EP2486089A1

EP2486089A1 - Rubber composition comprising a thiazoline

Info

Publication number: EP2486089A1
Application number: EP10768717A
Authority: EP
Inventors: Anne Veyland; Nicolas Seeboth; José Carlos ARAUJO DA SILVA
Original assignee: Michelin Recherche et Technique SA Switzerland; Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2009-10-08
Filing date: 2010-10-08
Publication date: 2012-08-15
Also published as: JP5678072B2; WO2011042526A1; FR2951184B1; US20130053504A1; JP2013507472A; EA023534B1; US9034969B2; EA201270392A1; FR2951184A1

Abstract

The invention relates to a rubber composition for the manufacture of tyres, based on a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and of one or more diene elastomer(s) chosen from the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers, on one or more reinforcing fillers and on a vulcanization system, said vulcanization system comprising one or more thiazoline compound(s) of formula (I).

Description

Rubber composition comprising a thiazoline

The present invention relates to a rubber composition that can be used in particular for the manufacture of tires or semi-finished products for tires such as treads, said composition being based on a blend of particular diene elastomers, a reinforcing filler and a vulcanization system comprising a particular thiazoline compound.

The vulcanization of diene elastomers by sulfur is widely used in the rubber industry, in particular that of the tire. The principle of vulcanization lies in the creation of bridges of sulfur between two macromolecules by reaction on the double bonds of these diene elastomers.

In order to vulcanize the diene elastomers, a relatively complex vulcanization system comprising, in addition to sulfur, a primary vulcanization accelerator, such as sulphonamides with a benzothiazole nucleus, as well as various secondary accelerators or vulcanization activators, especially derivatives thereof, is used. zinc such as zinc oxide (ZnO) alone or used with fatty acids.

The sulphonamides with benzothiazole nucleus used as primary accelerators of vulcanization are, for example, N-cyclohexyl-2-benzothiazyl sulphenamide (abbreviated "CBS"), N, N-dicyclohexyl-2-benzothiazyl sulphenamide (abbreviated "DCBS"). , N-tert-butyl-2-benzothiazylsulfenamide (abbreviated as "TBBS") and mixtures of these compounds.

However, sulfur vulcanization has the known disadvantage of leading to a limited resistance of the vulcanisais obtained, due to thermal aging ("thermal aging") of the latter. In particular, vulcanisers of diene elastomers crosslinked from sulfur have a high temperature sensitivity when the latter reaches a value close to the initial firing temperature or vulcanization. The result is a drop in density sulfur bridges formed initially during vulcanization, the distribution of the vulcanization network evolving towards a shortening, that is to say a reduction of polysulfide bridges in favor of monosulfide bridges. This phenomenon, known as reversion, is accompanied by a degradation of the mechanical properties of vulcanisais.

There is a need to provide new rubber compositions that can be used especially for the manufacture of tires, in particular treads, which have improved resistance to reversion.

The other rheometric, rheological, dynamic, mechanical and plastic properties of these compositions must also remain comparable or even improved with respect to the properties of the known compositions, in particular with respect to the rolling resistance / wear compromise.

The subject of the invention is therefore a rubber composition for the manufacture of tires, based on a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and one or more chosen diene elastomers ( s) in the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers, one or more reinforcing fillers and a vulcanization system, said vulcanization system comprising one or more thiazoline compounds of the formula

R 1 and R ₂ independently represent H or a C 1 -C 25 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, and aryl groups, optionally interrupted by one or more heteroatoms, Ri and R ₂ may together form a ring,

3 represents:

a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₆ -C _2, or

- a cyclic alkyl C3-C1 _0, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C1-C25 or aryl C6-C12, optionally interrupted by one or more heteroatoms .

Such a thiazoline compound is known from US 2,700,659 as a vulcanization accelerator in natural rubber compositions. There is no question in this document of compositions comprising a blend of natural rubber and another elastomer and a fortiori a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and one or a plurality of diene elastomers selected from the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers.

The invention also relates to a method for preparing a rubber composition for the manufacture of tires as defined in any one of the preceding claims, characterized in that it comprises the following steps:

- Incorporating the natural rubber and synthetic diene elastomer (s), during a first so-called "non-productive" step, the reinforcing filler (s), by thermomechanically kneading the whole, in one or more times, until reaching a maximum temperature between 130 ° C and 200 ° C,

- cool the assembly to a temperature below 100 ° C,

- Then incorporate, during a second so-called "productive" step, the vulcanization system, then - mix everything up to a maximum temperature below 120 ° C.

The invention further relates to the use of a composition according to the invention for the manufacture of a finished article or a semi-finished product for a connection system to the motor vehicle, such as pneumatic , internal safety support for tire, wheel, rubber spring, elastomeric joint, other suspension and anti-vibration element. In particular, the composition according to the invention can be used for the manufacture of semi-finished rubber products intended for tires, such as treads, crown reinforcing plies, sidewalls, reinforcing plies. carcases, beads, protectors, underlayments, rubber blocks and other internal rubbers, in particular decoupling rubbers, intended to provide the connection or the interface between the aforementioned zones of the tires.

The invention further relates to a finished article or semifinished product for a ground connection system of a motor vehicle, in particular tires and semi-finished products for tires, comprising a composition according to the invention. The tires according to the invention are particularly intended for passenger vehicles as well as for industrial vehicles chosen from light trucks, "heavy vehicles" - i. e. metro, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, airplanes, other transport or handling vehicles.

The invention finally relates to the use as a vulcanization accelerator in a composition based on a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and from one or more diene elastomers. selected from the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers, one or more reinforcing fillers and a vulcanization system, one or more thiazoline compounds of formula (I) . The invention as well as its advantages will be readily understood in the light of the description and the following embodiments.

I. Measurements and tests used

The rubber compositions, in which the thiazoline vulcanization accelerators are tested, are characterized, before and after curing, as indicated below. rheometry

The measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983). The evolution of the rheometric torque, ACouple, as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to DIN 53529 - Part 2 (March 1983): To is the induction time, that is to say the time required for the beginning of the vulcanization reaction; T _a (e.g., T 99) is the time required to achieve a conversion of α%, i.e.% (e.g. 99%) of the difference between the minimum and maximum torque. The conversion rate constant denoted K (expressed in min-1), of order 1, calculated between 30% and 80% conversion, which makes it possible to evaluate the kinetics of vulcanization, is also measured.

Measure of reversion

The reversion can be analyzed according to different methods, the aim being to determine, indirectly, the evolution of the density of bridges of sulfur, between a cooking said to optimum (corresponding to the maximum torque Cmax) and a prolonged cooking. One approach consists in measuring the evolution (decrease) of the rheometric torque: the parameter Δ R120 represents the evolution in% of the torque between Cmax and the torque measured after 120 minutes of cooking, at a determined cooking temperature (for example 150 ° VS) . The higher the Δ R120 parameter, the greater the reversion phenomenon.

II. As described above, the composition according to the invention is based on a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and one or more chosen diene elastomers. (s) in the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers, one or more reinforcing fillers and a vulcanization system.

By the term "composition based on" is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another, at least partly, during the various phases of manufacture of the composition, in particular during its vulcanization.

In this description, unless expressly indicated otherwise, all percentages (%) are percentages by weight. On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., terminals a and b excluded) while any range of values designated by the term "from a to b" means the range of values from a to b (ie including the strict limits a and b). II- 1. Diene elastomer

As explained above, the composition according to the invention is based on at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and from one or more diene elastomers chosen from the group consisting of lybutadienes, butadiene copolymers and isoprene copolymers.

By elastomer or "diene" rubber, should be understood in known manner an elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).

These 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 proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (% by mo) ; for example, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-o-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%.

Given these definitions, the term "diene elastomer" can be understood more particularly to be 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-o-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 at from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type, such as, in particular, hexadiene-1,4, 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, the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.

By way of conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, 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 "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, 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, sequenced, microsequenced, and be prepared in dispersion, in emulsion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization. For coupling with carbon black, there may be mentioned, for example, functional groups comprising a C-Sn bond or amino functional groups such as aminobenzophenone for example; for coupling to a reinforcing inorganic filler such as silica, there may be mentioned, for example, silano or polysiloxane functional groups having a silanol end (as described, for example, in F 2 740 778, US Pat. No. 6,013,721 or WO 2008 / 141702), 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 Pat. 2006/0089445) or polyether groups (as described for example in EP 1 127 909, US 6,503,973, WO 2009/000750 or WO 2009/000752). As other examples of 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 of between 4% and 80% or those having a content (mol%) in cis -1, 4 greater than 80%, polyisoprenes, copolymers of butadiene-styrene and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418) of between 0 ° C. and -70 ° C. and more particularly between -10 ° C. and -60 ° C., a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in 1,2-bonds of the butadiene part of between 4% and 75%, a content ( mol%) in trans-1,4 bonds between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40 ° C. to At 80 ° C., the isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg range between 5 ° C and - 50 ° C. In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%, are especially suitable. by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (% by weight) in units - 1, 2 of the butadiene part of between 4% and 85%, a content (mol%) in trans - 1,4 units of the butadiene part of between 6% and 80%, a content (% molar) in units - 1, 2 plus - 3, 4 of the isoprenic part between 5% and 70% and a content (% molar) in trans-1,4 units of the isoprenic part of between 10% and 50%, and more generally any butadiene-styrene copolymer isoprene having a Tg between -5 ° C and -70 ° C.

In summary, the diene elastomer (s) of the composition according to the invention are chosen from natural rubber and / or synthetic polyisoprene, ie an isoprene homopolymer, in a blend with elastomers preferably chosen from the group. highly unsaturated diene elastomers consisting of polybutadienes (abbreviated "BR"), butadiene copolymers, isoprene copolymers 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. butadiene-styrene (SBIR) According to one particular embodiment, the composition according to the invention is based on a blend of natural rubber and / or synthetic polyisoprene, with one or more polybutadienes and one or more SBRs, which it is a SBR prepared in emulsion ("ESBR") or a SBR prepared in solution ("SSBR"). 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, or a high styrene content, for example 35 to 35% by weight, is used in particular. 45%, a vinyl content of the butadiene part from 15% to 70%, a content (mole%) of trans-1,4-links of between 15% and 75% and a Tg of -10 ° C to -55 ° C.

More particularly, the composition according to the invention may also be based on a blend of natural rubber, a butadiene-styrene copolymer and a polybutadiene (NR / SBR / BR). Preferably, the natural rubber represents 30 to 60 phr, the polybutadienes represent 10 to 30 phr and the butadiene-styrene copolymer or copolymers represent 30 to 60 phr.

The synthetic diene elastomer (s) present in the composition according to the invention in a blend with natural rubber may also be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example polymers. thermoplastics.

II-2. Reinforcing charge

Any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a cutting of these two types of filler, including a cut of carbon black and silica.

Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks). Among these, the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), for example blacks NI 15, N 134, N 234, N 326, N 30 O, N 339, N 347, N 375, or even more particularly , depending on the intended applications, blacks of higher series (for example N660, N683, N772). The carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).

As examples of organic fillers other than carbon blacks, there may be mentioned organic functionalized polyvinylaromatic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793.

By "reinforcing inorganic filler" is meant in this application, by definition, 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 a known manner, by the presence of hydroxyl groups (-OH) on its surface.

The physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also refers to mixtures of different 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 of silica (SiO 2), or of the aluminous type, in particular alumina.

(Al2O3). 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. As highly dispersible precipitated silicas (called "HDS"), there may be mentioned, for example, the silicas Ultrasil 7000 and Ultrasil 7005 of the Degussa company, the Zeosil 1 165MP, 1 135MP and 1 1 15MP silicas from Rhodia, the Hi-Sil EZ 150G silica from PPG, the Zeopol 8715, 8745 and 8755 silicas from Huber, the high surface silicas specific as described in WO 03/16837.

When the composition according to the invention is intended for tire treads with a low rolling resistance, the reinforcing inorganic filler used, in particular if it is silica, preferably has a BET surface area of between 45 and 400. m ² / g, more preferably between 60 and 300 m ² / g.

Preferably, the level of total reinforcing filler

(Carbon black and / or reinforcing inorganic filler such as silica) is between 20 and 200 phr, more preferably between 30 and 150 phr, the optimum being in a known manner different according to the particular applications concerned: 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 a truck.

According to a preferred embodiment of the invention, carbon black is used as the reinforcing filler.

According to another embodiment of the invention, a reinforcing filler comprising between 30 and 150 phr is used, more preferably between 50 and 120 phr of inorganic filler, particularly of silica, and optionally carbon black; the carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).

In order to couple the reinforcing inorganic filler to the diene elastomer, an at least bifunctional coupling agent (or bonding agent) is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes. In particular, polysulphurized silanes, known as

"symmetrical" or "asymmetrical" according to their particular structure, as described for example in WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).

In particular, polysulphide silanes known as "symmetrical" silanes having the following general formula (III) are suitable in the following non-limiting definition:

(III) Z - A - S _x - A - Z, wherein

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 is one of the following formulas:

R1 R1 R2

I i I

Si- Si ^¬ Si ^¬ te te te te in which:

- R.1 radicals, substituted or unsubstituted, identical or different, represent an alkyl group Ci-Cis cycloalkyl, C5-C18 aryl or C _O -CJS (preferably alkyl, CI-C _O , cyclohexyl or phenyl, especially C1-C4 alkyl groups, more particularly methyl and / or ethyl).

the radicals R.2, substituted or unsubstituted, identical or different from each other, represent a C 1 -C 18 alkoxyl or C 5 -C 18 cycloalkoxyl group (preferably a group chosen from C 1 -C 8 alkoxyls and C 5 -C 8 cycloalkoxyls); more preferably still a group selected from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl). In the case of a mixture of polysulfurized alkoxysilanes corresponding to formula (III) above, in particular 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 implemented for example with disulfide alkoxysilanes (x = 2).

By way of examples of polysulphurized silanes, mention may be made more particularly of the bis (C 1 -C ₄ ) alkoxyl (C 1 -C ₄ ) alkyl (C 1 -C ₄ ) silyl-alkyl (Ci-C ₂ ) polysulfides (especially disulfides, trisulphides or tetrasulfides). ₄ )), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of the formula [(C 20 H 20 O 5 S 4 CH 2 S 6) or bis (triethoxysilylpropyl) disulfide, abbreviated TESPD, of formula (C2H ₅ 0) 3 Si (CH ₂ ) 3 S] 2. Preferred polysulfides (especially disulfides, trisulphides or tetrasulfides) of bis- (monoalkoxyl (C 1 -C 4) -dialkyl) are also preferred ( Ci - C4) silylpropyl), more particularly bis - monoethoxydimethylsilylpropyl tetrasulfide as described in patent application WO 02/083782 (or US 2004/1 32880).

As coupling agent other than polysulfurized alkoxysilane, there may be mentioned in particular bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides ( ² = OH in formula III above) as described in the patent applications WO 02/30939 (or US Pat. No. 6,774,255) and WO 02/3 1041 (or US 2004/05 1210), or else silanes or POS bearing azodicarbonyl functional groups, as described, for example, in patent applications WO 2006 / 125532, WO 2006/125533, WO 2006/125534.

In the rubber compositions according to the invention, the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.

Those skilled in the art will understand that as an equivalent load of the reinforcing inorganic filler described herein. paragraph, could be used a reinforcing filler of another nature, especially organic, since this reinforcing filler would be covered with an inorganic layer such as silica, 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.

II.3 Vulcanization system

The vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system are 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 oxide. stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine).

Sulfur is used at a preferential level of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr, in particular between 0.5 and 3 phr, when the composition of the invention is intended, according to one embodiment. of the invention, to constitute a tread of a tire.

The primary vulcanization accelerator must allow crosslinking of the rubber compositions in commercially acceptable times, while maintaining a minimum safety period ("toasting time") during which the compositions can be shaped without the risk of premature vulcanization. ("Roasting").

According to the invention, the vulcanization system comprises, as a primary vulcanization accelerator, one or more thiazolyl compounds of the formula

or

R 1 and R 2 independently represent H or a C 1 -C 25 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, and aryl groups, optionally interrupted by one or more heteroatoms, R 1 and R ₂ may together form a ring,

R3 represents:

a C1-C25 linear or branched, optionally interrupted by one or more heteroatoms, optionally substituted with one or more cyclic alkyl C3-C10 aryl or C ₂ _O -Cl, OR

- a cyclic alkyl C3-C10, optionally interrupted by one or more heteroatoms, optionally substituted by one or more linear alkyl groups, branched or cyclic C 1 -C 25 aryl or C _O -C ₁₂ alkyl, optionally interrupted by one or more heteroatoms.

The compounds of formula (I) may advantageously replace all or part of the sulphonamide compounds conventionally used.

By cyclic alkyl group is meant an alkyl group consisting of one or more rings.

The heteroatom (s) may be a nitrogen, sulfur or oxygen atom.

Advantageously, R 1 and R 2 independently represent H or a methyl group.

According to a particular embodiment, R 1 and R 2 each represent a hydrogen. According to a particular embodiment, R ₃ represents a tert-butyl group.

According to another particular embodiment, R ₃ represents a C 3 -C 10 cyclic alkyl group, optionally interrupted by one or more heteroatoms, optionally substituted with one or more linear, branched or cyclic C 1 -C 25 alkyl groups. or C 6 -C 12 aryls, optionally interrupted by one or more heteroatoms.

Advantageously, R ₃ represents a cyclohexyl group.

Thus, a preferred compound of formula (I) is that wherein R 1 and R ₂ are H and R ₃ is cyclohexyl. In this case, the thiazoline compound of formula (I) is N-cyclohexyl-4,5-dihydro-2-thiazolesulfenamide.

The compound (s) of formula (I) generally represent from 0.1 to 10 phr, preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr (parts by weight per cent of elastomers).

The synthesis of the compounds of formula (I) is well known and is described in particular in the following documents:

US 2,700,659

Journal of Organic Chemistry (1949), 14, 921-34.

The vulcanization system of the composition according to the invention may also comprise one or more additional primary accelerators, in particular the compounds of the thiuram family, zinc dithiocarbamate derivatives or thiophosphates. II-4. Various additives

The rubber composition according to the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, in particular treads, for example plasticizers or extension oils. , whether the latter are of aromatic or non-aromatic nature, pigments, protective agents such as anti-ozone waxes (such as C32 ST Ozone wax), chemical antiozonants, anti-oxidants (such as the paraphenylenediamine), anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described for example in the application WO 02/10269.

Preferably, the composition according to the invention comprises, as preferential non-aromatic or very weakly aromatic plasticizing agent, at least one compound chosen from the group consisting of naphthenic, paraffinic, MES, TDAE, and ester oils. in particular trio leates) glycerol, the hydrocarbon plasticizing resins having a high Tg preferably greater than 30 ° C, and mixtures of such compounds.

The composition according to the invention may also contain, in addition to the coupling agents, enhancers for coupling the reinforcing inorganic filler or, more generally, processing aid agents that are capable in a known manner, thanks to an improvement in the dispersion of the inorganic filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes (especially alkyltriethoxysilanes), polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol amines), hydroxylated or hydrolyzable POs, for example α, ω-dihydroxy-polyorganosiloxanes ( especially α, ω-dihydroxy-polydimethylsiloxanes), fatty acids such as stearic acid.

II-5. Manufacture of rubber compositions The rubber composition according to the invention is manufactured in appropriate 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 thermo-mechanical mixing (sometimes referred to as a "non-productive" phase) to high temperature, up to a maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 1 85 ° C, followed by a second phase of mechanical work (sometimes referred to as "productive" phase) to 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.

According to a preferred embodiment of the invention, all the basic constituents of the composition of the invention, with the exception of the vulcanization system, namely the reinforcing filler or fillers, the coupling agent, where appropriate, are intimately incorporated, by mixing, with the natural rubber and with the diene elastomer or with the diene elastomers during the first so-called non-productive phase, that is to say that one introduces into the mixer and that at least one of these basic constituents is kneaded thermomechanically in one or more steps until the maximum temperature of between 130 ° C. and 200 ° C., preferably between 145 ° C. and 185 ° C. is reached.

By way of example, the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible setting agents, are introduced into a suitable mixer such as a conventional internal mixer. Complementary applications and other miscellaneous additives, with the exception of the vulcanization system. The total mixing time in this non-productive phase is preferably between 1 and 15 minutes. After cooling the mixture thus obtained during the first non-productive phase, 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. tire for passenger vehicle. III. Examples of embodiment of the invention

In the examples which follow, the invention is implemented with N-cyclohexyl-4,5-dihydro-2-thiazolesulfenamide (compound A) of the following formula:

III- 1. Synthesis of thiazoline compound A

The preparation of this compound is carried out from 4,5-dihydrothiazole-2-thiol and cyclohexylamine, according to the following synthesis scheme:

4,5-Dihydrothiazole-2-thio (CAS number [96-53 -7] is commercially available and marketed for example by the company ALDRICH.

To a solution of 4,5-dihydrothiazole-2-thiol (30.0 g, 0.252 mol) and sodium hydroxide (30.24 g, 0.765 mol) in water (700 mL) is added the solution. cyclohexylamine (74.98 g, 0.756 mol) in water (100 mL). The mixture is cooled to + 4 ° C. and then the iodine solution prepared as follows is added dropwise (63.96 g, 0.252 mol) and potassium iodide (83.66 g, 0.504 mol). are dissolved in a 600 ml flask supplemented ^with demineralized water for 2,5-3, 0 hours. The reaction medium is then stirred for one hour at a temperature between 0 and + 8 ° C.

Then the precipitate is filtered and washed with water (3.0 L). The pale yellow crude product is crystallized from a mixture of pentane and cyclohexane in 1: 1 volume ratios.

A white solid (28.2 g, 0.11 mol, 52.5% yield) with a melting point of 69.5 ° C. (lit: 69-70 ° C.) is obtained.

The molar purity is greater than 98% (1 H NMR). III-2. Preparation of compositions

The following tests are carried out in the following manner: the natural rubber and the synthetic diene elastomer (s) are introduced into an internal mixer, filled to 70% and whose initial tank temperature is about 90 ° C. or the reinforcing fillers, the optional coupling agent and then, after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 5 minutes), until a maximum temperature of "fall" of about 165 ° C. is reached. The mixture thus obtained is recovered, cooled and then the vulcanization system (sulfur and thiazoline compound) on an external mixer (homo-finisher) at 70 ° C., mixing the whole (productive phase) for about 5 to 6 minutes. .

The 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. III-3. Characterization tests - Results

The objective of this example is to compare the properties of a rubber composition according to the invention (composition 4) that can be used for the manufacture of a tire tread, based on a cutting of elastomers according to the invention. the invention and comprising, as vulcanization accelerator, N-cyclohexyl-4,5-dihydro-2-thiazo-desulfenamide (compound A) with the properties of several compositions not in accordance with the invention:

a first control composition comprising, as primary accelerator of vulcanization, N-cyclohexyl-2-benzothiazylsulfenamide ("CBS") and as diene elastomer only natural rubber (composition 1), a second control composition comprising the compound As a vulcanization accelerator and as a diene elastomer only natural rubber (composition 2), a third control composition comprising CBS as a vulcanization accelerator and as diene elastomers a natural rubber blend , polybutadiene and styrene-butadiene copolymer (thus a blend according to the invention).

The formulations of the compositions are given in Table 1. The amounts are expressed in parts per 100 parts by weight of elastomer (phr).

Table 1

* CBS ("Santocure CBS" from Flexsys)

* * N-cyclohexyl-4,5-dihydro-2-thiazolesulfenamide

(1) natural rubber

(2) polybutadiene with 0.7% of 1-2; 1.7% trans 1 -4; 98% cis 1 -4 (Tg = -105 ° C) (% mole)

(3) butadiene-styrene copolymer SSBR (SBR prepared in solution) with 25% of styrene, 59% of polybutadiene units 1 -2 and 20% of trans-polybutadiene-4 units (Tg = -24 ° C.) (% molar) ); rate expressed as dry SBR (SBR extended with 9% by weight of MES oil, ie a total of S SBR + oil equal to 76 phr)

(4) carbon black N234

(5) Antioxidant agent 6-para-phenylenediamine

The rubber composition 2 comprising N-cyclohexyl-4,5-dihydro-2-thiazolesulfenamide is identical to the composition 1, it being understood that the CBS is replaced by an isomolar amount of N-cyclohexyl-4,5-dihydro-2 -thiazolesulfénamide.

The rubber composition 4 comprising N-cyclohexyl-

4,5-dihydro-2-thiazolesulfenamide is identical to composition 3, it being understood that CBS is replaced by an isomolar amount of N-cyclohexyl-4,5-dihydro-2-thiazolesulfenamide.

The rheometric properties at 150 ° C. and the reversion at 150 ° C. are given in Table 2. Table 2

It should be noted that the compositions 1 and 2 based on natural rubber that do not conform to the invention both have a significant reversion, and in particular that the composition 2 comprising the compound A has a greater reversion than the composition 1 comprising the accelerator usually used that is the CBS.

Furthermore, it is noted that, contrary to what could be supposed the composition 2 including the compound A, when the composition is based on a blend of natural rubber, polybutadiene and butadiene-styrene copolymer, the use of N-cyclohexyl-4,5-dihydro-2-thiazo-lesulfenamide (composition 4) makes it possible to obtain a reversion of 0%, which is a very important improvement over composition 3 including CBS.

It is furthermore noted that the compound A, as well as the compounds of formula (I) in general, advantageously replace with respect to the environmental impact, the mercaptobenzothiazole ring sulfenamides, by not generating, unlike the latter, of mercaptobenzothiazole by decomposing during cooking.

Claims

A rubber composition for the manufacture of tires, based on a blend of at least one diene elastomer selected from natural rubber and synthetic polyisoprene and one or more diene elastomers selected from the group consisting of by the polybutadienes, the butadiene copolymers and the isoprene copolymers, one or more reinforcing fillers and a vulcanization system, said vulcanization system comprising one or more thiazoline compounds of the formula

R 1 and R ₂ independently represent H or a C 1 -C 25 hydrocarbon-based group chosen from linear, branched or cyclic alkyl groups, and aryl groups, optionally interrupted by one or more heteroatoms, Ri and R _{2 being} able to form a ring together,

R3 represents:

a linear or branched C1-C25 alkyl group optionally interrupted by one or more heteroatoms, optionally substituted by one or more C3-C10 cyclic alkyl groups or C ₆ -C ₁₂ aryl groups, or

a C 3 -C 10 cyclic alkyl group, optionally interrupted by one or more heteroatoms, optionally substituted with one or more linear, branched or cyclic C 1 -C 25 or C ₆ -C ₁₂ aryl groups, optionally interrupted by one or more heteroatoms; .

2. Composition according to claim 1 characterized in that R 1 and R ₂ independently represent H or a methyl group.

3. Composition according to claim 2 characterized in that Ri and R ₂ each represent H.

4. Composition according to any one of the preceding claims, characterized in that R3 represents a cyclohexyl group or a tertbutyl group.

5. Composition according to any one of the preceding claims, characterized in that the said thiazoline compound (s) represent from 0.1 to 10 phr, preferably from 0.5 to 7 phr, more preferably from 0.5 to 5 phr (parts in percent by weight of diene elastomer).

6. Composition according to any one of the preceding claims, characterized in that the cutting is a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene with one or more polybutadienes and one or more butadiene copolymers. -styrene.

7. Composition according to any one of the preceding claims, characterized in that the reinforcing fillers or fillers are chosen from silica, carbon black and their mixtures.

8. Composition according to any one of the preceding claims, characterized in that the reinforcing filler or fillers are present at a level of between 20 and 200 phr, preferably between 30 and 150 phr.

9. Process for preparing a rubber composition for the manufacture of tires as defined in any one of the preceding claims, characterized in that it comprises the following steps:

- Incorporating into the diene elastomers during a first so-called "non-productive" step, the reinforcing filler (s), by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C and 200 ° C,

- cool the assembly to a temperature below 100 ° C, - Then incorporate, during a second so-called "productive" step, the vulcanization system, then

- mix everything up to a maximum temperature below 120 ° C.

10. Use of a composition according to any one of claims 1 to 8, for the manufacture of a finished article or a semi-finished product for a vehicle ground connection system.

1 1. A finished article or semi-finished product for a motor vehicle attachment system comprising a composition according to any of claims 1 to 8.

12. A tire comprising a rubber composition as defined in any one of claims 1 to 8.

13. Use as a vulcanization accelerator in a composition based on a blend of at least one diene elastomer chosen from natural rubber and synthetic polyisoprene and one or more diene elastomers chosen from the group consisting of polybutadienes, butadiene copolymers and isoprene copolymers, one or more reinforcing fillers and a vulcanization system, one or more thiazoline compounds of formula (I) as defined in any one of Claims 1 to 4.