for crosslinking or final vulcanization), comprising a reinforced steel reinforcing element as described above. The invention also relates to the use of the reinforcing element made of coated steel as described above as reinforcing element for semi-finished articles or products made of rubber, particularly tires, especially those intended to equip vehicles with tourism type engine, SUV ("Sport Utility Vehicles"), two wheels (including bicycles, motorcycles), aircraft, such as industrial vehicles chosen from light trucks, "heavy vehicles" - that is to say, metro, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles; other transport or handling vehicles. The invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments.
    [0006] In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. By "diene" elastomer (or indistinctly rubber) is meant an elastomer derived at least in part (that is to say a homopolymer or a copolymer) from monomer (s) diene (s) (ie, carrier (s) two carbon-carbon double bonds, conjugated or not). By "isoprene elastomer" is meant a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various copolymers of isoprene, isoprene and mixtures of these elastomers.
    [0007] On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b).
    [0008] P10-3282_EN - 4 - I - REINFORCED STEEL REINFORCEMENT ELEMENT By the expression "composition based on", it is of course to understand a composition comprising the mixture and / or the reaction product of the various basic constituents used for this purpose. composition, some of them may be intended to react or likely to react with each other or with their surrounding chemical environment, at least in part, during the various phases of manufacture of the composition, the reinforcing element, the composites or finished articles, especially during a cooking step.
    [0009] The copper-tin alloy is generally known as bronze. For example, the copper-tin alloy comprises between 80% and 99.5% copper and between 0.5% and 20% tin by weight of the alloy. Usually, a steel reinforcing element whose steel core is coated with a copper-tin alloy coating layer, ie bronze, is referred to as "tanned" and is referred to as a tanned steel reinforcing element. The coated steel reinforcing element coated according to the invention may comprise, in one embodiment, a single wire reinforcement element. In another embodiment, the tanned steel reinforcing member coated according to the invention comprises a plurality of wire reinforcing elements assembled together, for example by wiring or twisting. Among the coated bronzed steel reinforcement elements comprising several wire reinforcing elements, for example, layered cables and multi-strand cables. Each wired reinforcement element is unitary, that is to say that the constituents of each wired reinforcement element are indissociable from each other. The adhesive layer is coating at least a portion of the copper-tin alloy coating layer of the or each wire reinforcing member. Thus, the adhesive layer may partially or completely coat the layer of the copper-tin alloy coating of the or each wire reinforcing element. Thus, in the embodiment in which the coated tanned steel reinforcing member comprises a single wire reinforcing member, the adhesive layer may coat portions of the copper-tin alloy coating layer of that element or its screen. In the embodiment in which the coated tanned steel reinforcing member comprises a plurality of wire reinforcing elements, the adhesive layer may coat the copper-tin alloy coating layer with a plurality of wire elements without coating other ones or coat only parts of the copper-tin alloy coating layer of some or all of the wire elements. By wire reinforcement element is meant elongated elements of great length relative to their cross section, whatever the shape of the latter, by circular, oblong, rectangular or square example, or even flat, this wire element that can be rectilinear as non-rectilinear, for example twisted or corrugated. When it is circular in shape, the diameter of each wire reinforcement element is preferably less than 5 mm, more preferably in a range from 0.1 to 0.5 mm.
    [0010] Mention may also be made of strips or strips which have a great length relative to their thickness. The steel core is monolithic, that is to say that it comes for example from material or molding.
    [0011] The steel may have a pearlitic, ferritic, austenitic, bainitic, martensitic microstructure or a microstructure derived from a mixture of these microstructures. Preferably, the steel comprises a carbon content ranging from 0.2% to 1% by weight and more preferably from 0.3% to 0.7% by weight. Preferably, the steel comprises a manganese content ranging from 0.3% to 0.7% by weight, a silicon content ranging from 0.1% to 0.3% by weight, and a phosphorus level of at most up to 0.045% inclusive of the mass, with a maximum sulfur content of up to 0.045% inclusive and a maximum nitrogen content of up to 0.008% inclusive. Optionally, the steel comprises at most 0.1% inclusive, preferably 0.05% inclusive, and more preferably 0.02% including mass bound vanadium and / or molybdenum. In one embodiment, the steel used comprises less than 0.5%, preferably not more than 0.05% inclusive, and more preferably not more than 0.02% inclusive of chromium. In another embodiment using so-called stainless steel, the steel comprises at least 0.5% inclusive, preferably at least 5% inclusive, and more preferably at least 15% inclusive, inclusive of chromium.
    [0012] Preferably, a stainless steel comprises at least 2% inclusive, preferably at least 4% inclusive and more preferably at least 6% by weight nickel. Preferably, the copper-tin alloy coating layer directly covers at least a portion of the steel core of the or each wire reinforcing member. In one embodiment, the adhesive layer directly coats at least a portion of the copper-tin alloy coating layer of the or each wire reinforcing member. Thus, in this embodiment, the coated reinforcing member is free of a non-metallic interlayer which would be interposed between the copper-tin alloy coating layer of the P10-3282_FR - 6 - or each wired reinforcement element and the adhesive layer comprising the adhesive composition. In another embodiment, the adhesive layer directly coats a non-metallic adhesion interlayer directly coating at least a portion of the copper-tin alloy coating layer of the or each wire reinforcing member. The non-metallic interlayer, generally referred to as the adhesion primer, in combination with the adhesive layer comprising the adhesive composition, improves the adhesion of the coated tanned steel reinforcement element to the rubber matrix. Such adhesion primers are those commonly used by those skilled in the art for pre-gluing certain textile fibers (polyester fibers, for example PET, aramid, aramid / nylon). For example, it will be possible to use an epoxy-based primer, in particular based on polyglycerol polyglycidyl ether. It is also possible to use a primer based on blocked isocyanate.
    [0013] By layer "directly" coating an object or coating "directly" covering an object, it is meant that the layer or coating is in contact with the object without any other object, in particular another layer or another coating being interposed between the two.
    [0014] The adhesive composition therefore comprises at least one (i.e., one or more) phenol-aldehyde resin; this phenol-aldehyde resin is based on at least one (that is to say one or more) aromatic aldehyde and at least one (that is to say one or more) polyphenol, which constituents will be described in detail below. 1. 1 - Aromatic Aldehyde The first component of the phenol-aldehyde resin is an aromatic aldehyde bearing at least one aldehyde function, comprising at least one aromatic ring.
    [0015] According to a preferred embodiment, the aromatic nucleus carries the aldehyde function. Preferably, the aromatic aldehyde carries at least two aldehyde functions. Preferably, the aromatic ring of the aromatic aldehyde carries two aldehyde functions, the latter being able to be in the ortho, meta or para position on the aromatic ring. Preferably, the aromatic nucleus of the aromatic aldehyde is a benzene nucleus. In some embodiments, this aromatic aldehyde is selected from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-P10-3282_FR-7-benzenedicarboxaldehyde, 2-hydroxybenzene-1,3,5-tricarbaldehyde, and mixtures of these compounds. Even more preferentially, the aromatic polyaldehyde used is 1,4-benzenedicarboxaldehyde, also called terephthaldehyde, as a reminder of the chemical formula developed: (I) In other embodiments, the aromatic aldehyde has formula (A): XH (A) wherein X comprises N, S or O and R is -H or -CHO. Such aromatic aldehydes are derived from renewable resources and not from oil. Aromatic aldehydes are for example from the bio-resource or transformation products of the bio-resource. Preferably, the aromatic aldehyde is of general formula (A '): X (A') According to a preferred embodiment, X represents O. In a variant of the aromatic aldehyde of general formula (A), X represents O and R is -H. The aromatic aldehyde used is then of formula (131): ## STR2 ## In a variant of the aromatic aldehyde of general formula (A '), X represents O and R represents -H. The aromatic aldehyde used is then furfuraldehyde and is of formula (B '1): In another variant of the aromatic aldehyde of general formula (A), X represents O and R represents -CHO. The aromatic aldehyde used is then of formula (B2): H H (B2) In another variant of the aromatic aldehyde of general formula (A '), X represents O and R represents -CHO. The aromatic aldehyde used is then 2,5-furanedicarboxaldehyde and is of formula (B'2): ## STR2 ## In another embodiment, X comprises N. In a variant of the aromatic aldehyde of general formula (A), X represents NH. The aromatic aldehyde used is of formula (C1): H (C1) P10-3282_FR - 9 - In a variant of the aromatic aldehyde of general formula (A '), X represents NH. The aromatic aldehyde used is of formula (C '1): (C' 1) Preferably, R represents -CHO in the variant of the aromatic aldehyde of formula (C'1) and the aromatic aldehyde obtained is then the 2,5-1H-pyrroledicarboxaldéhyde. In another variant of the aromatic aldehyde of the general formula (A), X represents NR1 with R1 representing an alkyl, aryl arylalkyl, alkylaryl or cycloalkyl group.
    [0016] The aromatic aldehyde used is of formula (C2): R 1 N 0 H (C2) In another embodiment, X comprises S.
    [0017] In a variant of the aromatic aldehyde of general formula (A), X represents S. The aromatic aldehyde used is of formula (D1): H (D1) In a variant of the aromatic aldehyde of general formula (A ') , X represents S.
    [0018] The aromatic aldehyde used has the formula (D'1): 0 (D'1) P10-3282_FR -10- Preferably, R represents -CHO in the variant of the aromatic aldehyde of formula (D'1) and is then 2,5-thiophene dicarboxaldehyde. In another variant of the aromatic aldehyde of the general formula (A), X is SR 2 with R 2 being alkyl, aryl arylalkyl, alkylaryl or cycloalkyl. The aromatic aldehyde used is of formula (D2): R2 H (D2) In yet another variant of the aromatic aldehyde of general formula (A), X represents R3-S-R2 with R2, R3 each independently representing from each other an alkyl, aryl arylalkyl, alkylaryl or cycloalkyl group. The aromatic aldehyde used is of formula (D3): H (D3) In yet another variant of the aromatic aldehyde of general formula (A), X represents S = O. The aromatic aldehyde used is of formula (D4): ## STR2 ## In yet another variant of the aromatic aldehyde of general formula (A), X represents O = S = O. The aromatic aldehyde used is of formula (D5): ## STR2 ## Among the different embodiments described above, the embodiments and the variants in which X represents NH, S or O. In these embodiments and variants, there may be R representing -H or -CHO and preferably R representing -CHO. In these embodiments and variants, R will preferably be in the 5-position and the -CHO group in the 2-position on the aromatic ring (general formula (A ')). The phenol-aldehyde resin may comprise a mixture of the compounds indicated above, in particular a mixture of furfuraldehyde and 2,5-furanedicarboxaldehyde.
    [0019] Preferably, when the phenol-aldehyde resin is based on a single aromatic aldehyde, the composition is free of formaldehyde. When the phenol-aldehyde resin is based on several aldehydes, at least one of which is an aromatic aldehyde, each aldehyde is preferentially different from formaldehyde. The composition is then also preferably free of formaldehyde. In other words and preferably, the or each aldehyde of the phenol-aldehyde resin is different from formaldehyde.
    [0020] By formaldehyde-free, it is meant that the formaldehyde mass content by weight of the aldehyde (s) is strictly less than 1%. In some embodiments, the composition may comprise formaldehyde. Preferably, the composition then comprises a weight ratio of formaldehyde by total weight of the aldehyde (s) is less than or equal to 10%, preferably to 5% and more preferably to 2%. 1.2 - Polyphenol The second component of the phenol-aldehyde resin is a polyphenol having one or more aromatic ring (s). In the case of a polyphenol comprising a single aromatic ring, the latter carries two or three hydroxyl functions in the meta position with respect to each other (in the case of two functions) or with respect to each other. (in the case of three functions), the remainder of the aromatic ring being by definition unsubstituted; by this is meant that the other carbon atoms of the remainder of the aromatic ring (those other than carbon atoms bearing hydroxyl functions) carry a single hydrogen atom.
    [0021] As a preferred example of a polyphenol comprising a single aromatic nucleus, there may be mentioned in particular resorcinol, as a reminder of the structural formula: embedded image As an even more preferred example comprising a single aromatic nucleus, mention may be made of phloroglucinol, as a reminder of the structural formula: OH HOS OH (III) In the case of a polyphenol comprising several (two or more) aromatic rings, at least two of them are each carrying two or three hydroxyl functions in position meta relative to each other (in the case of two functions), or relative to each other (in the case of three functions), it being understood that the two positions in ortho d ' at least one of these hydroxyl functions are unsubstituted; by this is meant that the two carbon atoms located on both sides (in ortho position) of the hydroxyl carbon atom (i.e., carrying the hydroxyl function) carry a single hydrogen atom.
    [0022] As preferred examples, in the case where the polyphenol molecule comprises several aromatic nuclei, at least two of these aromatic nuclei, which are identical or different, are chosen from those of general formulas: ## STR1 ## OH (IV-a) (IV-b) (IV-c) (IV-d) in which the symbols Zi, Z2, which are identical or different if they are several on the same aromatic ring, represent an atom (for example carbon , sulfur or oxygen) or a bivalent at least divalent linking group which connects at least these two aromatic rings to the rest of the polyphenol molecule. According to a particular and preferred embodiment of the invention, the polyphenol is for example a flavonoid, characterized for recall by a basic structure with 15 carbon atoms, formed by two benzene rings connected by three carbon atoms. More particularly, the flavonoid used is 2 ', 4', 3, 5, 7-pentahydroxyflavone, also called "Morin", of formula (V) hereinafter: ## STR2 ## is a polyphenol having two aromatic rings (of respective formulas IV-c and IV-d above), each of which is indeed carrying two hydroxyl functional groups in the meta position with respect to each other, the two positions in ortho d at least one of these two hydroxyl functions being unsubstituted. According to another particular and preferred embodiment of the invention, the polyphenol is for example phloroglucide, also called 2,4,6,3 ', 5'-biphenylpentol, of the following structural formula: ## STR2 ## note that this compound is a polyphenol having two aromatic rings (of respective formulas IV-a and IV-b above) each of which is well carrier of at least two (in this case, a carrier of two, the other carrier of three) hydroxyl functions meta position relative to each other, the two ortho positions of at least one of these two hydroxyl functions being unsubstituted. According to yet another particular and preferred embodiment of the invention, the polyphenol is, for example, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide of the following structural formula: ## STR2 ## In a preferred embodiment, the polyphenol is selected from the group consisting of phloroglucinol (III), 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide (VII) and mixtures of these compounds. . 1.3 - Unsaturated elastomer latex It is recalled that a latex is a stable dispersion of elastomer microparticles (s) suspended in an aqueous solution.
    [0023] The unsaturated elastomer latexes (that is to say bearing carbon-carbon double bonds), in particular diene elastomer, are well known to those skilled in the art. Preferably, the adhesive composition comprises an unsaturated elastomer latex. The unsaturated elastomer of the latex is preferably a diene elastomer, more preferably a diene elastomer selected from the group consisting of polybutadienes, butadiene copolymers, polyisoprenes, isoprene copolymers and mixtures of these elastomers. It is even more preferably selected from the group consisting of butadiene copolymers, vinylpyridine-styrene-butadiene terpolymers, natural rubber, and mixtures of these elastomers. 1.4 - Additives - Manufacture of the adhesive composition The adhesive composition and / or its phenol-aldehyde resin and / or its starting unsaturated elastomer latex may, of course, comprise all or part of the usual additives for adhesive compositions such as those used in the present invention. conventional RFL glues; examples are bases such as ammonia, sodium hydroxide, potassium hydroxide or ammonium hydroxide, dyes, fillers such as carbon black or silica, antioxidants or other stabilizers. Typically, during a first manufacturing step, the resin itself is prepared by gradually mixing the polyphenol and the aromatic aldehyde in a basic solvent such as a sodium hydroxide solution, preferably having a pH between 9 and 13, more preferably between 10 and 12. All the constituents are mixed with stirring for a variable time depending on the temperature used and the specific composition targeted, for example for a period which may vary between 1 min and 6 h at a temperature between 15 ° C and 90 ° C, preferably between 20 ° C and 60 ° C. The phenol-aldehyde resin thus precondensed is generally diluted in water to obtain an aqueous adhesive composition. Then, a latex or latices (if more) of unsaturated elastomer (s) are added to form the aqueous adhesive composition, according to a general procedure which is well known to those skilled in the art. field of RFL glues.
    [0024] For example, the constituents of the adhesive composition are added in the following order: water, any additives soluble in water (for example ammonia), the latex (s) (in any order), the resin phenol-aldehyde (diluted). The mixture is mixed with stirring for 1 to 30 minutes, for example at 23 ° C.
    [0025] In a final manufacturing step, the adhesive composition is generally stored at room temperature (23 ° C.) for a maturation time that can typically vary from 1 to several hours or even several days, before its final use. In the final adhesive composition thus prepared, the content of solids content of phenol-aldehyde resin preferably represents between 5 and 60%, more preferably between 10 and 30% by weight of the dry extract of adhesive composition. The level of unsaturated elastomer (that is to say the solids content of the latex) is in turn preferably between 40 and 95%, more preferably between 70 and 90%, by weight of the extract. dry of the adhesive composition. The weight ratio of polyphenol to aromatic aldehyde is preferably between 0.1 and 3, more preferably between 0.25 and 2.
    [0026] The weight ratio of the resin solids content to the dry latex extract is preferably between 0.1 and 2.0, more preferably between 0.15 and 1.0. The water content of the adhesive composition is preferably between 60 and 90%, more preferably between 60 and 85%.
    [0027] P10-3282_FR -16- Advantageously, the adhesive composition comprises a gelatin. The gelatin slows down the dewetting of the wire reinforcing elements and thus to ensure better adhesion between the bronzed steel reinforcing element and the rubber matrix. Gelatin means any mixture of proteins comprising products of the total or partial hydrolysis of collagen. II-PROCESS FOR MANUFACTURING THE COATED REINFORCING ELEMENT During the process described above, at least a portion of the steel core of the or each wire reinforcement element is coated with a layer of the copper-tin alloy coating. and then coating the copper-tin alloy coating of the or each wire reinforcing element with the adhesive layer comprising the adhesive composition described above. The step of coating by the layer of the copper-tin alloy coating can be carried out conventionally by several successive stages of immersion of the wire in lead, bronze, soda and acid baths, and then a step drying and finally a surface treatment step, for example using benzofuran. The step of coating with the adhesive layer may be carried out by any suitable method, in particular by any known coating technique such as, for example, spraying, dip impregnation, scrolling in a bath or other equivalent thin-film deposition technique. or ultra-thin, or a combination of one or more of these techniques.
    [0028] The weight of dry extract of the adhesive composition deposited on a kilogram of non-coated steel wire reinforcement element is preferably between 2 and 100 g, more preferably between 2 and 50 g, more preferably between 3 and 15 g. . After the previously described step of coating the layer of the copper-tin alloy coating with the adhesive composition, the coated bronzed steel reinforcing member undergoes a first heat treatment to remove any solvent or water, at a temperature of preferably between 110 ° C and 260 ° C, more preferably between 130 ° C and 250 ° C, for example by crossing a tunnel furnace, typically several meters long, such as those commonly used for heat treatment after gluing textile materials with RFL glue. Then, the anhydrous-coated tanned steel reinforcement element thus obtained undergoes a second heat treatment to complete the crosslinking of the adhesive composition, preferably led to air in a tunnel oven as described above. The treatment temperature is preferably between 150 ° C and 350 ° C. The treatment times are from a few seconds to a few minutes depending on the case (for example between 10 s and 10 min). Those skilled in the art will be able to adjust, if necessary, the temperature and the duration of the heat treatment above, depending on the particular conditions of implementation of the invention, in particular the exact nature of the adhesive composition or the nature of steel. In particular, those skilled in the art will benefit from performing scans in temperature and treatment time, so as to seek, by successive approaches, the operating conditions leading to the best adhesion results, for each particular embodiment of the invention. invention. The thickness of the layer consisting of the adhesive composition coating the layer of the copper-tin alloy coating is in a range of values ranging from 5 to 100 μm, preferably from 5 to 50 μm, and more preferably from 10 to 35 μm.
    [0029] Prior to the step of coating the steel reinforcing element with the adhesive layer comprising the adhesive composition, each wire reinforcement element may undergo processing steps, for example descaling, drawing in a humid medium or in a dry medium. or heat treatment. Examples of these processing steps are described in particular in documents US20100170624, US5535612 or JP2000219938. III - COMPOSITE As indicated above, the present invention also relates to the use, for the adhesion of the tanned steel reinforcing element to a rubber matrix, of the adhesive composition described above, for forming a rubber composite reinforced with such an element which constitutes another object of the invention.
    [0030] This rubber composite may be prepared according to a process comprising at least the following steps: in a first step, combining at least a portion of the tanned steel reinforcing element coated according to the invention with a rubber matrix (or elastomer, both terms are synonymous) to form a reinforced rubber composite of the coated tanned steel reinforcing member; - Then, in a second step, crosslink by baking, preferably under pressure, the composite thus formed. The invention therefore applies to any type of rubber composite that can be obtained by the method described above, comprising at least one rubber matrix, especially of diene elastomer, bonded to the element. reinforcement made of bronzed steel via an adhesive interphase based on the adhesive composition described above.
    [0031] The diene elastomer of the composite is preferably chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene-styrene copolymers (SBR) and isoprene copolymers. butadiene (BIR), isoprene-styrene copolymers (SIR), butadiene-styrene-isoprene copolymers (SBIR) and mixtures of these elastomers. A preferred embodiment consists in using an "isoprene" elastomer, that is to say a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR). , the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers. The isoprene elastomer is preferably natural rubber or synthetic polyisoprene of the cis-1,4 type. IV - PNEUMATIC The coated bronzed steel reinforcing element and the composite described above are advantageously used for reinforcing tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy vehicles. By way of example, the single appended figure shows very schematically (without respecting a specific scale), a radial section of a tire according to the invention for a vehicle of the heavy vehicle type. This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5. The crown 2 is surmounted by a tread not shown in this schematic figure. A carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9. The carcass reinforcement 7 is in known manner constituted of at least one sheet reinforced by so-called "radial" cables, for example metallic, that is to say that these cables are arranged substantially parallel to each other and extend from a bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two beads 4 and passes through the middle of the crown frame 6). P10-3282_EN -19- This tire 1 of the invention has for example the characteristic that at least one crown reinforcement 6 and / or its carcass reinforcement 7 comprises a coated bronzed steel reinforcing element or a composite according to the invention. invention. According to another example of a possible embodiment of the invention, it is for example the rods 5 which could consist, in whole or in part, of a tanned steel reinforcing element coated according to the invention. Of course, the invention relates to the objects previously described, namely the coated bronzed steel reinforcing element and the rubber composite such as pneumatic comprising it, both in the green state (before firing or vulcanization) and in the cooked state (after cooking).
    [0032] EXAMPLES OF THE INVENTION AND COMPARATIVE TESTS These tests demonstrate that: the adhesion to a rubber matrix, of bronzed steel reinforcing elements coated with an adhesive composition according to the invention, is greatly improved compared with these same reinforcing elements in bronzed steel coated with a conventional RFL glue; and the adhesive composition allows the adhesion of the bronzed steel reinforcing elements to any rubber matrix, especially non-acrylic rubber matrices, without the use of halogenated polymer or metal oxide (unlike EP2006341). For this, several adhesive compositions, hereinafter noted C-1.1 to C-1.7, have been prepared as indicated above. Their formulations (expressed in percentage by weight) are presented in the attached Table 1. The amounts listed in this table are those of dry constituents, reduced to a total of 100 parts by weight of adhesive composition (i.e. constituents plus water). Each adhesive composition C-1.1 to C-1.7 is based on an aromatic aldehyde whose nucleus carries two aldehyde functions.
    [0033] The aldehydes of compositions C-1.1 to C-1.6 are selected from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-benzenedicarboxaldehyde, 2-hydroxybenzene-1, 3,5-tricarbaldehyde and mixtures thereof. In this case, the aldehyde is selected from the group consisting of 1,2-benzene-dicarboxaldehyde, 1,3-benzene-dicarboxaldehyde and 1,4-benzene-dicarboxaldehyde. The aldehyde of the composition C-1.7 is selected from the group consisting of furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these compounds. In this case, the aldehyde is 2,5-furanedicarboxaldehyde.
    [0034] The polyphenols of compositions C-1.1 to C-1.7 comprise one or more aromatic ring (s), it being understood that: in the case of a single aromatic ring (in the case of phloroglucinol and resorcinol), the latter carries two or three hydroxyl functions in the meta position with respect to each other or to each other, the rest of the aromatic ring being unsubstituted; o in the case of several aromatic nuclei (case of 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, phloroglucide and Morin), at least two of them are each carrying two or three hydroxyl functions in meta position; with respect to one another or to each other, it being understood that the two ortho positions of at least one of these hydroxyl functions are unsubstituted. These adhesive compositions C-1.1 to C-1.7 are also based on natural rubber latex (NR), styrene-butadiene copolymer latex (SBR) and vynilpyridine-styrene-butadiene latex (VP-SBR). In addition, each composition C-1.1 to C-1.7 comprises a gelatin.
    [0035] These adhesive compositions were compared with a C-1.0 composition known from the state of the art and comprising formaldehyde and resorcinol (in the form of pre-condensed SFR 1524 resin). The quality of the bond between the rubber matrix and the tanned steel reinforcement element is determined by a test in which the force required to extract a tanned steel reinforcing element consisting of a single wire reinforcing element is measured. diameter equal to 1.75 mm of the vulcanized rubber matrix. Steel reinforcement elements were tested, the core steel of which was coated with a copper-tin alloy coating layer (Tanned Steel). Here, the copper-tin alloy comprises 98.5% copper and 1.5% tin by weight of the alloy. In addition, each wired reinforcement element tested has no intermediate layer of non-metallic adhesion. The steel of the core is a standard steel comprising less than 0.5% by weight of chromium and less than 2% by weight of nickel.
    [0036] The rubber composition of the rubber matrix is a conventional composition useful for calendering tire metal plies, based on natural rubber, carbon black and conventional additives. In the present case, the rubber composition comprises 100 phr of natural rubber, 70 phr of 300 series carbon black, 1.5 phr of N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine, 1 phr of a cobalt salt, 0.9 phr of stearic acid, 6 phr of insoluble molecular sulfur, 0.8 phr of N-tertiarybutyl-2-benzothiazole sulfonamide and 7.5 phr of ZnO. The copper-tin alloy coating layer of the wire reinforcing element was coated directly with each adhesive composition tested, and the coated steel reinforcing elements thus coated were dried in a drying oven at 180 ° C. 30 sec. The adhesive composition was then cured by passing the coated tanned steel reinforcing elements in a treatment oven at 240 ° C for 30 seconds. Then the assembly was fused to a rubber matrix by vulcanization heat treatment to form composite specimens as described below. More specifically, the vulcanized rubber matrix is a rubber block consisting of two plates of dimensions 200 mm by 12.5 mm and 7 mm thick, applied one on the other before firing (the thickness of the resulting block is then 14 mm). It is during the manufacture of this block that the coated tanned steel reinforcement elements (15 sections in total) are trapped between the two rubber plates in the raw state, at equal distance and allowing them to pass from one side to the other. Another of these plates is an end of the coated tanned steel reinforcing element of sufficient length for subsequent traction. The block comprising the tanned coated steel reinforcement elements is then placed in a suitable mold and then baked under pressure. The temperature and the cooking time are adapted to the targeted test conditions and left to the initiative of those skilled in the art; for example, in the present case, the firing of the block is carried out at 160 ° C for 20 min. At the end of the cooking, the test piece thus constituted of the vulcanized block and the sections of coated bronzed steel reinforcing elements is put in place in the jaws of a traction machine adapted to enable each section to be tested in isolation. at a given speed and temperature (for example, in the present case at 100 mm / min and 23 ° C). Adhesion levels are characterized by measuring the so-called pulling force (denoted Fmax) to tear off the tanned steel reinforcing elements coated with the test piece. A higher value than that of the control sample (corresponding to the use of conventional RFL glue C-1.0), arbitrarily set at 100, indicates an improved result, ie a tearing force greater than that of the test specimen. The results of the tests carried out on the specimens are summarized in Table 1.
    [0037] It can be seen that the tanned steel reinforcing elements coated with the adhesive compositions C-1.1 to C-1.7 exhibit a particularly high and unexpected pulling force Fmax for those skilled in the art, since they are very greatly increased compared to an RFL adhesive. conventional composition C-1-0, without using a specific rubber matrix, halogenated polymer and metal oxide. Among the other advantages related to the invention, it should be noted that the adhesive composition may be free of formaldehyde, the use of which it is desirable to reduce or even eventually eliminate in the adhesive compositions, because recent developments in European legislation on this type of compound. In addition, formaldehyde is a compound derived from petroleum which we want as possible to get rid of for reasons of rarefaction. As another advantage of the invention, it should be noted that the adhesive composition can be used and performed on reinforcing elements made of bronzed steel, which makes it possible to guarantee that the adhesion between the metal reinforcing elements and the rubber matrices is perennial, unlike reinforcing elements of brass steel. Indeed, the copper-tin alloy does not include zinc participating in the adhesion which could undergo a dezinsification over time.
    [0038] The invention is not limited to the embodiments described above. It may also be envisaged to coat several wire reinforcing elements each comprising a steel core. In one embodiment, the wire reinforcing elements are assembled together and the copper-tin alloy coating layers coating the steel cores of the wire reinforcing elements by the adhesive composition are collectively coated. In another embodiment, the copper-tin alloy coating layer coating the steel core of each wire reinforcing member is individually coated with the adhesive composition and then the wire reinforcing elements are assembled together.
    [0039] It is also possible to envisage the use of coated bronzed steel reinforcing elements comprising a non-metallic adhesion interlayer directly coating the copper-tin alloy coating layers of the wire reinforcing elements, the layer of the adhesive composition coating then directly this intermediate layer of non-metallic adhesion. P10-3282_EN - 23 - Table 1 Adhesive compositions C-1.0 C-1.1 C-1.2 C-1.3 C-1.4 C-1.5 C-1.6 C-1.7 Aldehyde 1,2-benzenedicarboxaaldehyde (1) - - 0.9 - - - - 1,3-Benzenedicarboxaldehyde (2) - - - - 0.9 - - - 1,4-Benzenedicarboxaldehyde (3) - 0.9 - 0.9 - 0.9 0.9 - 2,5-Furanedicarboxaldehyde (4) - - - - - - - 0.9 Formaldehyde (5) 0.71 - - - - - - - Polyphenol Phloroglucinol (6) - 1.7 - - - - - - 2,2 ', 4,4'-tetrahydroxydiphenyl - - 1.7 1.7 - - - - sulphide (7) Phloroglucide (8) - - - - 1.7 1.7 - - Morin (9) - - - - - - 1.7 Resorcinol (10) - - - - - - - 1.7 SRF 1524 (11) 2.05 - - - - - - - Latex of elastomers NR (12) 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 SBR (13) 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 VP-SBR (14) 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 Additives Sodium hydroxide (15) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Gelatin (16) 1 1 1 1 1 1 1 1 Ammonia (17) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Total dry weight of 19.5 20.3 20.3 20.3 20.3 20.3 20.3 20.3 Adhesive composition Weight water 80.5 79.7 79.7 79.7 79.7 79.7 79.7 79.7 Adhesion tests Fma 'at 23 ° C (Tanned steel) 100 178 189 173 143 130 167 128 (1) 1,2-benzenedicarboxaldehyde (from ABCR; purity 98%); (2) 1,3-benzenedicarboxaldehyde (from ABCR, 98% purity); (3) 1,4-Benzenedicarboxaldehyde (from ABCR, 98% purity); (4) 2,5-Furanedicarboxaldehyde (Aldrich company, 97% purity); (5) Formaldehyde (from Caldic, diluted to 36%); (6) Phloroglucinol (from Alfa Aesar, 99% pure); (7) 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide (from Alfa Aesar, 98% purity); (8) Phloroglucide (from Alfa Aesar, 95% pure); P10-3282_EN - 24 - (9) Morin (from Fluka) (10) Resorcinol (from Sumitomo, purity 99.5%); (11) Precondensed resin SRF 1524 (from Schenectady, diluted to 75%); (12) Latex NR ("Trang Latex" from the company Bee tex, diluted to 61% by weight); (13) Latex SBR ("Encord-201" from Jubilant, diluted to 41% by weight) (14) Vinylpyridine-styrene-butadiene latex ("VP 106S" from Eliokem, diluted to 41%); (15) Sodium hydroxide (from Aldrich, diluted to 30%); (16) Gelatin (Bovine skin gelatin from Aldrich) (17) Ammonia (from Aldrich, diluted to 21%).
    [0040] 10 P10-3282_EN
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. Coated steel reinforcing element, characterized in that it comprises: - one or more wire reinforcing elements each comprising a steel core; a layer of a coating of a copper-tin alloy coating at least a portion of the steel core of the or each wire reinforcing element; and an adhesive layer coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element, the adhesive layer comprising an adhesive composition comprising at least one phenol-aldehyde resin based on least: an aromatic aldehyde bearing at least one aldehyde function, comprising at least one aromatic ring; a polyphenol having one or more aromatic ring (s), it being understood that: in the case of a single aromatic ring, the latter is carrying two or three hydroxyl functions in the meta position with respect to the other or to each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that both Ortho positions of at least one of these hydroxyl functions are unsubstituted.
    [0002]
    The coated steel backing element of claim 1, wherein the adhesive layer directly coats at least a portion of the copper-tin alloy coating layer of the or each wire backing member.
    [0003]
    A coated steel reinforcing element according to claim 1, wherein the adhesive layer directly coats a non-metallic adhesion interlayer directly coating at least a portion of the copper-tin alloy coating layer of the or each element wired reinforcement.
    [0004]
    4. Reinforced steel reinforcing element according to any one of the preceding claims, wherein the aromatic aldehyde carries at least two aldehyde functions.
    [0005]
    A coated steel reinforcing element according to any one of the preceding claims, wherein the aromatic ring of the aromatic aldehyde carries two aldehyde functions.
    [0006]
    A coated steel reinforcing member according to any one of the preceding claims, wherein the aromatic ring of the aromatic aldehyde is a benzene ring. P10-3282_EN- 26 -
    [0007]
    7. Reinforced steel reinforcing element according to the preceding claim, wherein the aromatic aldehyde is selected from the group consisting of 1,2-benzenedicarboxaldehyde, 1,3-benzene-dicarboxaldehyde, 1,4-benzene-dicarboxaldehyde , 2-hydroxybenzene-1,3,5-tricarbaldehyde and mixtures of these compounds.
    [0008]
    8. Reinforced steel reinforcing element according to the preceding claim, wherein the aromatic aldehyde is 1,4-benzenedicarboxaldehyde.
    [0009]
    A coated steel reinforcing element according to any one of claims 1 to 3, wherein the aldehyde is of the general formula (A): ## STR2 ## where X is N, S or OR is -H or CHO
    [0010]
    10. Reinforced steel reinforcing element according to the preceding claim, wherein the aldehyde is selected from the group consisting of furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these compounds.
    [0011]
    A coated steel reinforcing member according to any one of the preceding claims, wherein the polyphenol is selected from the group consisting of phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide and mixtures thereof .
    [0012]
    The coated steel reinforcing member of any one of the preceding claims, wherein the adhesive composition comprises an unsaturated elastomer latex.
    [0013]
    13. Reinforced steel reinforcing element according to the preceding claim, wherein the unsaturated elastomer of the latex is a diene elastomer, preferably selected from the group consisting of polybutadienes, butadiene copolymers, polyisoprenes, isoprene copolymers vinylpyridine-styrene-butadiene terpolymers and mixtures of these elastomers. P10-3282_EN- 27 -
    [0014]
    A method of manufacturing a coated steel reinforcing member, characterized in that the coated steel reinforcing member comprises: - one or more wire reinforcing elements each comprising a steel core; a layer of a coating of a copper-tin alloy coating at least a portion of the steel core of the or each wire reinforcing element; and an adhesive layer coating at least a portion of the layer of the copper-tin alloy coating of the or each wire reinforcing element, the method comprising a step of coating at least a portion of the coating layer of copper-tin alloy of the or each wire reinforcing element by the adhesive layer comprising an adhesive composition comprising at least one phenol-aldehyde resin based on at least: an aromatic aldehyde bearing at least one aldehyde function, comprising at least one minus an aromatic nucleus; a polyphenol having one or more aromatic ring (s), it being understood that: in the case of a single aromatic ring, the latter is carrying two or three hydroxyl functions in the meta position with respect to the other or each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that both Ortho positions of at least one of these hydroxyl functions are unsubstituted.
    [0015]
    15. Use, for adhesion of a steel reinforcing member to a rubber matrix, of an adhesive composition forming an adhesive layer coating at least a portion of a layer of a copper-copper alloy coating. tin coating at least a portion of each steel core of one or more wire reinforcing elements, the adhesive composition comprising at least one phenol-aldehyde resin based on at least: - an aromatic aldehyde carrying at least one aldehyde function, comprising at least one aromatic nucleus; a polyphenol having one or more aromatic ring (s), it being understood that: in the case of a single aromatic ring, the latter is carrying two or three hydroxyl functions in the meta position with respect to the other or each other, the remainder of the aromatic ring being unsubstituted; in the case of several aromatic rings, at least two of them are each carrying two or three hydroxyl functions in the meta position relative to one another or to each other, it being understood that both Ortho positions of at least one of these hydroxyl functions are unsubstituted.
    [0016]
    16. Reinforced rubber composite of at least one coated steel reinforcing element according to any one of claims 1 to 13 comprising a rubber matrix in which the coated steel reinforcing element is embedded.
    [0017]
    17. A tire comprising at least one coated steel reinforcing element according to any one of claims 1 to 13 or a rubber composite according to claim 16. P10-3282_EN
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    同族专利:
    公开号 | 公开日
    CN105940074A|2016-09-14|
    EP3102646A1|2016-12-14|
    JP2017506706A|2017-03-09|
    WO2015118044A1|2015-08-13|
    FR3017071B1|2016-01-29|
    US20170166011A1|2017-06-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1466114A|1973-02-02|1977-03-02|Toyo Tire & Rubber Co|Pneumatic tyre|
    EP0648891A1|1993-10-15|1995-04-19|Compagnie Generale Des Etablissements Michelin-Michelin & Cie|Stainless steel yarn for pneumatic tyre carcass|
    WO2012112240A1|2011-02-17|2012-08-23|Milliken & Company|Adhesion composition and textile materials and articles treated therewith|
    WO2013017423A1|2011-08-04|2013-02-07|Compagnie Generale Des Etablissements Michelin|Aqueous adhesive composition based on polyaldehyde and 2,2',4,4'-tetrahydroxydiphenyl sulfide|
    WO2013017422A1|2011-08-04|2013-02-07|Compagnie Generale Des Etablissements Michelin|Aqueous adhesive composition based on polyaldehyde and phloroglucinol|WO2017198967A1|2016-05-20|2017-11-23|Compagnie Generale Des Etablissements Michelin|Composite and power transmission belt|
    WO2017198968A1|2016-05-20|2017-11-23|Compagnie Generale Des Etablissements Michelin|Composite and power transmission belt|US2343551A|1938-07-02|1944-03-07|Us Rubber Co|Adhesive composition|
    US3411980A|1965-03-26|1968-11-19|Goodyear Tire & Rubber|In-situ resin adhesion of reinforcing element-to-rubber|
    US5535612A|1994-10-21|1996-07-16|The Goodyear Tire & Rubber Company|Method and apparatus for drawing wire through a plurality of standard dies at the die positions|
    JP2000219938A|1999-01-28|2000-08-08|Nippon Steel Corp|Wire rod for high tensile strength steel wire and its production|
    EP1841605B1|2005-01-25|2008-11-26|Pirelli Tyre S.p.A.|Pneumatic tyre with improved bead structure|
    JP4929807B2|2006-04-13|2012-05-09|Ｎｏｋ株式会社|Vulcanized adhesive composition|
    FR2913355B1|2007-03-08|2009-08-21|Michelin Soc Tech|PROCESS FOR WET TREADING WIRE OF STEEL WIRES FOR REINFORCING PNEUMATIC BANDAGES|
    US20100101696A1|2007-06-05|2010-04-29|Simone Agresti|Tire, metal cord and process for manufacturing a metal cord|
    US8247490B1|2011-02-17|2012-08-21|Milliken & Company|Adhesion composition and textile materials and articles treated therewith|
    FR2978769B1|2011-08-04|2013-09-27|Michelin Soc Tech|AQUEOUS ADHESIVE COMPOSITION BASED ON POLYALDEHYDE AND POLYPHENOL|
    FR3017070B1|2014-02-06|2017-08-25|Michelin & Cie|STEEL REINFORCING ELEMENT COATED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL|
    FR3017133B1|2014-02-06|2016-03-11|Michelin & Cie|RUBBER COMPOSITE REINFORCED WITH AT LEAST ONE STEEL REINFORCING ELEMENT ADHESIVED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL|FR3017133B1|2014-02-06|2016-03-11|Michelin & Cie|RUBBER COMPOSITE REINFORCED WITH AT LEAST ONE STEEL REINFORCING ELEMENT ADHESIVED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL|
    FR3049611A1|2016-04-01|2017-10-06|Michelin & Cie|AQUEOUS ADHESIVE COMPOSITION COMPRISING A THERMOSETTING RESIN|
    FR3054233A1|2016-07-21|2018-01-26|Compagnie Generale Des Etablissements Michelin|HIGH RIGIDITY RUBBER COMPOSITION|
    法律状态:
    2015-02-19| PLFP| Fee payment|Year of fee payment: 2 |
    2016-02-18| PLFP| Fee payment|Year of fee payment: 3 |
    2017-02-17| PLFP| Fee payment|Year of fee payment: 4 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 5 |
    2019-10-25| ST| Notification of lapse|Effective date: 20191006 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450903A|FR3017071B1|2014-02-06|2014-02-06|BRONZE METALLIC REINFORCING ELEMENT ADHERED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL|FR1450903A| FR3017071B1|2014-02-06|2014-02-06|BRONZE METALLIC REINFORCING ELEMENT ADHERED BY AN ADHESIVE COMPOSITION BASED ON AROMATIC ALDEHYDE AND POLYPHENOL|
    CN201580006771.4A| CN105940074A|2014-02-06|2015-02-05|Bronzed metal reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol|
    JP2016550712A| JP2017506706A|2014-02-06|2015-02-05|Brass-treated metal reinforcement elements imparted with adhesive properties by adhesive compositions containing aromatic aldehydes and polyphenols|
    PCT/EP2015/052363| WO2015118044A1|2014-02-06|2015-02-05|Bronzed metal reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol|
    EP15704499.1A| EP3102646A1|2014-02-06|2015-02-05|Bronzed metal reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol|
    US15/117,045| US20170166011A1|2014-02-06|2015-02-05|Bronzed metal reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol|
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