CA2193183A1 - Vulcanisable rubber compositions for the production of vehicle tyres - Google Patents
Vulcanisable rubber compositions for the production of vehicle tyresInfo
- Publication number
- CA2193183A1 CA2193183A1 CA002193183A CA2193183A CA2193183A1 CA 2193183 A1 CA2193183 A1 CA 2193183A1 CA 002193183 A CA002193183 A CA 002193183A CA 2193183 A CA2193183 A CA 2193183A CA 2193183 A1 CA2193183 A1 CA 2193183A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- composition according
- silica
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Vulcanisable rubber compositions consisting of styrene-butadiene copolymers, vinyl polybutadiene and finely divided, precipitated silica or mixtures of finely divided, precipitated silica and carbon black, are outstandingly suitable for the production of tyres, in particular tyre treads.
Description
Le A 31 402 - Forei gn Countri es _ ` -1- 2193183 Vulc~ni.c~ble rubber compositions for the production of vehicle tyres This invention relates to vulcanisable rubber compositions, to a process for theproduction thereof and to the use of the rubber compositions for the production of 5 tyres, in particular tyre treads.
There has in recent times been no lack of ~U~ L~ to produce tyre compositions, in particular for tyre treads, which have reduced rolling resistance combined with good adhesion in wet, icy and snowy conditions. The tyre should also generate little 10 running noise. Such tyre compositions are conventionally produced using a rubber composition comprising styrene-butadiene rubber polymerised in an organic solvent (solution SBR) in combination with at least one other diene elastomer and finelydivided, precipitated silica as the reinfo~ g filler material. The silica is used either alone or in combination with carbon black. V~llc~nis~tion is brought about by 15 sulphur and vulcanisation auxiliaries. Such a rubber composition is described, for example, in European patent application 0 501 227 and in US patent 5 227 425.
The rubber compositions described in the stated US patent and the stated European patent application in particular exhibit the disadvantage of limited processing 20 reliability and vulcanisation times in comparison with conventional carbon black filled compositions which are excessively long for short cycle times. This decreases their economic viability for tyre production.
The object of the present invention was thus to provide vulcanisable rubber 25 compositions which are in particular suitable for the treads of pneumatic tyres.
Tyres of this type having such treads should exhibit good characteristics with regard to wet skid resistance, rolling resistance, running noise, wear resistance and steering precision. Furthermore, due to the use of lower cost raw materials and a simplerproduction method, tyre production costs should be lower than the solution 30 described above.
This object has been achieved according to the invention by a vulcanisable rubber composition, in particular for tyre treads, consisting of LeA31402 21 931 83 a) 20 to 95 parts by weight of a styrene-butadiene copolymer having a styrene content of 15 to 45 wt. %, b) 10 to 70 parts by weight of a vinyl polybutadiene having a vinyl content of 30to80wt.%.
c) 50 to 100 parts by weight, relative to 100 parts by weight of the rubbers used, of finely divided, precipitated silica or a mixture of finely divided, precipitated silica and carbon black as the reinforcing filler and d) optionally further conventional additives.
The styrene-butadiene copolymers a) used according to the invention preferably have a styrene content of 18 to 40 wt. % .
The styrene-butadiene copolymers may be produced using known polymerisation processes, for example using the emulsion polymerisation process or the solutionpolymerisation process. It is preferred to use styrene-butadiene copolymers produced using the emulsion polymerisation process. The styrene-butadiene copolymers haveglass transition temperatures in the temperature range from -60C to -10C, preferably from -50C to -25C.
Reference should be made to the relevant technical literature for details relating to the production of styrene-butadiene copolymers, for example Appl. Sci. Publ. 1983, Ullmann (4th edition) 13, 605-611, Blackley, Synthetic Rubbers: Their Chemistry and Technology, pp. 95-126.
The rubber compositions according to the invention preferably consist of 30 to 90 parts by weight, in particular of 40 to 80 parts by weight of a styrene-butadiene copolymer.
The vinyl polybutadienes preferably used as component b) are those having a vinyl content of 40 to 80 wt. %, in particular of 60 to 70 wt. %. Such vinyl polybutadienes Le A 31 402 2 1 93 1 ~3 conventionally have a glass transition te~ lu~c in the temperature range from -65C to -20C, preferably from -40C to -25C.
The vinyl polybutadienes to be used according to the invention are produced using known processes, which are described, for example, in Houben-Weyl E20/2, 800.
The vinyl polybutadienes are used in particular in qll~ntities of 10 to 70 parts by weight, very particularly preferably in qll~ntities of 20 to 60 parts by weight.
According to the invention, it is in principle possible to use any finely divided (precipitated) silica, as is conventionally used in the production of rubber compositions and which may be assumed to be known to the person skilled in the art working in this sector. In this connection, it is in particular possible to use the silica described in EP-A-0 501 227, EP-A-0 157 703 and DE-A-24 10 014.
In general, the precipitated and finely divided silicas which may be used as the filler in the composition according to the invention are accordingly those having a BETsurface area of 40 to 350 m2/g, in particular of 100 to 250 m2/g, a CTAB surfacearea of 50 to 350 m2/g, preferably of 100 to 250 m2/g and an average particle diameter of 10 to 150 nm, preferably of 10 to 100 nm and a DBP adsorption value of 50 to 350 ml/100 g, preferably of 150 to 250 ml/100 g. The silica may be usedeither alone or in combination with carbon black.
It is particularly advantageous if silane coupling agents (organosilanes) are additionally added to the rubber compositions according to the invention. Silanecoupling agents which may in particular be considered are organosilanes of the following formulae (I) to (III):
[Rnl-(Ro)3-nsi-(Alk)m-(Ar)p]q[B] (I), Rnl-(RO)3 nSi-(Alkyl) (II) or Rnl-(RO)3 nSi-(Alkenyl) (III), Le A 31 402 4 2 1 ~3 ~ 83 in which B means -SNC, -SH, -Cl, -NH2 (if q = 1) or -Sx (if q = 2), 5 R and R1 mean an alkyl group having 1 to 4 carbon atoms, a phenyl residue, wherein all residues R and R1 may each have the same or a different meaning, n means 0, 1, 2 or 3, Alk means a divalent, linear or branched hydrocarbon residue having 1 to 6 carbon atoms, m means 0 or 1, Ar means an aryl residue having 6 to 12 C atoms, preferably 6 C Atoms, p means 0 or 1, providing that p and n do not simlllt~n~ously mean 0, 20 x means a number from 2 to 8, Alkyl means a monovalent, linear or branched saturated hydrocarbon residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, 5 Alkenyl means a monovalent, linear or branched unsaturated hydrocarbon residue having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
Reference is also made to the following literature in relation to the organosilanes, the production thereof and combination thereof with silicas:
S. Wolff: "Reinforcing and vulcanisation effects of silane Si 69 in silica-filled compounds", Kautschuk + Gummi, Kunststo~e 34, 280-284 (1981);
LeA31402 21 931 83 S. Wolff: "Optimisation of silane-silica OTR compounds. Part 1: Variations of mixing temperature and time during the modification of silica with bis(3-tri-ethoxysilylpropyl) tetrasulphide", Rubber Chem. Technol. 55, 967-989 (1982);
5 S. Wolff: "The influence of fillers on rolling resistance", paper presented at a conference of the Rubber Division, American Chemical Society, New York/NJ, USA, 8-11 April 1986.
The silane coupling agents used according to the invention are known to the person skilled in the art from the prior art, in particular from EP-A-0 447 066, DE-A-2 062 883 or DE-A-2 457 446. For the purposes of the present invention, plerel,~d silane coupling agents are in particular those silanes having at least one aL~coxy group per molecule. These silanes are selected from bis(3-triethoxysilylpropyl) tetrasulphide, bis(2-triethoxysilylethyl) tetrasulphide, bis(3-trimethoxysilylpropyl) 15 tetrasulphide, bis(2-trimethoxysilylethyl) tetrasulphide, 2-mercaptoethyltriethoxy-silane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-niLlopropyltrimethoxysilane, 3-niLloplopyltri-ethoxysilane, 3-chloropropyltrimethoxysilanet 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane,2-chloroethyltriethoxysilane,3-trimethoxysilylpropyl-20 N, N-dimethylthiocarbamoyl tetrasulphide,3 -triethoxysilylpropyl-N, N-dimethylthio-carbamoyl tetrasulphide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulphide, 3-trimethoxysilylpropylbenzothiazole tetrasulphide, 3-triethoxysilyl-propylbenzothiazoletetrasulphide,3-triethoxysilylpropylmethacrylatemonosulphide,3-trimethoxysilylpropylmethacrylate monosulphide. Of these, bis(3-triethoxysilyl-25 propyl) tetrasulphide and 3-trimethoxysilylpropylbenzothiazole tetrasulphide are preferred. Bis(3-diethoxymethylsilylpropyl) tetrasulphide, 3-mercaptopropyldimeth-oxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxy-methylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetra-sulphide, dimethoxymethylsilylpropylbenzothiazole tetrasulphide, 3-thiocyanato-30 propyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane may also be used as silane coupling agents.
Le A 31 402 2 1 ~3 ? 83 The silane coupling agents are preferably used in a quantity of 2 lo 20 parts byweight, in particular of 6 to 10 parts by weight, relative to 100 parls by weight of the silica. The reaction between the silica and the silane couplin~ agent may beperformed during production of the composition (in situ) or, alternatively, outside the production process. The latter gives rise to a plelleal~d (modified) silica which may be added directly to the composition.
The ratio of the quantities of silica to carbon black used, if they are used in combination with each other, is 1:4 to 7:1, preferably 1:2 to 3:1.
According to the invention, any carbon black suitable as a filler may in principle be used. It is preferred, however, to use a carbon black having a dibutyl phth~l~teadsorption value (DBPA value) of 30 to 180 cm3/100 g (ASTM D 2414), an iodine adsorption value of 10 to 250 g/kg (ASTM D 1510) and a CTAB value of 5 to 150 m2/g (ASTM D 3765).
The rubber composition according to the invention preferably contains the reinforcing filler material in a quantity of 65 to 80 parts by weight, relative to 100 parts by weight of the rubbers a), b) used and optionally of the 1,4-polybuta-diene used.
It is advantageous for the rubber composition according to the invention, in particular with regard to the wear resistance of the rubber composition, if 1 to40 parts by weight, preferably 20 to 30 parts by weight of 1,4-polybutadiene having a 1,4-cis content of 30 to 100 wt. %, preferably of 85 to 99 wt. %, are additionally added to the rubber composition.
The 1,4-polybutadienes may be produced using processes known to the person skilled in the art in the presence of Li-butyl or Ziegler/Natta systems as catalysts.
By way of example, the production of 1,4-polybutadiene having an elevated cis content is described in Adv. Polymer Sci. 38, 141-163 (1981); 71, 79-151 (1985).
Le A 31 402 2 ~ 93 1 83 The rubber composition may furthermore contain conventional qll~ntities of conventional additives, such as in particular plasticisers (for example mineral oils), antioxidants, sulphur, vulcanisation acceleMtors (for example sulphenamides, diazoles, guanidines), inorganic pigments, further fillers differing from the above-S stated activators (for example stearic acid, zinc oxide), waxes.
This invention moreover relates to a process for the production of the vulcanisablerubber compositions described above by mixing the styrene-butadiene copolymer, the vinyl polybutadiene and optionally the 1,4-polybllt~ en~ with silica or silica in 10 combination with carbon black, optionally together with the silane coupling agent and conventional additives with the exception of the vulcani.cing system while simultaneously heating the components to temperatures of 100 to 160C, preferably of 130 to 150C, and subsequently incorporating the vulcanising system at temperatures of below the vulcanisation temperature.
The rubber composition according to the invention may be vulcanised in the conventional manner in the presence of a suitable vulcanising system under conventional tyre production conditions known to the person skilled in the art. Once fully cured, the rubber composition according to the invention may also be used in 20 conveyor belts, seals. v-belts, hoses and shoe soles.
The present invention furthermore relates to the use of the rubber compositions according to the invention for the production of tyres, in particular tyre treads.
25 Tyres produced using the compositions according to the invention are in particular distinguished by the fact that they have good skid and rolling resistance, combined with excellent abrasion resistance. It should be particularly emphasised in thisconnection that skid, rolling and abrasion resistance are particularly well b~l~n~ecl.
It was particularly surprising to the person skilled in the art that, in contrast with 30 known rubber compositions, a considerable reduction in the cycle time during tyre production is achieved with the compositions according to the invention.
Le A 31 402 2 ' 93 1 83 Examples Raw materials used in the production of the rubber compositions according to theinvention:
s - Nd-BR
Commercial product "Buna CB24", Bayer AG, Germany (neodymium polybutadiene having a cis-1,4 content of approximately 98%) Commercial product "Krynol 1721", Bayer Polymères France, France (emulsion SBR having a copolymerised styrene content of approximately 40%, oil-extended with 27.3% aromatic mineral oil) - S-SBR
Commercial product "Buna SL 705", Bayer Elastomères France, France (solution SBR having a copolymerised styrene content of approximately 25%) - Vi-BR 1 Commercial product "Buna VI 70-1", Bayer Elastomères France, France (vinyl polybutadiene having a 1,2-vinyl content of approximately 70%) - Vi-BR 2 Commercial product "Buna VI 70-0", Bayer Elastomères France, France (vinyl polybutadiene having a 1,2-vinyl content of approximately 70%) - Carbon black N121 (ASTM-D 1765) Commercial product "Columbia N 121", Carbon Columbia (produced using the furnace process) Le A 31402 9 2ls3la3 - Silica Commercial product "Vulkasil S", Bayer AG, Germany (produced using the precipitation process) 5 - Activator Si69 Commercial product of Degussa, Germany - Aromatic mineral oil Commercial product "Renopal 450", Fuchs Vinyl solution SBR (oil-extended), Asaki, Japan - VS-SBR NOE
Vinyl solution SBR (not oil-extended), Bayer AG
Vinyl solution SBR (oil-extended), Bayer AG
Table 1: Formulation of compositions A* B* C* D E F G
VS-SBR OE 1 96.3 VS-SBR OE 2 96.3 Buna Vi 70-1 57.8 19.3 38.5 19.3 Krynol 1721 38.5 77 Buna SL 705 42 56 Buna CB 24 30 30 30 30 30 30 30 Renopal 450 11.3 11.3 37.5 11.3 11.3 27 32.3 Vulkasil S 70 70 70 70 70 70 70 Black N 121 10 10 10 10 10 10 10 Silane Si69 6 6 6 6 6 6 6 O
ZnO RS 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid Antilux 654 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Vulkanox HS/LG
Vulkanox 4020/LG 1 1 1 1 1 1 1 r~
Vulkacit CZ/EGC 1.8 1.8 1.8 1.8 1.8 1.8 1.8 .~, Vulkacit D/C 2 2 2 2 2 2 2 Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 cx * Comparative tests Table 2 Oil-extended polymers Non oil-extended polymers A* B* D E C* F G ~, MStS ~ 130C DIN 53 523 10.4 13.5 23.4 25 12 13.1 12.2 w MDR 2000 ~ 170C DIN 53 529 ts01 0.72 0.64 0.51 0.75 0.73 0.65 0.68 tlO 0.91 0.87 1.12 1.18 0.88 0.82 0.82 t50 2.16 2.06 2.83 2.66 1.76 1.78 1.59 t80 6.6 3.7 4.26 3.65 3.4 3.09 3.09 t90 13.5 9.1 6.1 4.3 5.9 4.7 s t95 19.6 15.1 8.5 5.3 11.8 8.2 8.3 Smax. 19.3 20.9 22.4 19.1 18.2 19.3 18.1 Vulcani.~ate properties Tensile, MPa, DIN 53 504 17.6 19.2 17.3 20.5 17.2 18 18.7 Elongation, %, DIN 53 504 375 410 410 480 445 460 480 Modulus 100, MPa, DIN 53 504 3.1 3.1 2.7 2.5 2.7 2.5 2.6 Modulus 300, MPa, DIN 53 504 13.1 12.7 10.6 10.9 10.1 9.8 9.7 r~?
Ring tear, N, (Pohle) 136 167 179 181 179 172 197 Hardness 23, Shore A, DIN 53 505 65 68 67 65 66 66 65 Hardness 70, Shore A, DIN 53 505 65 67 67 63 65 65 64 cx~
Table 2 - continued Oil-extended polymers Non oil-extended polymers ~;~
A* B* D E C* F G ~,, Elasticity 23, %, DIN 53 512 29 34 46 33 47 40 42 Elasticity 70, %, DIN 53 512 55 55 56 56 53 56 54 DIN abrasion, DIN 53 516 emery 40 135 114 139 117 95 89 81 emery 60 74 53 81 71 40 43 34 tan delta 0C, DIN 53 513 0.426 0.326 0.31 0.39 0.264 0.25 0.235 tan delta 60~C, DIN 53 513 0.104 0.103 0.116 0.114 0.128 0.128 0.120 o~ ~
There has in recent times been no lack of ~U~ L~ to produce tyre compositions, in particular for tyre treads, which have reduced rolling resistance combined with good adhesion in wet, icy and snowy conditions. The tyre should also generate little 10 running noise. Such tyre compositions are conventionally produced using a rubber composition comprising styrene-butadiene rubber polymerised in an organic solvent (solution SBR) in combination with at least one other diene elastomer and finelydivided, precipitated silica as the reinfo~ g filler material. The silica is used either alone or in combination with carbon black. V~llc~nis~tion is brought about by 15 sulphur and vulcanisation auxiliaries. Such a rubber composition is described, for example, in European patent application 0 501 227 and in US patent 5 227 425.
The rubber compositions described in the stated US patent and the stated European patent application in particular exhibit the disadvantage of limited processing 20 reliability and vulcanisation times in comparison with conventional carbon black filled compositions which are excessively long for short cycle times. This decreases their economic viability for tyre production.
The object of the present invention was thus to provide vulcanisable rubber 25 compositions which are in particular suitable for the treads of pneumatic tyres.
Tyres of this type having such treads should exhibit good characteristics with regard to wet skid resistance, rolling resistance, running noise, wear resistance and steering precision. Furthermore, due to the use of lower cost raw materials and a simplerproduction method, tyre production costs should be lower than the solution 30 described above.
This object has been achieved according to the invention by a vulcanisable rubber composition, in particular for tyre treads, consisting of LeA31402 21 931 83 a) 20 to 95 parts by weight of a styrene-butadiene copolymer having a styrene content of 15 to 45 wt. %, b) 10 to 70 parts by weight of a vinyl polybutadiene having a vinyl content of 30to80wt.%.
c) 50 to 100 parts by weight, relative to 100 parts by weight of the rubbers used, of finely divided, precipitated silica or a mixture of finely divided, precipitated silica and carbon black as the reinforcing filler and d) optionally further conventional additives.
The styrene-butadiene copolymers a) used according to the invention preferably have a styrene content of 18 to 40 wt. % .
The styrene-butadiene copolymers may be produced using known polymerisation processes, for example using the emulsion polymerisation process or the solutionpolymerisation process. It is preferred to use styrene-butadiene copolymers produced using the emulsion polymerisation process. The styrene-butadiene copolymers haveglass transition temperatures in the temperature range from -60C to -10C, preferably from -50C to -25C.
Reference should be made to the relevant technical literature for details relating to the production of styrene-butadiene copolymers, for example Appl. Sci. Publ. 1983, Ullmann (4th edition) 13, 605-611, Blackley, Synthetic Rubbers: Their Chemistry and Technology, pp. 95-126.
The rubber compositions according to the invention preferably consist of 30 to 90 parts by weight, in particular of 40 to 80 parts by weight of a styrene-butadiene copolymer.
The vinyl polybutadienes preferably used as component b) are those having a vinyl content of 40 to 80 wt. %, in particular of 60 to 70 wt. %. Such vinyl polybutadienes Le A 31 402 2 1 93 1 ~3 conventionally have a glass transition te~ lu~c in the temperature range from -65C to -20C, preferably from -40C to -25C.
The vinyl polybutadienes to be used according to the invention are produced using known processes, which are described, for example, in Houben-Weyl E20/2, 800.
The vinyl polybutadienes are used in particular in qll~ntities of 10 to 70 parts by weight, very particularly preferably in qll~ntities of 20 to 60 parts by weight.
According to the invention, it is in principle possible to use any finely divided (precipitated) silica, as is conventionally used in the production of rubber compositions and which may be assumed to be known to the person skilled in the art working in this sector. In this connection, it is in particular possible to use the silica described in EP-A-0 501 227, EP-A-0 157 703 and DE-A-24 10 014.
In general, the precipitated and finely divided silicas which may be used as the filler in the composition according to the invention are accordingly those having a BETsurface area of 40 to 350 m2/g, in particular of 100 to 250 m2/g, a CTAB surfacearea of 50 to 350 m2/g, preferably of 100 to 250 m2/g and an average particle diameter of 10 to 150 nm, preferably of 10 to 100 nm and a DBP adsorption value of 50 to 350 ml/100 g, preferably of 150 to 250 ml/100 g. The silica may be usedeither alone or in combination with carbon black.
It is particularly advantageous if silane coupling agents (organosilanes) are additionally added to the rubber compositions according to the invention. Silanecoupling agents which may in particular be considered are organosilanes of the following formulae (I) to (III):
[Rnl-(Ro)3-nsi-(Alk)m-(Ar)p]q[B] (I), Rnl-(RO)3 nSi-(Alkyl) (II) or Rnl-(RO)3 nSi-(Alkenyl) (III), Le A 31 402 4 2 1 ~3 ~ 83 in which B means -SNC, -SH, -Cl, -NH2 (if q = 1) or -Sx (if q = 2), 5 R and R1 mean an alkyl group having 1 to 4 carbon atoms, a phenyl residue, wherein all residues R and R1 may each have the same or a different meaning, n means 0, 1, 2 or 3, Alk means a divalent, linear or branched hydrocarbon residue having 1 to 6 carbon atoms, m means 0 or 1, Ar means an aryl residue having 6 to 12 C atoms, preferably 6 C Atoms, p means 0 or 1, providing that p and n do not simlllt~n~ously mean 0, 20 x means a number from 2 to 8, Alkyl means a monovalent, linear or branched saturated hydrocarbon residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, 5 Alkenyl means a monovalent, linear or branched unsaturated hydrocarbon residue having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
Reference is also made to the following literature in relation to the organosilanes, the production thereof and combination thereof with silicas:
S. Wolff: "Reinforcing and vulcanisation effects of silane Si 69 in silica-filled compounds", Kautschuk + Gummi, Kunststo~e 34, 280-284 (1981);
LeA31402 21 931 83 S. Wolff: "Optimisation of silane-silica OTR compounds. Part 1: Variations of mixing temperature and time during the modification of silica with bis(3-tri-ethoxysilylpropyl) tetrasulphide", Rubber Chem. Technol. 55, 967-989 (1982);
5 S. Wolff: "The influence of fillers on rolling resistance", paper presented at a conference of the Rubber Division, American Chemical Society, New York/NJ, USA, 8-11 April 1986.
The silane coupling agents used according to the invention are known to the person skilled in the art from the prior art, in particular from EP-A-0 447 066, DE-A-2 062 883 or DE-A-2 457 446. For the purposes of the present invention, plerel,~d silane coupling agents are in particular those silanes having at least one aL~coxy group per molecule. These silanes are selected from bis(3-triethoxysilylpropyl) tetrasulphide, bis(2-triethoxysilylethyl) tetrasulphide, bis(3-trimethoxysilylpropyl) 15 tetrasulphide, bis(2-trimethoxysilylethyl) tetrasulphide, 2-mercaptoethyltriethoxy-silane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-niLlopropyltrimethoxysilane, 3-niLloplopyltri-ethoxysilane, 3-chloropropyltrimethoxysilanet 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane,2-chloroethyltriethoxysilane,3-trimethoxysilylpropyl-20 N, N-dimethylthiocarbamoyl tetrasulphide,3 -triethoxysilylpropyl-N, N-dimethylthio-carbamoyl tetrasulphide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulphide, 3-trimethoxysilylpropylbenzothiazole tetrasulphide, 3-triethoxysilyl-propylbenzothiazoletetrasulphide,3-triethoxysilylpropylmethacrylatemonosulphide,3-trimethoxysilylpropylmethacrylate monosulphide. Of these, bis(3-triethoxysilyl-25 propyl) tetrasulphide and 3-trimethoxysilylpropylbenzothiazole tetrasulphide are preferred. Bis(3-diethoxymethylsilylpropyl) tetrasulphide, 3-mercaptopropyldimeth-oxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxy-methylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetra-sulphide, dimethoxymethylsilylpropylbenzothiazole tetrasulphide, 3-thiocyanato-30 propyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, trimethoxyvinylsilane, triethoxyvinylsilane may also be used as silane coupling agents.
Le A 31 402 2 1 ~3 ? 83 The silane coupling agents are preferably used in a quantity of 2 lo 20 parts byweight, in particular of 6 to 10 parts by weight, relative to 100 parls by weight of the silica. The reaction between the silica and the silane couplin~ agent may beperformed during production of the composition (in situ) or, alternatively, outside the production process. The latter gives rise to a plelleal~d (modified) silica which may be added directly to the composition.
The ratio of the quantities of silica to carbon black used, if they are used in combination with each other, is 1:4 to 7:1, preferably 1:2 to 3:1.
According to the invention, any carbon black suitable as a filler may in principle be used. It is preferred, however, to use a carbon black having a dibutyl phth~l~teadsorption value (DBPA value) of 30 to 180 cm3/100 g (ASTM D 2414), an iodine adsorption value of 10 to 250 g/kg (ASTM D 1510) and a CTAB value of 5 to 150 m2/g (ASTM D 3765).
The rubber composition according to the invention preferably contains the reinforcing filler material in a quantity of 65 to 80 parts by weight, relative to 100 parts by weight of the rubbers a), b) used and optionally of the 1,4-polybuta-diene used.
It is advantageous for the rubber composition according to the invention, in particular with regard to the wear resistance of the rubber composition, if 1 to40 parts by weight, preferably 20 to 30 parts by weight of 1,4-polybutadiene having a 1,4-cis content of 30 to 100 wt. %, preferably of 85 to 99 wt. %, are additionally added to the rubber composition.
The 1,4-polybutadienes may be produced using processes known to the person skilled in the art in the presence of Li-butyl or Ziegler/Natta systems as catalysts.
By way of example, the production of 1,4-polybutadiene having an elevated cis content is described in Adv. Polymer Sci. 38, 141-163 (1981); 71, 79-151 (1985).
Le A 31 402 2 ~ 93 1 83 The rubber composition may furthermore contain conventional qll~ntities of conventional additives, such as in particular plasticisers (for example mineral oils), antioxidants, sulphur, vulcanisation acceleMtors (for example sulphenamides, diazoles, guanidines), inorganic pigments, further fillers differing from the above-S stated activators (for example stearic acid, zinc oxide), waxes.
This invention moreover relates to a process for the production of the vulcanisablerubber compositions described above by mixing the styrene-butadiene copolymer, the vinyl polybutadiene and optionally the 1,4-polybllt~ en~ with silica or silica in 10 combination with carbon black, optionally together with the silane coupling agent and conventional additives with the exception of the vulcani.cing system while simultaneously heating the components to temperatures of 100 to 160C, preferably of 130 to 150C, and subsequently incorporating the vulcanising system at temperatures of below the vulcanisation temperature.
The rubber composition according to the invention may be vulcanised in the conventional manner in the presence of a suitable vulcanising system under conventional tyre production conditions known to the person skilled in the art. Once fully cured, the rubber composition according to the invention may also be used in 20 conveyor belts, seals. v-belts, hoses and shoe soles.
The present invention furthermore relates to the use of the rubber compositions according to the invention for the production of tyres, in particular tyre treads.
25 Tyres produced using the compositions according to the invention are in particular distinguished by the fact that they have good skid and rolling resistance, combined with excellent abrasion resistance. It should be particularly emphasised in thisconnection that skid, rolling and abrasion resistance are particularly well b~l~n~ecl.
It was particularly surprising to the person skilled in the art that, in contrast with 30 known rubber compositions, a considerable reduction in the cycle time during tyre production is achieved with the compositions according to the invention.
Le A 31 402 2 ' 93 1 83 Examples Raw materials used in the production of the rubber compositions according to theinvention:
s - Nd-BR
Commercial product "Buna CB24", Bayer AG, Germany (neodymium polybutadiene having a cis-1,4 content of approximately 98%) Commercial product "Krynol 1721", Bayer Polymères France, France (emulsion SBR having a copolymerised styrene content of approximately 40%, oil-extended with 27.3% aromatic mineral oil) - S-SBR
Commercial product "Buna SL 705", Bayer Elastomères France, France (solution SBR having a copolymerised styrene content of approximately 25%) - Vi-BR 1 Commercial product "Buna VI 70-1", Bayer Elastomères France, France (vinyl polybutadiene having a 1,2-vinyl content of approximately 70%) - Vi-BR 2 Commercial product "Buna VI 70-0", Bayer Elastomères France, France (vinyl polybutadiene having a 1,2-vinyl content of approximately 70%) - Carbon black N121 (ASTM-D 1765) Commercial product "Columbia N 121", Carbon Columbia (produced using the furnace process) Le A 31402 9 2ls3la3 - Silica Commercial product "Vulkasil S", Bayer AG, Germany (produced using the precipitation process) 5 - Activator Si69 Commercial product of Degussa, Germany - Aromatic mineral oil Commercial product "Renopal 450", Fuchs Vinyl solution SBR (oil-extended), Asaki, Japan - VS-SBR NOE
Vinyl solution SBR (not oil-extended), Bayer AG
Vinyl solution SBR (oil-extended), Bayer AG
Table 1: Formulation of compositions A* B* C* D E F G
VS-SBR OE 1 96.3 VS-SBR OE 2 96.3 Buna Vi 70-1 57.8 19.3 38.5 19.3 Krynol 1721 38.5 77 Buna SL 705 42 56 Buna CB 24 30 30 30 30 30 30 30 Renopal 450 11.3 11.3 37.5 11.3 11.3 27 32.3 Vulkasil S 70 70 70 70 70 70 70 Black N 121 10 10 10 10 10 10 10 Silane Si69 6 6 6 6 6 6 6 O
ZnO RS 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid Antilux 654 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Vulkanox HS/LG
Vulkanox 4020/LG 1 1 1 1 1 1 1 r~
Vulkacit CZ/EGC 1.8 1.8 1.8 1.8 1.8 1.8 1.8 .~, Vulkacit D/C 2 2 2 2 2 2 2 Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 cx * Comparative tests Table 2 Oil-extended polymers Non oil-extended polymers A* B* D E C* F G ~, MStS ~ 130C DIN 53 523 10.4 13.5 23.4 25 12 13.1 12.2 w MDR 2000 ~ 170C DIN 53 529 ts01 0.72 0.64 0.51 0.75 0.73 0.65 0.68 tlO 0.91 0.87 1.12 1.18 0.88 0.82 0.82 t50 2.16 2.06 2.83 2.66 1.76 1.78 1.59 t80 6.6 3.7 4.26 3.65 3.4 3.09 3.09 t90 13.5 9.1 6.1 4.3 5.9 4.7 s t95 19.6 15.1 8.5 5.3 11.8 8.2 8.3 Smax. 19.3 20.9 22.4 19.1 18.2 19.3 18.1 Vulcani.~ate properties Tensile, MPa, DIN 53 504 17.6 19.2 17.3 20.5 17.2 18 18.7 Elongation, %, DIN 53 504 375 410 410 480 445 460 480 Modulus 100, MPa, DIN 53 504 3.1 3.1 2.7 2.5 2.7 2.5 2.6 Modulus 300, MPa, DIN 53 504 13.1 12.7 10.6 10.9 10.1 9.8 9.7 r~?
Ring tear, N, (Pohle) 136 167 179 181 179 172 197 Hardness 23, Shore A, DIN 53 505 65 68 67 65 66 66 65 Hardness 70, Shore A, DIN 53 505 65 67 67 63 65 65 64 cx~
Table 2 - continued Oil-extended polymers Non oil-extended polymers ~;~
A* B* D E C* F G ~,, Elasticity 23, %, DIN 53 512 29 34 46 33 47 40 42 Elasticity 70, %, DIN 53 512 55 55 56 56 53 56 54 DIN abrasion, DIN 53 516 emery 40 135 114 139 117 95 89 81 emery 60 74 53 81 71 40 43 34 tan delta 0C, DIN 53 513 0.426 0.326 0.31 0.39 0.264 0.25 0.235 tan delta 60~C, DIN 53 513 0.104 0.103 0.116 0.114 0.128 0.128 0.120 o~ ~
Claims (8)
1. A vulcanisable rubber composition comprising a) 20 to 95 parts by weight of a styrene-butadiene copolymer having a styrene content of 15 to 45 wt.%, b) 10 to 70 parts by weight of a vinyl polybutadiene having a vinyl content of 30 to 80 wt.%, and c) 50 to 100 parts by weight, relative to 100 parts by weight of the rubbers used, of finely divided, precipitated silica or a mixture of finely divided, precipitated silica and carbon black as the reinforcing filler.
2. A rubber composition according to claim 1, further comprising 1 to 40 parts by weight of 1,4-polybutadiene having a 1,4-cis content of 80 to 100 wt.%.
3. A rubber composition according to claim 1 or 2, further comprising from 2 to 20 parts by weight of a silane coupling agent, relative to 100 parts by weight of the silica used.
4. A process for preparing a vulcanisable rubber composition according to claim 1, 2 or 3 comprising mixing the styrene-butadiene copolymer a), the vinyl polybutadiene b) and optionally the 1,4-polybutadiene with silica or silica in combination with carbon black c), optionally together with a silane coupling agent in the absence of any vulcanising agent heating the components to a temperature of from 100 to 160°C
and subsequently incorporating a vulcanising agent at a temperature of below the vulcanisation temperature.
and subsequently incorporating a vulcanising agent at a temperature of below the vulcanisation temperature.
5. A method of preparing a tyre which comprises vulcanising a composition according to claim 1, 2 or 3.
6. A method of preparing a tyre tread which comprises vulcanising a composition according to claim 1, 2 or 3.
7; A use of a composition according to claim 1, 2 or 3 to prepare a tyre.
8. A use of a composition according to claim 1, 2 or 3 to prepare a tyre tread.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19547630.1 | 1995-12-20 | ||
| DE19547630A DE19547630A1 (en) | 1995-12-20 | 1995-12-20 | Vulcanizable rubber compounds for the manufacture of vehicle tires |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193183A1 true CA2193183A1 (en) | 1997-06-21 |
Family
ID=7780685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193183A Abandoned CA2193183A1 (en) | 1995-12-20 | 1996-12-17 | Vulcanisable rubber compositions for the production of vehicle tyres |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0785230B1 (en) |
| JP (1) | JPH09183868A (en) |
| CA (1) | CA2193183A1 (en) |
| DE (2) | DE19547630A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359045B1 (en) | 1998-11-16 | 2002-03-19 | Bayer Aktiengesellschaft | Vulcanizable rubber compounds containing styrene-butadiene and butadiene rubbers |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518350B1 (en) | 1999-07-30 | 2003-02-11 | Jsr Corporation | Rubber composition and tire |
| JP4963535B2 (en) * | 2001-09-28 | 2012-06-27 | 株式会社ブリヂストン | Rubber composition for belt of belt conveyor, belt and belt conveyor |
| US20050049351A1 (en) * | 2003-09-02 | 2005-03-03 | D'sidocky Richard Michael | Tire with at least one of sidewall insert and/or apex of a rubber composition which contains a high vinyl polybutadiene |
| JP4616550B2 (en) * | 2003-12-16 | 2011-01-19 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
| JP4583023B2 (en) * | 2003-12-16 | 2010-11-17 | 住友ゴム工業株式会社 | Rubber composition for tire sidewall |
| JP4602718B2 (en) * | 2004-08-30 | 2010-12-22 | 東洋ゴム工業株式会社 | Rubber composition for tire sidewall and pneumatic tire |
| JP4643207B2 (en) * | 2004-09-08 | 2011-03-02 | 東洋ゴム工業株式会社 | Rubber composition for pneumatic tire and pneumatic tire |
| IT1394126B1 (en) * | 2008-10-22 | 2012-05-25 | Bridgestone Corp | TREAD COMPOUND FOR WINTER TIRES |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2062883C3 (en) | 1970-12-21 | 1981-06-25 | PPG Industries, Inc., 15222 Pittsburgh, Pa. | Coupling agent for tire treads |
| GB1424503A (en) | 1973-03-05 | 1976-02-11 | Cabot Corp | Precipitated silica reinforcing agents and rubber compositions containing same |
| DE2457446A1 (en) | 1974-12-05 | 1976-06-10 | Metzeler Kautschuk | IMPROVING THE GRIP OF RUBBER MIXTURES OR CUTTING |
| US3978165A (en) * | 1975-04-14 | 1976-08-31 | Phillips Petroleum Company | Elastomeric blend |
| FR2364630A1 (en) * | 1976-09-15 | 1978-04-14 | Nippon Rubber Co | Injection moulding rubber compsn. for shoe soles - contains (1,2)-polybutadiene and a diene rubber |
| FR2562534B1 (en) | 1984-04-06 | 1986-06-27 | Rhone Poulenc Chim Base | NOVEL PRECIPITATED SILICA WITH IMPROVED MORPHOLOGICAL CHARACTERS, PROCESS FOR OBTAINING THE SAME AND APPLICATION THEREOF, IN PARTICULAR AS FILLER |
| US4522970A (en) * | 1984-06-25 | 1985-06-11 | The Goodyear Tire & Rubber Company | Tire with tread rubber containing medium vinyl polybutadiene with clay and carbon black |
| DE69119125T3 (en) | 1990-03-02 | 2001-01-11 | Bridgestone Corp | tire |
| FR2673187B1 (en) | 1991-02-25 | 1994-07-01 | Michelin & Cie | RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION. |
| CA2108763A1 (en) * | 1993-09-07 | 1995-03-08 | David John Zanzig | Tire with silica reinforced tread |
| CA2160324C (en) * | 1995-06-07 | 2007-05-01 | Joseph Kevin Hubbell | Tire having silica reinforced tread |
-
1995
- 1995-12-20 DE DE19547630A patent/DE19547630A1/en not_active Withdrawn
-
1996
- 1996-12-09 DE DE59606632T patent/DE59606632D1/en not_active Expired - Fee Related
- 1996-12-09 EP EP96119697A patent/EP0785230B1/en not_active Expired - Lifetime
- 1996-12-13 JP JP8352440A patent/JPH09183868A/en active Pending
- 1996-12-17 CA CA002193183A patent/CA2193183A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6359045B1 (en) | 1998-11-16 | 2002-03-19 | Bayer Aktiengesellschaft | Vulcanizable rubber compounds containing styrene-butadiene and butadiene rubbers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09183868A (en) | 1997-07-15 |
| DE59606632D1 (en) | 2001-04-26 |
| DE19547630A1 (en) | 1997-06-26 |
| EP0785230A1 (en) | 1997-07-23 |
| EP0785230B1 (en) | 2001-03-21 |
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