• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a hydrocarbon resin, said hydrocarbon resin having a number-average molecular weight (Mn) of between 700 and 1000 g. mol, a mean molecular mass Mz greater than 6000 g / mol and a polymolecularity index (Ip) greater than 2.4.
    公开号:FR3030545A1
    申请号:FR1463078
    申请日:2014-12-22
    公开日:2016-06-24
    发明作者:Julien Chatard；Gaudemaris Benoit De；Alain Hut
    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 invention relates to compositions, in particular for tires and more particularly to compositions comprising a specific hydrocarbon resin for improving the tackiness of the composition before firing. [2] The ability of the rubber compositions to be tacky before firing is an indispensable property for the manufacture of tire. Indeed, to make the tires, it is necessary to be able to apply the different layers of the tire on each other and that these layers adhere to each other, before the baking of the tire, which will combine by crosslinking the layers some to others. This stickiness property of the composition before firing, is also called "raw tack" or "tack" or "green tack". [3] Recent developments in low rolling resistance tires have led tire manufacturers to substantially modify the rubber compositions of their tires. This development of blends with low rolling resistance is generally accompanied by a decrease in raw tack. Indeed, the tackifying resins used to increase the raw tack are generally accompanied by an increase in hysteresis. The other solution for increasing raw tack, by brightening solvent, has the defect of releasing volatile organic compounds. [4] The Applicants have now shown that a particular composition comprising a specific hydrocarbon resin makes it possible to have a very good green tack and a low rolling resistance. [5] The invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a hydrocarbon resin, said hydrocarbon resin having a number average molecular weight (Mn) between 700 and 1000 g / mol, an average molecular mass Mz greater than 6000 g / mol and a polymolecularity index (Ip) greater than 2.4. [6] Preferably, the invention relates to a composition as defined above, wherein said diene elastomer is selected from the group consisting of essentially unsaturated diene elastomers. Preferably, said diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. More preferably, the majority diene elastomer is selected from the group consisting of polybutadienes, butadiene and styrene copolymers, and natural rubber. [7] Also preferably, the invention relates to a composition as defined above, wherein the reinforcing filler is selected from the group consisting of silicas, carbon blacks and mixtures thereof. More preferably, the level of reinforcing filler is in a range from 5 to 200 phr, preferably from 40 to 160 phr. [8] Preferably, the invention relates to a composition as defined above, wherein the level of said hydrocarbon resin is in a range from 1 to 15 phr, preferably from 2 to 12 phr. More preferably, the level of said hydrocarbon resin is in a range from 3 to 10 phr, preferably from 3 to 8 phr. [9] Preferably, the invention relates to a composition as defined above, wherein said hydrocarbon resin has an Mn of between 800 and 1000 g / mol. Also preferably, the invention relates to a composition as defined above, wherein said hydrocarbon resin has an Mz in a range from 6000 to 8000 g / mol. Also preferably, the invention relates to a composition as defined above, wherein said hydrocarbon resin has a lp included in a range from 2.4 to 2.8. Preferably, the invention relates to a composition as defined above, wherein the resin is selected from the group consisting of aliphatic hydrocarbon resins and mixtures thereof. According to a preferred variant, the invention relates to a composition as defined above further comprising a plasticizer system. Preferably, the plasticizer system comprises a hydrocarbon resin of Tg greater than 20 ° C and / or a plasticizing oil. The invention also relates to a tire comprising a composition as defined above. Preferably, the tire according to the invention will be selected from tires intended to equip a two-wheeled vehicle, a passenger vehicle, or a vehicle called "heavyweight" (that is to say, subway, bus , off-the-road vehicles, road transport vehicles such as trucks, tractors, trailers), or aircraft, civil engineering, agrarian, or handling equipment. 1- Constituents of the Composition [0016] The rubber compositions according to the invention are based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a specific hydrocarbon resin, said hydrocarbon resin having an average molecular weight in number (Mn) between 700 and 1000 g / mol, an average molecular weight Mz greater than 6000 g / mol and a polymolecularity index (1p) greater than 2.4. By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product in situ of the various basic constituents used, some of these constituents being able to react and / or being intended to react. between them, at least partially, during the various phases of manufacture of the composition, or during the subsequent firing, modifying the composition as it was initially prepared. Thus, the compositions as implemented for the invention may be different in the uncrosslinked state and in the crosslinked state. In the present description, unless otherwise expressly indicated, all the percentages (%) indicated are percentages by weight. On the other hand, any range of values designated by the expression "between a and h" 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 expression "from a to h" means the range from a to b (i.e., including the strict limits a and b). 1-1 Diene Elastomer The compositions may contain a single diene elastomer or a mixture of several diene elastomers. By elastomer (or "rubber", the two terms being considered synonymous) of the "diene" type, it is recalled here that must be understood in a known way (one or more) elastomer at least in part ( ie, a homopolymer or copolymer) of diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or otherwise). The 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%); Thus, 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 "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, 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%. These definitions being given, the term "diene elastomer" can be understood more particularly as used in the compositions according to the invention: (a) any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms ; (b) any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (C) a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example the elastomers obtained from ethylene, propylene with a nonconjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (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. Although it applies to any type of diene elastomer, a person skilled in the art of the tire will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b) above. As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as Examples are 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-1,3-diethyl-1,3-butadiene and the like. 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 "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene. The copolymers may contain between 99% and 20% by weight of diene units and between 1% 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, sequence, microsequential, 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. By function is meant here preferably a chemical group interactive with the reinforcing filler of the composition. In summary, the diene elastomer of the composition is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR). Thus, the invention preferably relates to compositions in which the elastomer said diene elastomer is selected from the group consisting of essentially unsaturated diene elastomers, and in particular in the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Preferably, the majority diene elastomer is selected from the group consisting of polybutadienes, butadiene and styrene copolymers, and natural rubber. 1-2 Reinforcing Charge [0028] The composition according to the invention comprises a reinforcing filler. Any type of reinforcing filler known for its ability to reinforce a rubber composition which can be used for the production of tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, may be used. alumina, or a blend of these two types of filler. As carbon blacks are suitable for all carbon blacks, including so-called pneumatic grade blacks. Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or even targeted applications, blacks of higher series (eg N660, N683, N772). The carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example applications VVO 97/36724 or VVO 99/16600). As examples of organic fillers other than carbon blacks, there may be mentioned organic functionalized polyvinyl fillers as described in applications VVO-A-2006/069792, VVO-A-2006/069793, VVO-A- 2008/003434 and VVOA-2008/003435. The composition may contain a type of silica or a blend of several silicas. 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 / boy Wut. As highly dispersible precipitated silicas (referred to as "HDS"), mention may be made, for example, of the "Ultrasil 7000" and "Ultrasil 7005" silicas of Degussa, the "Zeosil" silicas 1165MP, 1135MP and 1115MP of Rhodia, "Hi-Sil EZ150G" silica from PPG, the "Zeopol" silicas 8715, 8745 and 8755 from Huber, processed precipitated silicas such as, for example, the "aluminum doped" silicas described in the EP-A application; A-0735088 or silicas with high specific surface area as described in application VVO 03/16837. The silica preferably has a BET surface area of between 45 and 400 m 2 / g, more preferably between 60 and 300 m 2 / g. These compositions may optionally also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aid agents capable in a known manner, by virtue of a improving the dispersion of the filler in the rubber matrix and lowering the viscosity of the compositions, improving their ability to use in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, hydroxyl or hydrolyzable polyorganosiloxanes. In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described for example in the applications W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005). / 016650). In particular, the term "symmetrical" polysulfide silanes satisfying the following general formula (III) may be used without limiting the following definition: (III) Z - A - Sx - A - Z, in which: X is an integer of 2 to 8 (preferably 2 to 5); A is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 alkylenes, especially C 1 -C 4 alkylenes, in particular propylene); Z corresponds to one of the following formulas: embedded image in which: the radicals R 1, substituted or unsubstituted, identical or different from one another; represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl group (preferably C 1 -C 6 alkyl, cyclohexyl or phenyl groups, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkoxyl or a C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, plus still more preferably a group selected from C1-C4 alkoxyls, in particular methoxyl and ethoxyl). In the case of a mixture of polysulfide alkoxysilanes corresponding to the formula (III) above, especially common commercially available mixtures, the average value of "x" is a fractional number preferably between 2 and 5 more preferably close to 4. But the invention can also be advantageously used for example with disulfide alkoxysilanes (x = 2). By way of examples of polysulfide silanes, mention may be made more particularly of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4) alkoxyl-C 1 -C 4 alkylsilyl-C 1 -C 4 alkylsulphides. )), such as, for example, bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides. Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S2] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. formula [(C2H50) 3Si (CH2) 3S] 2. Mention may also be made, by way of preferred examples, of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (monoalkoxyl (C1-C4) -dialkyl (C1-C4) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide, as described above. in the patent application VVO 02/083782 (or US 2004/132880). As coupling agent other than polysulfide alkoxysilane, mention may also be made of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R 2 = OH in formula III above) as described in the patent applications. patent VVO 02/30939 (or US 6,774,255) and VVO 02/31041 (or US 2004/051210), or silanes or POS bearing azo-dicarbonyl functional groups, as described for example in the patent applications VVO 2006 / 125532, VVO 2006/125533, VVO 2006/125534. In the rubber compositions according to the invention, the content of coupling agent is preferably between 1 and 15 phr, more preferably between 3 and 14 phr. Those skilled in the art will understand that as an equivalent load of the silica described in this paragraph, could be used a reinforcing filler of another nature, particularly organic, since this reinforcing filler would be covered with a silica layer, or would comprise on its surface functional sites, especially hydroxyl, requiring the use of a coupling agent to establish the bond between the filler and the elastomer. The physical state under which the reinforcing filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form. For the purposes of the invention, the total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is from 5 to 200 phr, more preferably from 40 to 160 phr. Below 5 phr of load, the composition may not be sufficiently reinforced while above 200 phr of the load, the composition may be less effective in rolling resistance. 1-3 Crosslinking System In the composition of the invention, it is possible to use any type of crosslinking system known to those skilled in the art for rubber compositions. Preferably, the crosslinking system is a vulcanization system, that is to say based on sulfur (or a sulfur donor agent) and a primary vulcanization accelerator. To this basic vulcanization system can be added, incorporated during the first non-productive phase and / or during the productive phase as described later, various known secondary accelerators or vulcanization activators such as zinc, stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine). Sulfur is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr, in particular between 0.5 and 3 phr. The vulcanization system of the composition according to the invention may also comprise one or more additional accelerators, for example the compounds of the thiuram family, zinc dithiocarbamate derivatives, sulfenamides, guanidines or thiophosphates. In particular, any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, in particular thiazole type accelerators and their derivatives, thiuram type accelerators, zinc dithiocarbamates, may be used in particular. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated as "M BTS"), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated "CBS"), N, N-dicyclohexyl benzothiazyl sulphenamide (abbreviated "DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated "TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated "TBSI"), zinc dibenzyldithiocarbamate ( abbreviated "ZBEC") and mixtures of these compounds. Preferably, a primary accelerator of the sulfenamide type is used. 1-4 Specific Hydrocarbon Resin The composition according to the invention comprises a specific hydrocarbon resin. This hydrocarbon resin has a number-average molecular weight (Mn) of between 700 and 1000 g / mol, an average molecular weight Mz of greater than 6000 g / mol and a polymolecularity index (Ip) of greater than 2.4. Mn, Mz and lp are measured by the technique of size exclusion chromatography (SEC), according to the methods defined below. In commerce, there are many hydrocarbon resins available. These resins may have characteristics, in particular of Mn, Mz and lp which differ according to the suppliers, and sometimes according to the batch for the same commercial denomination. The macrostructure (Mw, Mn, lp and Mz) of the hydrocarbon resin is determined by steric exclusion chromatography (SEC) on the basis of ISO 16014 standards (Determination of average molecular mass and molecular mass distribution of polymers using size exclusion chromatography), ASTM D5296 (Molecular Weight Averages and molecular weight distribution of polystyrene by High performance size exclusion chromatography), and DIN 55672 (size exclusion chromatography). For these measurements, the resin sample is solubilized in non-antioxidized tetrahydrofuran to a concentration of 1.5 g / I. The solution is filtered with a Teflon filter with a porosity of 0.45 μm, for example using a disposable syringe fitted with a filter. A volume of 100 μl is injected through a set of size exclusion chromatography columns. The mobile phase is eluted with a flow rate of 1 ml / min. The columns are thermostatically controlled in an oven at 35 ° C. The detection is ensured by a refractometer thermostated at 35 ° C. The stationary phase of the columns is based on a divinylbenzene polystyrene gel with controlled porosity. The polymer chains are separated according to the size they occupy when they are solubilized in the solvent: the more they occupy a large volume, the less accessible the pores of the columns and their elution time is low. A Moore calibration curve connecting the logarithm of the molar mass (logM) to the elution time (te) is previously performed with polystyrene standards, and modeled by a polynomial of order 3: Log (molar mass). of polystyrene) = a + b te + c te2 + d te3. For the calibration curve, polystyrene standards with narrow molecular distributions (polymolecularity index, lp, less than or equal to 1.1) are used. The molar mass range of these standards ranges from 160 to about 70,000 g / mol. These standards can be grouped by "families" of 4 or 5 standards having an increment of approximately 0.55 in log of M between each. It is possible to use certified standard kits (ISO 13885 and DIN 55672), such as, for example, the PSS (standard polymer service, PSS-pskitr11-3) vial kits, as well as an additional standard PS of Mp. = 162 g / mol (Interchim, reference 178952). These kits are in the form of 3 vials each containing a family of polystyrene standards in appropriate quantities: - Vial black: Mp = 1,220, 4,850, 15,500 and 67,500 g / mol. Vial blue: Mp = 376, 3470, 400, 46,000 g / mol. Yellow visc: Mp = 266, 1920, 7200, 28,000 g / mol. PS162: Mp = 162 g / mol [0054] The number-average molar masses (Mn), by mass (Mw), the Mz, and the polydispersity of the resin analyzed are calculated from this calibration curve. This is why we speak of molar masses relative to a polystyrene calibration. For the calculation of the average masses and the Ip, is defined on the chromatogram corresponding to the injection of the sample the integration terminals of the elution of the product. The refractometric signal defined between the 2 integration terminals is "cut" every second. For each of the "elementary cuts", the elution time ti and the signal area of the detector Ai are recorded. It is recalled here that: lp = Mw / Mn with Mw weight average molecular weight, and Mn molecular mass by number. It is also recalled that the masses Mw, Mn and Mz are average masses calculated from the formulas below: in which Ai is the amplitude of the signal of the refractometric detector corresponding to the mass Mi and the time of elution ti. The equipment used for the SEC measurement is a liquid chromatography chain, for example the WATERS Alliance 2690 chain comprising a pump, a degasser and an injector; a differential refractometer (for example the WATERS refractometer 2410), data acquisition and processing software, for example WATERS 'WATERS software, a column oven, for example the WATERS "columns Heater Module" and 4 mounted columns in series in the following order: Number Brand Molar mass range (g / mol) Length (mm) internal Particle particle size (ftm) Designation References Internal commercial (at title (mm) ... Indlcattf) Columns 1 and 2 Polymer 200 - 300 7.5 5 MIXED-D PL1110- Laboratories 400000 6504 Columns 3 and 4 Polymer 200 -30000 300 7.5 3 MIXED-E PL1110-Laboratories 6300 The commercial resins below were analyzed with method described above to determine their characteristics, Table 1 summarizes the results obtained.
    [0002] Table 1 Mn (g / mol) Mz (g / mol) lp Resin 1 (1) 1830 7200 2.1 Resin 2 (2) 1344 8835 2.6 Resin 3 (3) 895 4228 2 Resin 4 (4) 586 5200 3 Resin 5 (5) 341 597 1,3 Resin 6 (6) 1370 7250 2,3 Resin 7 (7) 901 7076 2.6 (1) Resin 1: "R 7578 P" from SI group (2) Resin 2: "Piccotac 1105-E" from Eastman (3) Resin 3: "Hl KOREZ A-1100" from Kolon (4) Resin 4: "Novares TD 120" from Rutgers (5) Resin 5 : "Novares TL 10" from Rutgers - 13 - (6) Resin 6: "Escorez 1102 type 1" from Exxon (7) Resin 7: "Escorez 1102 type 2" from Exxon [0059] The table 1, by the analysis of commercial resins, shows that only the resin 7 satisfies the criteria of the resin useful for the needs of the invention, in particular in comparison with the resin 6, which another type of resin although having the same commercial reference of the same company. Preferably, the resin has a glass transition temperature, Tg, in a range from -50 ° C to 100 ° C, more preferably from 40 to 60 ° C. Tg is measured according to ASTM D3418 (1999). Preferably, the resin has a softening point in a range from 0 to 160 ° C, preferably from 90 to 110 ° C. The softening point is measured according to ISO 4625 ("Ring and Bali" method). Preferably, the resin has an Mn in a range from 800 to 1000 g / mol. Preferably, the resin has a Mz in a range from 6000 to 8000 g / mol. Preferably, the resin has an Lp in a range from 2.4 to 2.8. The resin useful for the purposes of the invention may be chosen from natural or synthetic resins. Among the synthetic resins it may be preferentially chosen from aliphatic or aromatic thermoplastic hydrocarbon resins or else from the aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers. As aromatic monomers are suitable for example styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C9 cut (or more generally from a C8 to C10 cut). Preferably, the vinylaromatic monomer is styrene or a vinylaromatic monomer derived from a C9 cut (or more generally from a C8 to C10 cut). Preferably, the vinylaromatic monomer is the minor monomer, expressed as a mole fraction, in the copolymer under consideration. According to a particularly preferred embodiment, the resin that is useful for the purposes of the invention is chosen from the group consisting of aliphatic hydrocarbon resins and mixtures thereof, and in particular from homopolymer or copolymer resins. cyclopentadiene (abbreviated CPD) or dicyclopentadiene (abbreviated DCPD), homopolymer resins or copolymers cutting 05 and mixtures thereof. Preferably, the level of resin is in a range from 1 phr to 15 phr, preferably from 2 to 12 phr, more preferably from 3 to 10 phr, in particular from 3 to 8 phr. Indeed, below 1 phr of the resin useful for the purposes of the invention, the composition could have sticky problems and therefore industrial processability, while above 15 phr the resin could modify the rigidity properties. and glass transition temperature of the composition. 1-5 Other Possible Additives The rubber compositions in accordance with 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 anti-ozone waxes, chemical antiozonants, anti-oxidants, plasticizers other than those previously described, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolak resin) or methylene donors (eg HMT or H3M). The composition according to the invention may also comprise a plasticizer system. This plasticizer system may be composed of a hydrocarbon resin of Tg greater than 20 ° C, in addition to the specific hydrocarbon resin described above, and / or a plasticizing oil. Of course, the compositions according to the invention can be used alone or in cutting (i.e., mixed) with any other rubber composition used for the manufacture of tires. It goes without saying that the invention relates to the previously described rubber compositions both in the so-called "raw" or non-crosslinked state (ie, before cooking) in the so-called "cooked" or crosslinked state, or still vulcanized (ie, after crosslinking or vulcanization). II-Preparation of rubber compositions The compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes termed "non-productive" phase) at a high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C., followed by a second mechanical working phase ( sometimes referred to as a "productive" phase) at a lower temperature, typically below 110 ° C., for example between 60 ° C. and 100 ° C., a finishing phase during which the crosslinking or vulcanization system is incorporated; such phases have been described, for example, in EP-A0501227, EP-A-0735088, EP-A-0810258, W000 / 05300 or W000 / 05301. The first phase (non-productive) is preferably carried out in several thermomechanical steps. In a first step, the elastomers, the reinforcing fillers, the hydrocarbon resin (and optionally the coupling agents and / or other ingredients with the exception of the above) are introduced into a suitable mixer such as a conventional internal mixer. of the crosslinking system) at a temperature between 20 ° C and 100 ° C and preferably between 25 ° C and 100 ° C. After a few minutes, preferably from 0.5 to 2 min and a rise in temperature to 90 ° C to 100 ° C, the other ingredients (ie, those that remain if all were not put initially) are added at once or in portions, with the exception of the crosslinking system during mixing ranging from 20 seconds to a few minutes. The total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes at a temperature of less than or equal to 180 ° C, and preferably less than or equal to 170 ° C. After cooling the mixture thus obtained, then incorporating the low temperature crosslinking system (typically less than 100 ° C), generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 5 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 extruded, to form for example a rubber profile used for the manufacture of semi-finished tires. These products can then be used for the manufacture of tires, according to the techniques known to those skilled in the art, with the advantage of the invention, namely a good stickiness of the layers on each other before cooking. pneumatic. The crosslinking (or baking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the cooking temperature, the crosslinking system adopted, the kinetics of crosslinking of the composition in question or the size of the tire. The examples which follow illustrate the invention without however limiting it.
    [0003] III-Examples of Embodiment of the Invention III-1 Preparation of the Examples In the following examples, the rubber compositions were produced as previously described.
    [0004] III-2 Characterization of the Examples [0080] In the examples, the rubber compositions are characterized before and / or after cooking as indicated below. Raw tack (or tack): The tack is the ability of an assembly of uncured compounds to withstand a pulling stress. For the measurement of raw tack (tack), a test device is inspired by the probe tack tester (ASTM D2979-95). An instron traction machine with a fixed metal jaw and a movable metal jaw is used. A first test piece consisting of a 3mm thick mixing film is glued to the fixed jaw. A second specimen consisting of a 3mm thick mixing film is glued to the movable jaw. Mixing films are glued to the surface of the metal jaws with a double-sided adhesive (Tesafix® 4970). For the preparation of the mixing test pieces, the mixing films are obtained by calendering to a thickness of 3 mm. The test pieces are cut with a 1 cm diameter punch. The principle of the measurement is to bring the two mixing films into contact for 5 seconds by applying a compressive force of 40 N. After this contact phase, they are separated by driving the cross member of the traction machine. . The speed of movement of the crosspiece in this phase of tearing is 1mm / s. Transverse displacement and force are measured continuously as a function of time during the contact and tear phases. The result of raw sticky is the measure of the maximum force reached during tearing. The results are expressed in base 100, that is to say that the value 100 is arbitrarily assigned to the best control, to then compare the raw tack of the various solutions tested, the higher the value, the higher the value. raw sticky is strong. Dynamic properties (after firing): The dynamic properties G * and tan (δ) max are measured on a viscoanalyzer (Metravib V A4000), according to the ASTM D 5992 - 96 standard. The response of a sample is recorded. of vulcanized composition (cylindrical specimen 4 mm thick and 400 mm 2 section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz, under variable temperature conditions, in particular at 60 ° C., according to ASTM D 1349-99. A peak to peak deformation amplitude sweep of 0.1 to 50% (forward cycle) followed by 50% to 1% (return cycle) is performed. The results exploited are the complex dynamic shear modulus (G *) and the loss factor (tan Ô). For the return cycle, the maximum value of tan 6 observed (tan (8) max) and the complex modulus difference (3.G *) between the values at 0.1% and at 50% deformation are indicated. (Payne effect). For the value of tan (δ) max at 60 ° C, the lower the value, the lower the composition will have a low hysteresis and thus a low rolling resistance. The results are expressed as base 100, that is to say that the value 100 is arbitrarily assigned to the best control, to then compare the tan (δ) max at 60 ° C (that is to say the hysteresis - and therefore the rolling resistance) of the different solutions tested. III-3 Examples [0088] The compositions are manufactured with an introduction of all the constituents on an internal mixer, with the exception of the vulcanization system. The vulcanizing agents (sulfur and accelerator) are introduced on an external mixer at low temperature (the constituent rolls of the mixer being at about 30 ° C.). The examples presented in Table 2 are intended to compare the different rubber properties of control compositions (C1 to 07) to a composition 08 according to the invention. The properties measured before and after curing are shown in Table 3. Table 2 Cl 02 03 04 05 06 07 08 NR (1) 25 25 25 25 25 25 25 25 25 75 75 75 75 75 75 75 75 Carbon black (3) 65 65 65 65 65 65 65 65 Resin 1 (4) Resin 2 (5) Resin 3 (6) Resin 4 (7) Resin 5 (8) Resin 6 (9) Resin 7 (10) Antioxidant (11) 2,5 2,5 2,5 2,5 2,5 2,5 2,5 Stearic acid (12) 3 3 3 3 3 3 3 3 ZnO (13) 4 4 4 4 4 4 4 4 Accelerator (14) 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Soluble sulfur 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (1) NR: natural rubber (2) BR: polybutadiene (3) Carbon black ASTM N375 grade (Cabot company) (4) Resin 1: "R 7578 P" from SI group (5) Resin 2 : "Piccotac 1105-E" from Eastman (6) Resin 3: "Hl KOREZ A-1100" from Kolon (7) Resin 4: "Novares TD 120" from Rutgers (8) Resin 5: " Novares TL 10 "from Rutgers - 19 - (9) Resin 6:" Escorez 1102 type 1 "from the company E) o (On (10) Resin 7: "Escorez 1102 type 2" from the company Emoen (11) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) from the company Flexsys and Anti-ozone wax (12) Stearin "Pristerene 4931" from Uniqema (13) Industrial grade zinc oxide - company Umicore (14) N-cyclohexyl-2-benzothiazol sulfenamide ("Santocure CBS" from Flexsys) Table 3 Cl C2 C3 C4 C5 C6 C7 C8 Raw tights (base 100) 32 100 61 48 40 39 63 87 Tan (delta) max at 60 ° C (base 100) 100 118 98 100 114 101 98 101 [0090] By relative to the control compositions, it is noted that the composition C8, in accordance with the invention, has an improved raw / hysteresis sticky compromise with respect to all the controls and in particular with respect to the control C2, which, if it presents a better performance that the composition C8 according to the invention also has a greater hysteresis, penalizing the rolling resistance. We can also note the great difference between the compositions C7 and C8, indicating that according to the production version of the same resin, here "Escorez 1102", the properties can vary significantly, according to the precise characteristics of Mn, Mz and lp of the resin. Here, the control composition C7 exhibits a hysteresis comparable to the composition in accordance with the invention but a raw tack clearly not so good. The composition C8 of the invention therefore has the best performance compromise between the green tights and the rolling resistance, with a hysteresis level as low as the control C1 without resin, and a high level of raw tack.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a hydrocarbon resin, said hydrocarbon resin having a number-average molecular weight (Mn) of between 700 and 1000 g / mol, a mass average molecular weight Mz greater than 6000 g / mol and a polymolecularity index (Ip) greater than 2.4.
    [0002]
    The composition of claim 1, wherein said diene elastomer is selected from the group consisting of substantially unsaturated diene elastomers.
    [0003]
    A composition according to any one of the preceding claims wherein said diene elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures thereof. elastomers.
    [0004]
    4. A composition according to any one of the preceding claims wherein the majority diene elastomer is selected from the group consisting of polybutadienes, butadiene and styrene copolymers, and natural rubber.
    [0005]
    5. Composition according to any one of the preceding claims wherein the reinforcing filler is selected from the group consisting of silicas, carbon blacks and mixtures thereof.
    [0006]
    6. Composition according to any one of the preceding claims wherein the level of reinforcing filler is in a range from 5 to 200 phr, preferably from 40 to 160 phr.
    [0007]
    7. Composition according to any one of the preceding claims wherein the level of said hydrocarbon resin is in a range from 1 to 15 phr, preferably from 2 to 12 phr.
    [0008]
    8. A composition according to claim 7 wherein the level of said hydrocarbon resin is in a range from 3 to 10 phr, preferably from 3 to 8 phr.
    [0009]
    9. Composition according to any one of the preceding claims wherein said hydrocarbon resin has an Mn between 800 and 1000 g / mol.
    [0010]
    10. Composition according to any one of the preceding claims wherein said hydrocarbon resin has an Mz in a range of 6000 to 8000 g / mol.
    [0011]
    11. A composition according to any one of the preceding claims wherein said hydrocarbon resin has an IP in a range from 2.4 to 2.8.
    [0012]
    12. A composition according to any one of the preceding claims wherein the resin is selected from the group consisting of aliphatic hydrocarbon resins and mixtures thereof.
    [0013]
    13. Composition according to any one of the preceding claims further comprising a plasticizer system.
    [0014]
    14. Composition according to the preceding claim wherein the plasticizer system comprises a hydrocarbon resin of Tg greater than 20 ° C and / or a plasticizing oil.
    [0015]
    15. A tire comprising a composition according to any one of claims 1 to 14.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3362512B1|2022-01-26|Rubber composition comprising a specific hydrocarbon resin
    EP3310583B1|2019-04-17|Rubber composition comprising a styrene-butadiene copolymer having a low glass transition temperature, and a high content of filler and of plasticizer
    EP3237523B1|2021-02-24|Rubber composition comprising a specific hydrocarbon resin
    EP3328932B1|2019-09-04|Rubber composition comprising a hydrocarbon resin having low glass transition temperature
    EP3328933B1|2019-09-04|Rubber composition comprising hydrocarbon resin having low glass transition temperature
    EP3436517B1|2021-11-17|Rubber composition comprising a specific hydrocarbon resin
    FR3017870A1|2015-08-28|RUBBER COMPOSITION COMPRISING A PLASTICIZING SYSTEM BASED ON A CUTTING OF HYDROCARBONATED RESIN OF LOW AND HIGH TEMPERATURE OF VITREOUS TRANSITION
    FR3017871A1|2015-08-28|RUBBER COMPOSITION COMPRISING A PLASTICIZING SYSTEM BASED ON HYDROCARBONATED RESIN WITH LOW GLASS TRANSITION TEMPERATURE
    FR2984896A1|2013-06-28|PNEUMATIC COMPRISING A COMPOSITION ESSENTIALLY FREE OF GUANIDIC DERIVATIVE AND COMPRISING PRIMARY AMINE
    WO2015124679A1|2015-08-27|Rubber composition comprising a plasticising system based on oil and hydrocarbonated resin having a low glass transition temperature
    EP3558701B1|2020-11-18|Rubber composition comprising a specific hydrocarbon resin
    EP3609723B1|2021-07-07|Rubber composition comprising a specific hydrocarbon resin
    EP3558700B1|2020-11-18|Rubber composition comprising a specific hydrocarbon resin
    EP3478515B1|2020-10-21|Tire comprising a composition containing a specific elastomer system
    WO2018002539A1|2018-01-04|Tire comprising a composition containing a specific elastomer system
    WO2018115623A1|2018-06-28|Rubber composition comprising a specific hydrocarbon resin
    EP3691918A1|2020-08-12|Rubber compositions comprising a specific combination of a coupling agent and a hydrocarbon-based resin
    同族专利:
    公开号 | 公开日
    CN107001711A|2017-08-01|
    US20180001702A1|2018-01-04|
    FR3030545B1|2018-05-25|
    EP3237523A1|2017-11-01|
    US10889147B2|2021-01-12|
    CN107001711B|2019-04-19|
    WO2016102344A1|2016-06-30|
    EP3237523B1|2021-02-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1994001295A1|1992-07-14|1994-01-20|Exxon Chemical Patents Inc.|Improved tire sidewall composition|
    FR2955588A1|2010-01-28|2011-07-29|Michelin Soc Tech|ELASTOMER COMPOSITION FOR PNEUMATIC OBJECT, WITH SELF-SWITCHING PROPERTY|
    WO2012050658A1|2010-10-13|2012-04-19|Exxonmobil Chemical Patents Inc.|Hydrocarbon polymer modifiers|
    US3927144A|1970-02-20|1975-12-16|Bridgestone Tire Co Ltd|Elastomer composition|
    FR2673187B1|1991-02-25|1994-07-01|Michelin & Cie|RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION.|
    FR2732351B1|1995-03-29|1998-08-21|Michelin & Cie|RUBBER COMPOSITION FOR A TIRE ENCLOSURE CONTAINING ALUMINUM DOPED SILICA AS A REINFORCING FILLER|
    EP1537908B1|1997-09-30|2012-04-04|Cabot Corporation|Elastomer composite blends and methods for producing them|
    JP4234200B2|1996-04-01|2009-03-04|キャボットコーポレイション|Novel elastomer composite and method for producing the same|
    FR2749313A1|1996-05-28|1997-12-05|Michelin & Cie|DIENE RUBBER COMPOSITION BASED ON ALUMINA AS A REINFORCING FILLER AND ITS USE FOR THE MANUFACTURE OF TIRE COVERS|
    EP1115785B1|1998-07-22|2002-10-09|Société de Technologie Michelin|Coupling system based on polysulphide alkoxysilane, enamine and guanidine derivative|
    EP1102812B1|1998-07-22|2002-10-16|Société de Technologie Michelin|Coupling system based on polysulphide alkoxysilane, zinc dithiophosphate and guanidine derivative|
    CN1257171C|2000-10-13|2006-05-24|米其林技术公司|Polyfunctional organosilane as coupling agent and method for obtaining same|
    CN1263792C|2000-10-13|2006-07-12|米其林技术公司|Rubber composition comprising as coupling agent polyfunctional organosilane|
    FR2823215B1|2001-04-10|2005-04-08|Michelin Soc Tech|TIRE AND TIRE TREAD COMPRISING AS COUPLING AGENT A BIS-ALKOXYSILANE TETRASULFURE|
    AT465208T|2001-06-28|2010-05-15|Michelin Soc Tech|TIRE RUNNING REINFORCED BY SILICA WITH LOW SPECIFIC SURFACE|
    WO2003002649A1|2001-06-28|2003-01-09|Societe De Technologie Michelin|Tyre tread reinforced with silica having a very low specific surface area|
    RU2004107514A|2001-08-13|2005-10-10|Сосьете Де Текноложи Мишлен |COMPOSITION BASED ON DIENE RUBBER FOR PNEUMATIC TIRES, INCLUDING SPECIAL SILICON DIOXIDE AS A REINFORCING FILLER|
    SE519792C2|2001-08-17|2003-04-08|Volvo Lastvagnar Ab|Method for estimating the mass of a vehicle which is carried on a road with a varying slope and method for estimating the slope of the road on which a vehicle is driven|
    JP4043403B2|2003-05-13|2008-02-06|住友ゴム工業株式会社|Pneumatic tire|
    FR2880354B1|2004-12-31|2007-03-02|Michelin Soc Tech|ELASTOMERIC COMPOSITION REINFORCED WITH A FUNCTIONALIZED POLYVINYLAROMATIC LOAD|
    FR2880349B1|2004-12-31|2009-03-06|Michelin Soc Tech|FUNCTIONALIZED POLYVINYLAROMATIC NANOPARTICLES|
    FR2886306B1|2005-05-26|2007-07-06|Michelin Soc Tech|PNEUMATIC RUBBER COMPOSITION COMPRISING AN ORGANOSILOXANE COUPLING AGENT|
    FR2886305B1|2005-05-26|2007-08-10|Michelin Soc Tech|PNEUMATIC RUBBER COMPOSITION COMPRISING AN ORGANOSILICALLY COUPLED AGENT AND AN INORGANIC CHARGE RECOVERY AGENT|
    FR2886304B1|2005-05-26|2007-08-10|Michelin Soc Tech|RUBBER COMPOSITION FOR PNEUMATIC COMPRISING AN ORGANOSILICIC COUPLING SYSTEM|
    FR2903411B1|2006-07-06|2012-11-02|Soc Tech Michelin|NANOPARTICLES OF FUNCTIONALIZED VINYL POLYMER|
    FR2903416B1|2006-07-06|2008-09-05|Michelin Soc Tech|ELASTOMERIC COMPOSITION REINFORCED WITH A FUNCTIONALIZED NON-AROMATIC VINYL POLYMER|
    CN101636284B|2007-03-29|2011-10-12|米其林研究和技术股份有限公司|Tire tread with resin|
    EP2357211B1|2010-02-17|2018-11-21|Continental Reifen Deutschland GmbH|Sulphur crosslinkable rubber composition|
    FR3019548B1|2014-04-03|2016-04-01|Michelin & Cie|RUBBER COMPOSITION COMPRISING AN AROMATIC DICYCLOPENTADIENE RESIN|FR3061184A1|2016-12-22|2018-06-29|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    FR3061185A1|2016-12-22|2018-06-29|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    US20200001650A1|2017-01-31|2020-01-02|Compagnie Generale Des Etablissements Michelin|A tire comprising a rubber composition|
    WO2018182042A1|2017-03-31|2018-10-04|Compagnie Generale Des Etablissements Michelin|A tire comprising a tread|
    WO2019115954A1|2017-12-14|2019-06-20|Compagnie Generale Des Etablissements Michelin|Civil engineering vehicle tire|
    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Search report ready|Effective date: 20160624 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 3 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 4 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463078A|FR3030545B1|2014-12-22|2014-12-22|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    FR1463078|2014-12-22|FR1463078A| FR3030545B1|2014-12-22|2014-12-22|RUBBER COMPOSITION COMPRISING A SPECIFIC HYDROCARBON RESIN|
    US15/538,687| US10889147B2|2014-12-22|2015-12-18|Rubber composition comprising a specific hydrocarbonated resin|
    PCT/EP2015/080421| WO2016102344A1|2014-12-22|2015-12-18|Rubber composition comprising a specific hydrocarbonated resin|
    EP15817251.0A| EP3237523B1|2014-12-22|2015-12-18|Rubber composition comprising a specific hydrocarbon resin|
    CN201580065103.9A| CN107001711B|2014-12-22|2015-12-18|Rubber composition comprising specific hydrocarbon resins|
    [返回顶部]