WO2017103495A1 - Composition elastomerique comprenant une charge recouverte au moins partiellement de silice - Google Patents
Composition elastomerique comprenant une charge recouverte au moins partiellement de silice Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/06—Copolymers with styrene
- C08J2309/08—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/10—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
Definitions
- the invention relates to a rubber composition in particular for a tire tread, and more particularly for a tire intended to equip vehicles carrying heavy loads and traveling at a high speed, such as, for example, trucks, tractors, trailers or road buses. , plane etc.
- carbon black has such aptitudes, which is not generally the case for inorganic fillers, in particular silicas. Indeed, for reasons of mutual affinities, these inorganic filler particles have an unfortunate tendency in the elastomeric matrix to agglomerate with each other. These interactions have the detrimental consequence of limiting the dispersion of the charge and therefore the reinforcing properties to a level substantially lower than that which it would be theoretically possible to achieve if all the bonds (inorganic filler / elastomer) that can be created during the mixing operation, were actually obtained; these interactions tend on the other hand to increase the consistency in the raw state of the compositions rubbery and thus to make their implementation ("processability") more difficult than in the presence of carbon black.
- reinforcing fillers at least partially covered with silica are particularly advantageous, in particular reinforcing fillers consisting of carbon black coated at least partially with silica as described in particular in the publications WO98 / 13428 and EP 711 805 B1, reinforcing fillers consisting of metal oxide coated at least partially with silica as described in particular in publication FR2888243.
- one type of solution consists in improving the dispersibility of the filler in the elastomeric matrix by mixing the elastomer and the "liquid" phase filler.
- an elastomer in the form of latex has been used in the form of elastomer particles dispersed in water, and an aqueous dispersion of the filler, that is to say a dispersed filler. in water, commonly called "slurry".
- 6,048,923 make it possible to obtain a masterbatch of elastomer and filler having a very good dispersion of the filler in the elastomeric matrix, which is greatly improved with respect to dispersion. of the charge in the elastomeric matrix that can be obtained during solid phase mixing of elastomer and reinforcing filler.
- This method consists in particular of incorporating a continuous flow of a first fluid constituted by an elastomer latex into the mixing zone of a coagulation reactor, to incorporate a second continuous flow of a second fluid consisting of an aqueous dispersion of pressurized charging in the mixing zone to form a mixture with the elastomer latex; the mixing of these two fluids being sufficiently energetic to allow the elastomer latex to be coagulated almost completely with the filler before the exit orifice of the coagulation reactor and then to dry the coagulum obtained.
- masterbatch is used herein to refer to an elastomer-based composite in which a filler and possibly other additives have been introduced.
- compositions based on diene elastomer and filler coated at least partially with silica and having a very good dispersion of the reinforcing filler in the elastomeric matrix, in particular obtained by a mixing step in which liquid phase, had improved reinforcing properties without degradation of hysteretic properties, and this without containing coupling agent, contrary to the knowledge of those skilled in the art.
- the subject of the invention is thus a rubber composition based on at least one diene elastomer, a reinforcing filler comprising mainly a filler at least partially covered with silica and a crosslinking system, characterized in that the dispersion of the filler in the elastomeric matrix has a Z-score greater than or equal to 70 and in that the composition has no charge coupling agent with the elastomer.
- the filler coated at least partially with silica is chosen from carbon black, metal hydroxides, in particular magnesium or aluminum hydroxides, and polymer particles. crosslinked, more preferably the filler at least partially covered with silica is constituted by carbon black.
- the diene elastomer is chosen from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers, preferably the diene elastomer is a natural rubber.
- the composition comprises less than 15 phr of plasticizing agents, preferably less than 5 phr.
- the invention also relates to a process for preparing a composition based on at least one diene elastomer, a reinforcing filler comprising mainly a filler at least partially covered with silica and a crosslinking system, the dispersion of the filler in the matrix.
- elastomeric being a note Z greater than or equal to 70 and the composition being devoid of agent for coupling the filler with the elastomer:
- preparing a masterbatch comprising the diene elastomer and the filler at least partially covered with silica, said first masterbatch having a dispersion of the filler in the elastomeric matrix having a Z-score greater than or equal to 70,
- the invention relates to a finished or semi-finished article comprising a composition as mentioned above, a tread comprising such a composition and a tire or semi-finished product comprising such a composition, in particular a tire intended to equip vehicles carrying heavy loads and driving at high speed.
- the rubber compositions are characterized, before and after firing, as indicated below. Dispersion
- the charge dispersion in an elastomeric matrix can be represented by the note Z, which is measured, after crosslinking, according to the method described by S. Otto and Al in Kautschuk Kunststoffe, 58 Ciphergang, NR 7- 8/2005, in accordance with ISO 11345.
- the calculation of the Z score is based on the percentage of area in which the charge is not dispersed ("% undispersed area"), as measured by the "disperGRADER +" apparatus supplied with its operating mode and software. 'disperDATA' exploitation by Dynisco according to the equation:
- the percentage of undispersed surface is measured by a camera observing the surface of the sample under 30 ° incident light.
- the bright spots are associated with filler and agglomerates, while the dark spots are associated with the rubber matrix; digital processing transforms the image into a black and white image, and allows the determination of the percentage of undispersed surface, as described by S. Oto in the aforementioned document.
- a Z score greater than or equal to 80 corresponds to a surface having a very good dispersion of the filler in the elastomeric matrix.
- tan ( ⁇ ) max The dynamic properties, of which tan ( ⁇ ) max, are measured on a viscoanalyzer (Metravib V A4000) according to ASTM D 5992 - 96.
- the response of a sample of vulcanized composition (4 mm cylindrical test specimen) is recorded. thickness and 400 mm 2 section), subjected to sinusoidal stress in alternating single shear, at the frequency of 10 Hz, under normal temperature conditions according to ASTM D 1349 - 99.
- a crest amplitude sweep is carried out at peak from 0.1 to 50% (forward cycle), then from 50% to 0.1% (return cycle).
- the result exploited is the loss factor, tan (ô).
- tan ( ⁇ ) max For the return cycle, the maximum value of tan ( ⁇ ) observed (tan ( ⁇ ) max) is indicated.
- the values of tan ( ⁇ ) max given below are measured at 100 ° C.
- the invention relates to a rubber composition based on at least one diene elastomer, a reinforcing filler comprising predominantly a filler coated at least partially with silica and a crosslinking system, characterized in that the dispersion of the filler in the elastomeric matrix has a note Z greater than or equal to 70 and in that the composition is free of charge coupling agent with ⁇ elastomer
- 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).
- the composition according to the invention comprises at least a first diene elastomer and optionally a second elastomer identical or different from the first, which may or may not be a diene elastomer.
- elastomer or "diene” rubber there must be understood in known manner an elastomer derived at least in part (ie, a homopolymer or a copolymer) from monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or otherwise).
- diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
- the term “essentially unsaturated” is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%);
- diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "substantially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
- the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
- diene elastomers there are also natural rubber and synthetic elastomers.
- synthetic diene elastomers which can be used in accordance with the invention, the term diene elastomer is more particularly understood to mean:
- (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
- conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as for example 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
- Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
- the copolymers may contain between 99% and 20% by weight of diene units and between 80% and 80% by weight of vinylaromatic units.
- the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
- the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
- alkoxysilane groups as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445).
- polyether groups as described for example in EP 1 127 909 or US 6,503,973, WO 2009/000750 and WO 2009/000752.
- functionalized elastomers mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
- Suitable polybutadienes and in particular those having a content (mol%) in units -1.2 between 4%> and 80%> or those having a content (%> molar) in cis-1,4 greater than 80%> polyisoprenes, butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) between 0 ° C. and -70 ° C. and more particularly between -10 ° C.
- Tg glass transition temperature
- styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (%> molar) in -1,2 bonds of the butadiene part between 4% and 75%, a content (mol%) of trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90%.
- the isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a e Tg between -5 ° C and -50 ° C.
- those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, in particular an isoprene content of between 15% and 50% by weight are suitable.
- the synthetic diene elastomer (s) according to the invention are preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR), butadiene copolymers, copolymers of isoprene and mixtures of these elastomers.
- BR polybutadienes
- IR synthetic polyisoprenes
- butadiene copolymers copolymers of isoprene and mixtures of these elastomers.
- Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
- SBIR butadiene-styrene
- the liquid phase mixing processes are preferably used to obtain masterbatches based on diene elastomer and reinforcing filler having a very good dispersion of the reinforcing filler in the elastomer.
- a diene elastomer latex will be used more particularly, the elastomer latex being a particular form of the elastomer which is present in the form of elastomer particles dispersed in water.
- the invention therefore preferably relates to diene elastomer latices, the diene elastomers being those defined above.
- NR natural rubber
- this natural rubber exists in different forms as detailed in Chapter 3 "Latex concentrates: properties and composition", K.F. Gaseley, A.D.T. Gordon and T. D. Pendle in “Natural Rubber Science and Technology", A. D. Roberts, Oxford University Press - 1988.
- field latex natural rubber latexes
- natural concentrated rubber latex epoxidized latexes.
- EMR epoxidized latexes.
- deproteinized latex or prevulcanized latex.
- Field natural rubber latex is a latex in which ammonia has been added to prevent premature coagulation and the concentrated natural rubber latex is a field latex which has been treated to a wash followed by a new concentration.
- the different categories of concentrated natural rubber latex are listed in particular according to ASTM D 1076-06.
- concentrated natural rubber latexes there are in particular concentrated natural rubber latexes of quality called “HA” (high ammonia) and quality called “LA”;
- concentrated natural rubber latex HA grade is advantageously used for the invention concentrated natural rubber latex HA grade.
- the NR latex may be modified beforehand physically or chemically (centrifugation, enzymatic treatment, chemical modification, etc.)
- the latex can be used directly or be previously diluted in water to facilitate its implementation.
- the latex may in particular consist of a synthetic diene elastomer already available in the form of an emulsion (for example a copolymer of butadiene and styrene, SBR, prepared in emulsion), or a diene elastomer synthetic solution initially (for example a SBR prepared in solution) which is emulsified in a mixture of organic solvent and water, generally by means of a surfactant.
- a synthetic diene elastomer already available in the form of an emulsion for example a copolymer of butadiene and styrene, SBR, prepared in emulsion
- SBR styrene
- SBR latex in particular an emulsion-prepared SBR (“ESBR”) or an SBR prepared in solution (“SSBR”), and more particularly an SBR prepared in emulsion.
- ESBR emulsion-prepared SBR
- SSBR SBR prepared in solution
- an SBR elastomer In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, is used, or a high styrene content, for example from 35 to 45%, a vinyl bond content of the butadiene part of between 15% and 70%, a content (mol%) of trans-1,4 bonds of between 15% and 75% and a Tg ranging from -10 ° C to -55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of cis-1,4 bonds.
- one or more natural rubber latexes may be used in the form of a blend, one or more synthetic rubber latexes in a blend or a blend of one or more natural rubber latexes with one or more synthetic rubber latexes.
- the composition comprises a second elastomer which may or may not be a diene elastomer, in the latter case particularly non-dienic butyl elastomers such as poly (isobutylene) homopolymers or copolymers based on poly (isobutylene) (of course if it is copolymers with isoprene, there are the diene elastomers described above), as well as halogenated derivatives, in particular generally brominated or chlorinated, of these poly homopolymers ( isobutylene) and copolymers based on poly (isobutylene).
- a diene elastomer which may or may not be a diene elastomer, in the latter case particularly non-dienic butyl elastomers such as poly (isobutylene) homopolymers or copolymers based on poly (isobutylene) (of course if it is copolymers with isoprene, there are
- non-diene elastomers include copolymers of isobutylene and styrene derivatives, such as isobutylene and brominated methylstyrene copolymers (BIMS), of which an elastomer named EXXPRO sold by the company Exxon in particular is part.
- BIMS isobutylene and brominated methylstyrene copolymers
- non-diene elastomer particularly suitable for the invention of non-dienic thermoplastic elastomers (TPE).
- TPE thermoplastic elastomers
- the weight fraction of the first diene elastomer in the elastomeric matrix is greater than or equal to 50% and preferably greater than or equal to 60%. loads
- the majority used is any filler covered at least partially with silica.
- the filler coated at least partially with silica may consist in particular of carbon black, metal hydroxides, in particular magnesium or aluminum, and crosslinked polymer particles.
- Carbon blacks coated partially or wholly with silica by a post-treatment, or silica blacks modified in situ by silica, such as, without limitation, the charges marketed by Cabot are particularly suitable. Corporation under the name EcoblackTM "CRX 2000” or “CRX4000”, or the charges described in publications US2003040553, WO9813428.
- Such a reinforcing filler preferentially contains a silica content of 10% by weight of the reinforcing filler.
- Such fillers can be obtained according to the method of coating carbon black with silica as described in Examples 1 and 2 of the patent application WO00 / 05312.
- silica-coated synthetic metal hydroxides whose metal M is selected from the group consisting of Al, Fe, Mg, and mixtures of these metals.
- M represents Al or Mg as described in particular in the publications WO06 / 002993 or WO07 / 003408.
- This filler covered at least partially with silica may advantageously constitute more than 60% of the total reinforcing filler.
- organic filler such as carbon black or organic functionalized polyvinylaromatic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793, and / or one or more reinforcing inorganic fillers such as silica and / or another filler coated at least partially with silica.
- carbon black all carbon blacks are suitable, especially blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
- the reinforcing carbon blacks of the 100, 200 or 300 series for example blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or else, according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
- any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or “non-black filler” as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words, able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
- -OH hydroxyl groups
- reinforcing inorganic filler also refers to mixtures of various reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
- Suitable reinforcing inorganic fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO 2), or of the aluminous type, in particular alumina (Al 2 O 3).
- the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
- HDS highly dispersible precipitated silicas
- the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia
- the Hi-Sil EZ150G silica from the PPG company
- the Zeopol 8715, 8745 and 8755 silicas of the Huber Company the high surface area silicas as described in the application WO 03/16837.
- the filler coated at least partially with silica represents more than 90% of the reinforcing filler.
- the filler coated at least partially with silica constitutes the only reinforcing filler of the composition.
- the total reinforcing filler content is between 20 and 200 phr, more preferably between 30 and 150 phr, and even more preferably between 30 and 100 phr, the optimum being in a known manner different according to the particular applications targeted: the level of reinforcement expected on a bicycle tire, for example, is of course less than that required on a tire capable of driving at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a commercial vehicle such as Heavy weights.
- the invention is used as reinforcing filler at least partially covered with silica, carbon black coated at least partially with silica with a rate ranging from 30 to 90 phr and it may preferably be combined with an organic filler, in particular carbon black, or an inorganic filler, in particular silica, the content of which varies from 1 to 50 phr, more particularly the total filler of the composition comprising carbon black.
- the composition comprises only carbon black coated at least partially with silica with a content ranging from 30 to 90 phr and more preferably the rate varies from 35 to 75 phr.
- composition according to the invention does not comprise a coupling agent.
- the rubber compositions according to the invention optionally also include all or part of the usual additives usually used in elastomer compositions intended in particular for the production of treads, such as, for example, pigments, protective agents such as waxes, -ozone, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M).
- additives usually used in elastomer compositions intended in particular for the production of treads, such as, for example, pigments, protective agents such as waxes, -ozone, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M).
- the composition according to the invention comprises less than 15 phr of plasticizing agents, preferably less than 5 phr, and even more preferably the composition is devoid of plasticizing agents.
- the plasticizers conventionally used in such compositions are solid hydrocarbon resins (or plasticizing resin), extension oils (or plasticizing oil), or a mixture of both.
- the crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
- a vulcanization system that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
- various known secondary accelerators or vulcanization activators such as zinc oxide.
- Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
- the primary vulcanization accelerator is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
- accelerator primary or secondary
- accelerators are for example selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), tetrabenzylthiuram disulfide (“TBZTD”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N dicyclohexyl-2-benzothiazyl sulphenamide (“DCBS”), N-tert-butyl-2-benzothiazyl sulphenamide (“TBBS”), N-tert-butyl-2-benzothiazyl sulphenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ ZBEC ”) and mixtures of these compounds.
- a primary accelerator of the sulfenamide type is used.
- the rubber compositions of the invention are manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as a "non-productive" phase) at a high temperature, up to a maximum temperature of between 130 ° C. and 200 ° C., preferably between 145 ° C. and 185 ° C., followed by second phase of mechanical work (sometimes called a "productive" phase) at a lower temperature, typically less than 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization.
- a first phase of work or thermomechanical mixing sometimes referred to as a "non-productive" phase
- second phase of mechanical work sometimes called a "productive” phase
- all the basic constituents of the compositions of the invention are intimately incorporated, by kneading, during the so-called non-productive first phase. , that is to say that is introduced into the mixer and that is kneaded thermomechanically, in one or more steps, at least these different basic constituents until the maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C.
- the diene elastomer and the filler coated at least partially with silica are mixed with the basic constituents of the compositions of the invention, with the exception of the vulcanization system, under the shape of a master mix that has been previously prepared ..
- this masterbatch is made in the "liquid” phase.
- the diene elastomer in the form of latex which is in the form of elastomer particles dispersed in water, and an aqueous dispersion of the filler, are used. at least partially covered with silica, that is to say a charge dispersed in water, commonly called “slurry”. More preferably still, the process steps described in document US Pat. No.
- 6,048,923 which consists in particular in incorporating a continuous flow of a first fluid constituted by the elastomer latex into the mixing zone of a coagulation reactor defining an elongated coagulation zone extending between the mixing zone and an outlet orifice, to incorporate a second continuous flow of a second fluid constituted by the aqueous dispersion of the pressure feedstock into the mixing zone to form a mixture with elastomer latex; the mixing of these two fluids being sufficiently energetic to allow the elastomer latex to be coagulated almost completely with the filler before the exit orifice of the coagulation reactor and then to dry the coagulum obtained.
- this or these incorporations can be carried out simultaneously with the introduction into the mixer of the other constituents (in particular the master mix) but also advantageously that this or these incorporations can be shifted in time from a few tens of seconds to a few minutes.
- an organic or inorganic filler and a second elastomer may be introduced separately or in the form of a second master batch containing the second elastomer and the organic filler or inorganic.
- the organic or inorganic filler may be introduced before, after or simultaneously with the second elastomer.
- the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents (in the form where appropriate) are introduced into a suitable mixer such as a conventional internal mixer. as described above), and other various additives, with the exception of the vulcanization system.
- the total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
- the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
- the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded in the form of a rubber profile that can be used, for example, as a tread. tires for passenger cars, trucks etc.
- control compositions TM are produced according to a conventional method of mixing (hereinafter described) in solid form in which the elastomer, natural rubber, and the reinforcing filler, the N234 carbon black marketed by the company Cabot Corporation and the Ultrasil precipitation silica 7000 sold by the company Evonik, or carbon black coated with CRX2125 silica marketed by Cabot Corporation, are introduced in solid form.
- control rubber compositions TA which are not in accordance with the invention and the compositions CA in accordance with the invention are produced according to the mixing method described hereinafter but in which the elastomer, natural rubber, and the reinforcing filler, black of carbon coated with CRX2125 silica, were previously prepared in the form of a masterbatch A.
- the masterbatch A comprising natural rubber and a CRX2125 filler is made in the liquid phase according to the process described in US Patent No. 6,048,923 .
- a masterbatch is prepared from carbon black coated with CRX2125 silica marketed by the company Cabot Corporation, and field natural rubber latex (“field latex”) from from Malaysia with a solids content of 28% and an ammonia content of 0.3%.
- a masterbatch A of natural rubber and a CRX2125 filler is thus obtained in which the carbon black content is 50 phr.
- the mixing process used for the various compositions is as follows.
- the mixture thus obtained is recovered, cooled and the vulcanization system (sulfur and sulfenamide accelerator) is added to an external mixer (homogenizer) at 70 ° C., mixing the whole (productive phase) for about 5 to 6 hours. min.
- an external mixer homogenizer
- the latter may also be introduced on external mixer instead of the introduction on internal mixer.
- compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or in the form of profiles that can be used directly, after cutting and / or or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
- the rubber compositions TM1 to TM3 are therefore prepared "in bulk" and the compositions TA1 and CA1 are prepared from the master batch A, they are distinguished from each other as follows:
- composition TM1 not in accordance with the invention comprises a blend of carbon black and silica as a reinforcing filler and a coupling agent,
- composition TM2 not in accordance with the invention comprises silica coated black as a reinforcing filler and a coupling agent
- the TM3 composition not in accordance with the invention is identical to the TM2 composition with the exception of the coupling agent of which it is devoid,
- composition CA1 according to the invention comprises carbon black coated with silica as a reinforcing filler but does not include a coupling agent.
- compositions TM1 to TM3, TA1 and CA1 are shown in Table 1 below, in which the levels are given in parts by weight per hundred parts of elastomers, phr. Table 1
- compositions TA1 and CA1 prepared from a masterbatch A made in the liquid phase have a dispersion of the filler in the elastomer matrix which is greatly improved compared with those of the compositions prepared in the TM mass.
- the difference is less marked with the TM1 composition comprising carbon black and silica, which represents, in a manner known to those skilled in the art, a charge cutting operation more easily implemented than silica-coated carbon blacks. ).
- CA1 has a reinforcement (values of MA300 and MA300 / MA100) almost identical to that of the composition TA1 which includes a coupling agent and significantly higher than the properties of reinforcement of the 3 control compositions TM1 to TM3.
- This observation is all the more surprising, since it appears clearly from the TM2 and TM3 compositions, that the absence of a coupling agent has a significant negative impact on the reinforcing properties of the composition that lacks a coupling agent. (TM3).
- composition CA1 according to the invention has a hysteresis (value of Tanô max round) improved compared to the composition TA1 itself.
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Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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BR112018012364A BR112018012364A2 (pt) | 2015-12-17 | 2016-12-15 | composição elastomérica que compreende uma carga coberta pelo menos parcialmente por sílica |
US16/062,354 US11702531B2 (en) | 2015-12-17 | 2016-12-15 | Elastomer composition comprising a filler at least partially covered by silica |
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Application Number | Priority Date | Filing Date | Title |
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FR1562570A FR3045627B1 (fr) | 2015-12-17 | 2015-12-17 | Composition elastomerique comprenant une charge recouverte au moins partiellement de silice |
FR1562570 | 2015-12-17 |
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WO2017103495A1 true WO2017103495A1 (fr) | 2017-06-22 |
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PCT/FR2016/053454 WO2017103495A1 (fr) | 2015-12-17 | 2016-12-15 | Composition elastomerique comprenant une charge recouverte au moins partiellement de silice |
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US (1) | US11702531B2 (fr) |
BR (1) | BR112018012364A2 (fr) |
FR (1) | FR3045627B1 (fr) |
WO (1) | WO2017103495A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109251370A (zh) * | 2017-07-13 | 2019-01-22 | 双钱集团(新疆)昆仑轮胎有限公司 | 应用于轮胎胎面胶中的改性n234炭黑 |
WO2019092363A1 (fr) | 2017-11-07 | 2019-05-16 | Compagnie Generale Des Etablissements Michelin | Pneu ayant une bande de roulement combinant des incisions inclinees avec un materiau specifique |
WO2019094551A1 (fr) | 2017-11-10 | 2019-05-16 | Cabot Corporation | Procédés de production d'un composé élastomère et composés élastomères |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US11383561B2 (en) | 2017-12-21 | 2022-07-12 | Compagnie Generale Des Etablissements Michelin | Crown architecture of an electrically conductive tire for a civil engineering vehicle |
WO2023107991A1 (fr) * | 2021-12-08 | 2023-06-15 | Beyond Lotus Llc | Procédés de préparation d'un composite ayant des résines |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6048923A (en) * | 1996-04-01 | 2000-04-11 | Cabot Corporation | Elastomer composites method and apparatus |
FR3003864A1 (fr) * | 2013-04-02 | 2014-10-03 | Michelin & Cie | Methode pour preparer un melange maitre d'elastomere dienique et de charge renforcante |
WO2015091270A2 (fr) * | 2013-12-20 | 2015-06-25 | Compagnie Generale Des Etablissements Michelin | Composition elastomerique ayant une dispersion de charge amelioree |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2981937B1 (fr) * | 2011-10-28 | 2013-11-08 | Michelin Soc Tech | Composition elastomerique presentant une tres bonne dispersion de la charge dans la matrice elastomerique |
CN103987531A (zh) * | 2011-12-12 | 2014-08-13 | 米其林集团总公司 | 具有填料在弹性体基体中非常好的分散性的弹性体组合物 |
FR3099164B1 (fr) * | 2019-07-26 | 2021-06-25 | Michelin & Cie | Composition de caoutchouc. |
-
2015
- 2015-12-17 FR FR1562570A patent/FR3045627B1/fr not_active Expired - Fee Related
-
2016
- 2016-12-15 WO PCT/FR2016/053454 patent/WO2017103495A1/fr active Application Filing
- 2016-12-15 BR BR112018012364A patent/BR112018012364A2/pt not_active Application Discontinuation
- 2016-12-15 US US16/062,354 patent/US11702531B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6048923A (en) * | 1996-04-01 | 2000-04-11 | Cabot Corporation | Elastomer composites method and apparatus |
FR3003864A1 (fr) * | 2013-04-02 | 2014-10-03 | Michelin & Cie | Methode pour preparer un melange maitre d'elastomere dienique et de charge renforcante |
WO2015091270A2 (fr) * | 2013-12-20 | 2015-06-25 | Compagnie Generale Des Etablissements Michelin | Composition elastomerique ayant une dispersion de charge amelioree |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109251370A (zh) * | 2017-07-13 | 2019-01-22 | 双钱集团(新疆)昆仑轮胎有限公司 | 应用于轮胎胎面胶中的改性n234炭黑 |
WO2019092363A1 (fr) | 2017-11-07 | 2019-05-16 | Compagnie Generale Des Etablissements Michelin | Pneu ayant une bande de roulement combinant des incisions inclinees avec un materiau specifique |
WO2019094551A1 (fr) | 2017-11-10 | 2019-05-16 | Cabot Corporation | Procédés de production d'un composé élastomère et composés élastomères |
DE112018005422T5 (de) | 2017-11-10 | 2020-07-30 | Cabot Corporation | Verfahren zur Herstellung eines Elastomercompound und Elastomercompounds |
Also Published As
Publication number | Publication date |
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US20200399442A1 (en) | 2020-12-24 |
FR3045627B1 (fr) | 2018-02-02 |
US11702531B2 (en) | 2023-07-18 |
FR3045627A1 (fr) | 2017-06-23 |
BR112018012364A2 (pt) | 2018-12-04 |
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