Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds

Definitions

• the invention also relates to the use of a composition in accordance with the invention for the manufacture of finished articles or semi-finished products, as well as these finished articles and semi-finished products themselves, comprising a composition of rubber according to the invention, these articles or products being intended for any ground connection system of motor vehicles, such as tires, internal safety supports for tires, wheels, rubber springs, elastomeric joints, other suspension and anti - vibratory.
• a composition in accordance with the invention for the manufacture of finished articles or semi-finished products, as well as these finished articles and semi-finished products themselves, comprising a composition of rubber according to the invention, these articles or products being intended for any ground connection system of motor vehicles, such as tires, internal safety supports for tires, wheels, rubber springs, elastomeric joints, other suspension and anti - vibratory.
• the charges described below consist, in a known manner, of agglomerates of particles, capable of disaggregating into these particles under the effect of an external force, for example under the action of mechanical work or ultrasound.
• particle used in the present application must be understood in its usual generic sense of aggregate (also called “secondary particle”), and not in that of elementary particle (still called “primary particle”) which can form, if necessary, part of this aggregate; "aggregate” means in a known manner the non-breaking set (ie, which cannot be cut, divided, shared) which is produced during the synthesis of the charge, generally formed of elementary (primary) particles aggregated between they.
• the deagglomeration speed (denoted ⁇ ) is measured in the so-called “ultrasonic deagglomeration test” test, at 100% power of a 600 W (watt) probe, operating here in pulsed mode (ie: 1 second ON, 1 second OFF) to avoid excessive heating of the probe ultrasound during measurement.
• This known test in particular the subject of patent application WO99 / 28376 (see also WO99 / 28380, WO00 / 73372, WO00 / 73373), makes it possible to continuously measure the evolution of the average size (in volume) of the particle agglomerates during sonication, as indicated below.
• the aforementioned application WO99 / 28376 describes in detail a measurement device which can be used for carrying out this deagglomeration test with ultrasound.
• This device consists of a closed circuit in which a flow of agglomerates of particles in suspension in a liquid can flow.
• This device essentially comprises a sample preparer, a
• the samples in powder form are placed in a cylindrical zirconium oxide sample holder (rotor) of about 0.3 cm 3 , which rotates at the magic angle at a frequency of 4 KHz.
• high power decoupling is used to average the dipole protons-silicon interactions; the number of "scans" is between 10 and 15 miles, in order to increase the sensitivity of the measurement.
• the rubber compositions are characterized, before and after curing, as indicated below.
• the level of elastomer which cannot be extracted with toluene is measured, after swelling for 15 days of a sample of rubber composition (typically 300-350 mg) in this solvent (for example in 80-100 cm 3 toluene), followed by a 24 hour drying step at 100 ° C, under vacuum, before weighing the sample of composition of rubber thus treated.
• a sample of rubber composition typically 300-350 mg
• this solvent for example in 80-100 cm 3 toluene
• the above swelling step is carried out at room temperature (about 20 ° C) and protected from light, and the solvent (toluene) is changed once, for example after the first five days swelling.
• diene elastomers such as butyl rubbers or copolymers of dienes and of alpha-olefins of the EPDM type do not enter into the preceding definition and can be qualified in particular as “essentially saturated diene elastomers”. "(rate of motifs of diene origin low or very low, always less than 15% (% in moles)).
• 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes are suitable.
• an SBR elastomer in particular an SBR is used having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%>, a content of trans-1,4 bonds between 15% and 75% and a Tg between -20 ° C and -55 ° C, this SBR copolymer, preferably prepared in solution (SSBR), being optionally used in admixture with a polybutadiene ( BR) preferably having more than 90% of cis-1,4 bonds.
• the diene elastomer is preferably an isoprene elastomer.
• the reinforcing aluminosilicates synthesized in the embodiments which follow are generally characterized by a number of Al-O-Si bonds included in a range from 1 to 4, for a given Si atom.
• the cation M used is preferably Na + : it has been found that such a cation is synonymous with a higher disagglomeration rate.
• the BET specific surface area of the reinforcing aluminosilicate is between 20 and 300 m 2 / g or between 40 and 200 mVcm 3 approximately, more precisely between 42 and 1191 mVcm 3 for a density range varying between 2.10 g / cm 3 (density of silica SiO 2 ) and 3.97 g / cm 3 (density of alumina Al 2 O 3 ).
• X represents a functional group ("X" function) capable of binding physically and / or chemically to the elastomer, for example via a sulfur atom;
• n is a fractional number preferably between 2 and 5, more preferably close to 4.
• the level of coupling agent, reduced to the weight of diene elastomer is preferably between 0.1 and 15 phr, more preferably between 0.5 and 10 phr.
• the coupling agent used could be grafted beforehand (via the "X" function) onto the diene elastomer of the composition of the invention, the elastomer thus functionalized or “precoupled” then comprising the free "Y” function for the reinforcing aluminosilicate.
• the coupling agent could also be grafted beforehand (via the "Y” function) onto the reinforcing aluminosilicate, the charge thus "precoupled” can then be linked to the diene elastomer via the free functions "X".
• compositions in accordance with the invention contain, in addition to the compounds already described, all or part of the additives usually used in diene rubber compositions intended for the manufacture of tires, such as, for example, extension oils, plasticizers, pigments, protective agents of the antioxidant, antiozonant type, anti-fatigue agents, coupling activators as described for example in applications WO 00/05300, WO 00/05301, WO 01/55252, WO 01/55253 , acceptors and donors of methylene, bismaleimides or other reinforcing resins as described for example in WO 02/10269, a crosslinking system based either on sulfur or on sulfur and / or peroxide donors, vulcanization accelerators, vulcanization activators, systems for promoting adhesion of rubber to metal or textile, etc.
• the additives usually used in diene rubber compositions intended for the manufacture of tires such as, for example, extension oils, plasticizers, pigments, protective agents of the antioxidant, antiozonant type, anti-fat
• the vulcanization system proper is preferably based on sulfur and a primary vulcanization accelerator, in particular an accelerator of the sulfenamide type.
• a primary vulcanization accelerator in particular an accelerator of the sulfenamide type.
• various known secondary accelerators or activators of vulcanization such as zinc oxide, stearic acid, derivatives guanidiques (in particular diphenylguanidine), etc.
• Sulfur is used at a preferential rate of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr, for example between 0.5 and 3.0 phr when the invention is applied to a strip. tire bearing.
• the primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr in particular when the invention applies to a tire tread.
• the invention relates to the rubber compositions described above, both in the so-called “raw” state (ie, before baking) and in the so-called “cooked” or vulcanized state (ie, after crosslinking or vulcanization). .
• sol.A and sol.B Two solutions, denoted sol.A and sol.B, are then prepared:
• the rotation of the centrifuge is 210 rpm.
• the washing water is introduced at a flow rate of 300 ml / min.
• a total of 20 liters of water is used for washing, the last washing water having a pH of about 5.8.
• the final spin takes place at 500 rpm.
• the product thus obtained is then lyophilized under the following conditions: 48 hours of main drying ("main drying") at -15 ° C and 1030 mbar; then 12 hours of final drying at 0 ° C and under a dynamic vacuum. After lyophilization, the product is ground in a mortar and sieved (fraction of size less than 425 ⁇ m). This product is then dried at 150 ° C for 21 hours. The loss of mass is around 13%. This gives about 50g of charge B, of formula:
• NMR analysis Si for this charge B reveals a chemical shift ⁇ equal to -110 ppm, corresponding to a silicon structure "Q4" with 1 aluminum atom, that is to say that there is at least one bond Si-O-Al for the majority of silicon atoms.
• the invention thus finds preferential applications in rubber compositions intended for the manufacture of tire treads having both a low rolling resistance and a high resistance to wear, in particular when these treads are intended tires for passenger vehicles or for industrial vehicles of the Truck type.

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• Engineering & Computer Science (AREA)
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• Health & Medical Sciences (AREA)
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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

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• 2003
  • 2003-12-09 EP EP03789182A patent/EP1576043B8/fr not_active Expired - Lifetime
  • 2003-12-09 WO PCT/EP2003/013945 patent/WO2004056915A1/fr not_active Ceased
  • 2003-12-09 AU AU2003293806A patent/AU2003293806A1/en not_active Abandoned
  • 2003-12-09 JP JP2004561251A patent/JP4633471B2/ja not_active Expired - Fee Related
• 2005
  • 2005-06-20 US US11/155,507 patent/US7256233B2/en not_active Expired - Fee Related

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