DE4424582A1 - Rubber mixt., esp. for tyre carcass prodn. - Google Patents

Abstract

Sulphur-vulcanisable rubber mixts. (I) contain (A) 20-60 pts.wt. natural and/or synthetic rubber, (B) 20-80 pts.wt. conjugated diene/styrene copolymer(s) contg. at least 30 wt.% styrene and present in amts. of at least 20 wt.% in the rubber mixt., (C) up to 70 pts.wt. diene elastomer, and (d) 20-150 pts.wt. (w.r.t. total polymer) finely divided pptd. silica filler or a mixt. thereof with carbon black. Also claimed is the prodn. of (I) by mixing the above components and heating at up to 180 deg C, and then adding the vulcanisation system at below the vulcanisation temp. (Tv). Also claimed are moulded prods. contg. mixt. (I), esp. tyre carcasses contg. textile and/or metallic fabric coated with vulcanised mixt. (I), and pneumatic tyres with no internal plate contg. such carcasses. Also claimed is a process for the prodn. of such prods. by placing mixt. (I) in a mould at a temp. below Tv and then vulcanising the mixt. at Tv or above.

Description

The present invention relates to a vulcanized with sulfur canisable rubber mixture, a process for their Manufacture, especially airtight tire carcasses based on this rubber compound and tires these tire carcasses.

The tire is an important component of the vehicle. It represents a suspension element that the engine forces to Transfers locomotion to the road. The real thing The suspension element when driving is not rubber, but the air trapped inside under pressure. Of the Tires should have self-resilient properties, however the suspension properties of the compressed air as much as possible support.

It is therefore a general endeavor to be powerful To provide tires where the textile or Metal carcass is surrounded on all sides by a rubber, which has a high impermeability to air, so that the Tire pressure is maintained and the suspension inherent the tire's properties over a long period of time.

At the carcass, the actual strength member is it is usually a rayon, polyester fabric, Polyamide, polyaramid or steel, which with a rubber is rubberized. However, the carcass alone does not have any sufficient airtightness, which is why additionally on the An inner plate (inner core) is attached to the inside of the tires is brought, which ge the necessary air impermeability ensures. These inner panels are one air-impermeable material made of halobutyl rubber. These Halobutyl rubbers are not only expensive, they also bring problems with their processing and disposal yourself. They also have a large hysteresis value  which results in a high rolling resistance of the tire.

GB-A-2 198 138 describes a rubber (rubber) zu composition for a carcass consisting of at least 20% by weight Parts per 100 parts by weight of rubber made from a styrene buta diene copolymer with a high styrene content or made of emul sion-polymerized styrene-butadiene copolymers with a Styrene content of at least 30 parts by weight per 100 parts by weight Parts of rubber and 40 parts by weight per 100 parts by weight of the Rubbers consist of elastomers or elastomer blends.

Based on this, it was now a task of the present Invention to provide a rubber compound which are particularly suitable for air-impermeable tire carcasses can be set. In particular, it was a goal before lying invention, the thickness of the inner plate at pneu to reduce or to completely reduce them waive without affecting the air permeability tire or its running properties. In particular in particular, the tires should be such carcasses comprise, have a reduced rolling resistance in Compared to the tires that have a common structure, i.e. H. usual carcasses of usual thickness and composition point.

The object was achieved according to the invention by a rubber mixture vulcanizable with sulfur
20 to 60 parts by weight of natural rubber and / or synthetic rubber,
20 to 80 parts by weight of at least one copolymer of a conjugated diene and styrene,
up to 70 parts by weight of at least one diene elastomer as a further polymer,
20 to 150 parts by weight, based on 100 parts by weight of the total amount of polymer, filler
and optionally further conventional additives, characterized in that the copolymer of the conjugated diene and the styrene contains at least 30 parts by weight, based on the copolymer, of styrene, the copolymer is present in the rubber mixture at least 20% by weight and that Filling material is finely divided, precipitated silica alone or a combination of finely divided silica with soot.

It has surprisingly been found that, in certain Limits the higher the styrene content in the copolymer a conjugated diene and styrene or the copolymer mixture and therefore in the rubber composition, the greater also the airtightness of the carcasses. Of the The area in which this effect is particularly pronounced lies with a styrene content in the copolymers of at least 30 % By weight, but at most 60% by weight, based on the because of copolymer. The copolymer is in the rubber mixture in a proportion of at least 20 wt .-%. prefers at most 70% by weight, based on the total weight of the Rubber compound.

The one with the increased styrene content in the rubber mixture accompanying increase in hysteresis and the ver tied increase in rolling resistance could be more surprising wise by using finely divided, precipitated Compensate silica alone or its combination with soot be siert, which reduces the rolling resistance of tires with Carcasses made from the rubber mixture according to the invention manufactured could be significantly reduced. About it due to the increased impermeability to air carcass, the thickness of the inner layer in the tire adorned, in some cases even completely dispensed with them will.

It was also found that the molded and cured Rubber mixture according to the invention as an inner layer (inside  plate) can be used for pneumatic tires. The cured composition according to the invention has the same airtightness as that for this one Halobutyl rubbers used for this purpose and therefore can replace.

According to the invention, the proportion of natural rubber is of synthetic rubber or mixtures thereof 20 to 60% by weight Parts, preferably 30 to 50 parts by weight, the proportion of Copolymer 20 to 60 parts by weight, preferably 20 to 50 parts by weight Parts by weight and the proportion of any contained other polymers up to 70 parts by weight.

100 parts by weight of the polymer mixture form the basis for the Calculation of the addition of filling material and the other Additions.

The rubber mixture according to the invention contains the filling material in an amount of 10-100 parts by weight, preferably 20-60 parts by weight, based on 100 parts by weight of the polymers (Natural and / or synthetic rubber, diene / styrene copolymers and optionally additional diene elastomers).

According to the invention, natural rubber (cis-1,4-polyisoprene), Synthetic rubber (engineered synthetic cis-1,4-polyisoprene) or mixtures of natural and synthetic Rubber can be used.

The conjugated diene used according to the invention is out selects from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, Chloroprene, 1,3-pentadiene, hexadiene or mixtures thereof.

The copolymers for the rubber mixture according to the invention can by solution polymerization of the conjugated diene with styrene in a suitable inert solvent will hold. Suitable solvents are in particular Pentane, hexane, cyclohexane, heptane or their mixtures as well  Benzene, xylene, toluene or their mixtures and tetrahydro furan, diethyl ether or their mixtures or mixtures of mentioned hydrocarbons with the aromatic Hydrocarbons. Copolymers can also be used are made by emulsion polymerization were. Process for performing such emulsion poly merizations are the specialist from the relevant Literature known.

According to the present invention, the rubber compound a copolymer of a conjugated diene and styrene also a mixture of at least two different ones Copolymers from a conjugated diene and styrene contain. These can differ in the type and proportion of Distinguish as well as in the styrene content.

However, a copolymer must have a styrene content of at least Have 30 wt .-% and in the rubber mixture in one Proportion of at least 20 wt .-%, based on the total weight of the rubber mixture. The other Copolymer of styrene and a conjugated diene can be one Styrene content of less than 30 wt .-% and can in the rubber compound in a proportion of less than 20 % By weight, based on the total weight of the rubber mixture, be included.

A rubber mixture is particularly preferred two different of the above, in particular by Solution polymerization copolymers made from Styrene and butadiene are available and make a difference Lichen styrene content. The two different ones Copolymers are in a ratio of 2: 1 to 1: 2, preferably in Ratio 1: 1 used to each other.

A butadiene-styrene is particularly preferred as the copolymer Copolymer or mixtures of two different butadiene Styrene copolymers with different styrene content. As  Examples include a styrene content of 23.5% by weight and 40 % By weight.

Particularly preferred compositions contain 40% by weight Parts of natural rubber, 60 parts by weight of styrene-butadiene copoly mer SBR 1013 (40% by weight of styrene), 20 parts by weight of silica, 2.0 parts by weight of silane coupling agent and 8 parts by weight Mineral oil. Comprehensive as an example of a composition two styrene-butadiene copolymers with different Styrene content is a composition comprising 40% by weight Parts of natural rubber, 20 parts by weight of styrene-butadiene Copolymer SBR 1500 (23.5% by weight styrene), 40 parts by weight Styrene-butadiene copolymer SBR 1013 (43% by weight styrene), 25 Parts by weight of carbon black, 45 parts by weight of silica, 4.5 parts by weight Silane coupling agent and 9 parts by weight mineral oil called.

The rubber mixture according to the invention can furthermore be up to 70 Parts by weight, at least one diene elastomer as another Contain polymer selected from polybutadiene or Copolymers of isoprene and butadiene. These diene elastomers can from the underlying monomers for the Processes known to the person skilled in the art by means of solution or emulsion polymerization in the presence of transition metal catalysts getting produced.

The rubber mixture can also contain the usual additives the usual dosage, such as especially soft makers (mineral oils), anti-aging agents, sulfur, vulka nization accelerators (sulfenamides, thiazoles, guanidines) as well as other, but different fillers than the above ge and activators (e.g. stearic acid, zinc oxide).

According to the invention, any finely divided, precipitated silica can be used, as is more common used in the production of rubber compounds and which the specialist working in this field as known can be assumed. In this context  refer in particular to those in EP-A-0 501 227, EP-A-0 157 703 and the silicas described in DE-A-24 10 014 grasslands.

Accordingly, as precipitated and finely divided silicas used in the composition according to the invention that have a BET area of 40-350 m² / g, in particular of 100-250 m² / g, a CTAB area of 50-350 m² / g, preferably of 100-250 m² / g and an average particle diameter of 10-150 µm, preferably 10-100 µm and a DBP absorption Have 50-350 ml / 100 g, preferably 150-250 ml / 100 g.

However, silicas with particular preference are particularly preferred Morphology that can be obtained by reaction of alkali silicate with mineral acids at temperatures from 60 ° C to 95 ° C while maintaining a pH of 7.5 to 10.5 with continuous stirring, which intensi as required can be fourth, and setting a solid content in the precipitation suspension of 90 to 120 g / l, one subsequent acidification to pH 5, filtration, Drying and, if necessary, grinding and / or granules lation.

These silicas are characterized in that they are N₂- Surfaces (Areameter, Ströhlein, according to ISO 5794 / Annex D) from 35 m² / g to 350 m² / g, in particular 100 to 200 m² / g, at a BET / CTAB ratio of 0.8 to 1.2 (pH 9, according to Jay, Janzen and Kraus in "Rubber Chemistry and Technology" 44 (1971) 1287), and at the same time, as below in the Table I indicated a pore depending on the surface area volume, measured by means of mercury porosimetry (DIN 66 133), silanol group densities, measured in the form of the Sears Numbers (G.W. Sears, Analyt. Chemistry 12, 1981-83 (1956)) as well as an average aggregate size, measured by means of Pho tone correlation spectroscopy, possess:  

Table I

The silicas are also characterized by good ones Grindability, represented by the middle particles size after Malvern laser diffraction [D (4,3)] of 11 µm, in particular 10 µm, measured after grinding on a Alpine-Kolloplex impact pin mill (Z 160) in one pass output of 6 kg / h.

This grindability can be characterized u. a. by the energy that is needed to make a particular particle to achieve fineness or vice versa through the particle fine unit that arises when a grinding unit with the same Performance and the same product throughput is operated. The latter is the method of choice for simplicity. As Mill type becomes an Alpine-Kolloplex impact pin mill (Z 160) used and with a constant product throughput of 6 kg / h operated.

To characterize the particle size, the mean volume-weighted particle diameter MTG [D (4,3)] selected from the measurement by laser diffraction (Malvern Instruments, Model 2600c).

For more details on this silica with the special morphology is ver on DE-A 43 34 201 grasslands.  

In contrast to soot, the surface is of finely divided, precipitated silica inactive to rubber. Out for this reason it is necessary to use a silica Silane coupling agent to treat the bond between the silica surface with the rubber put. This treatment of the silica with the silane Coupling agent can be used while mixing the rubber or rubber mixture with the silica or before mixing with the rubber as a preliminary plot.

Includes the surfaces of the aforementioned silicas Lich the silicas with the special morphology, can additionally with silane coupling agents (organosilanes) following formulas I to III

[R _n 1 (RO) _3-n Si (alk) _m - (Ar) _p ] _q [B] (I),

R _n 1 (RO) _3-n Si (alkyl) (II)

or

R _n 1 (RO) _3-n Si (alkenyl) (III),

be modified in which mean

B: -SCN, -SH, -Cl, -NH₂ (if q = 1) or
-S _x (if q = 2),
R and R ′: an alkyl group with 1 to 4 carbon atoms, the phenyl radical, where all radicals R and R ′ can each have the same or a different meaning,
R: a C₁-C₄-alkyl, C₁-C₄-alkoxy group,
n: 0.1 or 2,
Alk: a divalent straight or branched hydrocarbon residue with 1 to 6 carbon atoms,
m: 0 or 1,
Ar: an arylene radical with 6 to 12 C atoms, preferably 6 C atoms,
p: 0 or 1 with the proviso that p and n do not simultaneously mean 0,
x: a number from 2 to 8,
Alkyl: a monovalent straight or branched unsaturated hydrocarbon radical having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms,
Alkenyl: a monovalent straight or branched unsaturated hydrocarbon radical having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.

In connection with the organosilanes, their production and their combination with silicas is also based on the referenced the following literature:

S. Wolff "Reinforcing and Vulcanization Effects of Silane Si 69 in Silica-Filled Compounds", Kautschuk + Gummi, Kunst stoffe 4, 280-284 (1981);
S. Wolff "Silanes in Tire Compounding After Ten Years - Review", lecture held at the Third Annual Meeting and Conference on Tire Science and Technology, The Tire Society, 28-29. March 1984, Akron, Ohio, USA;
S. Wolff "Optimization of Silane-Silica OTR Compounds. Part 1: Variations of Mixing Temperature and Time During the Modification of Silica with Bis (3-triethoxysilylpropyl) - tetrasulfide", Rubber Chem. Technol. 55: 967-989 (1982);
S. Wolff, R. Panenka Present Possibilities to Reduce Heat Generation of Tire Compoundst, lecture given at the International Rubber Conference IRC ′85 in Kyoto, Japan;
S. Wolff, R. Panenka, EH Tan "Reduction of Heat Generation in Truck Tire Tread and Subtread Compounds", lecture held at the International Conference on Rubbers and Rubber-like Materials, Jamshedpur, India, 6-8. November 1986;
S. Wolff "The Influence of Fillers on Rolling Resistance", lecture given at a meeting of the Rubber Division, American Chemical Society, New York / NJ, USA, April 8-11, 1986.

The invention for the pretreatment of the silicas Silane coupling agents used are known to the expert from the further prior art, in particular from EP-A-0 447 066, known from DE-A 20 62 883 or DE-A 24 57 446.

Preferably in the context of the present invention as a silane coupling agents are especially those silanes that have at least one alkoxyl group in the molecule. These Silanes are selected from bis (3-triethoxysilylpropyl) - tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3- trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilyl ethyl) tetrasulfide, 2-mercaptoethyltriethoxysilane, 3- Mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxy silane, 2-mercaptoethyltriethoxysilane, 3-nitropropyltri methoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropyl trimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloro ethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3- Trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfid, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfid, 2-triethoxysilyl-N, N-dimethylthiocarbamoyltetrasulfid, 3- Trimethoxysilylpropybenzothiazole tetrasulfide, 3-triethoxy silylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide. Among them are bis (3-triethoxysilylpropyl) -  tetrasulfide and 3-trimethoxysilylpropylbenzothiazoltetra sulfide preferred. Furthermore, bis (3-diethoxy methylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxy methylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloro propyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N- dimethylthiocarbamoyltetrasulfid, Dimethoxymethylsilylpro pylbenzothiazole tetrasulfide, 3-thiocyanatopropyltriethoxy silane, 3-thiocyanatopropyltrimethoxysilane, trimethoxyvinyl silane, triethoxyvinylsilane as silane coupling agent be set. However, bis (triethoxysilyl is preferred propyl) tetrasulfide.

The silane coupling agent is used in an amount of 0.2-30 Parts by weight, preferably from 0.5-15 parts by weight used for 100 parts by weight of the silica. The reaction between the silica and the silane coupling agent during the preparation of the mixture (in situ) or, old natively, be done outside. The latter leads to a pretreated (pre-modified) silica, the as such can be added to the mixture.

The carbon black used in the rubber mixture according to the invention is usually used for this purpose Commercial carbon black used. Conventional carbon blacks for the application according to the invention have a dibutyl phthalate Absorption (DBPA number) from 30 to 180 cm³ / 100 g (ASTM D2414), an iodine value of 10 to 250 g / kg (ASTM D 1510) and one CTAB number from 5 to 150 m³ / g (ASTM D 3765). Is preferred however, a carbon black with a CTAB number of less than 30 m³ / g. If the carbon black has a CTAB number of less than 30 m³ / g this has a particularly positive influence on the air tightness of the cured rubber mixture. Example In this context, a soot of quality is mentioned act N990. This has a DBPA number of 36 cm³ / 100 g, an iodine value of 10 g / kg and a CTAB number of 10 m³ / kg.

The soot is combined with finely divided, more precipitated  Silicic acid as a further filling material of the rubber mixture added. The ratio of the volumes used by Silica to carbon black is 1: 4 to 5: 1, preferably 1: 2 to 3: 1.

The invention further relates to a method of manufacture the sulfur-vulcanizable chew described above chuk mix through

• 1) Mixing 20 to 60 parts by weight of natural rubber and / or synthetic rubber, 20 to 80 parts by weight at least one copolymer from a conjugated Diene and styrene, the copolymer being a styrene proportion of at least 30 wt .-% and in the Rubber mixture in a proportion of at least 20 Wt .-% is contained, 20 to 150 parts by weight, based per 100 parts by weight of the total amount of polymer in a filling materials selected from finely divided, precipitated silica and a combination of finely divided, precipitated silica with soot and if necessary up to 70 parts by weight of a diene Elastomers as a further polymer and optionally other common additives with the exception of the Vulkani sation system while heating the Composition at a temperature of up to 180 ° C,
• 2) Adding the vulcanization system at a temperature temperature below the vulcanization temperature.

With regard to the importance of natural and synthetic Rubber, the copolymer of the conjugated diene and the Styrene, filler, usual additives and vulka nization system is referred to the above statements.

Carrying out the mixing processes and vulcanization can be used in the apparatus known to the person skilled in the art (e.g. in Kneading, extruding). In the first stage of the Mixing should be a temperature of at least 130 ° C and  preferably a temperature between 145 and 170 ° C. be put.

The method may also be so during mixing leads that the mixture first to the predetermined Temperature warmed up and then back to a temperature is cooled below the vulcanization temperature. This cycle must be followed at least once if necessary, be repeated several times.

The rubber mixture according to the invention can after the Vulka nize in the presence of a suitable vulcanization system under usual conditions known to those skilled in the art provision of single or multi-ply carcasses for vehicles tires are used.

The present invention therefore also relates to shaped ones Bodies containing the cured rubber according to the invention include mixture, in particular reinforcement (Kar cash registers) with the cured chew according to the invention Chuk mix are rubberized (coated) and further Inner layers (inner plates) consisting of the hardened rubber composition according to the invention, conventionally Replace inner layers of halobutyl rubber in tires.

The invention also relates to a method for manufacturing position of such shaped body by shaping the Rubber mixture according to the invention in the desired shape at a temperature below the vulcanization temperature and then vulcanizing the molded rubber mix at or above the vulcanization temperature.

The invention further relates to pneumatic vehicle tires comprising at least one carcass according to the invention a textile and / or metallic fabric, which on all sides with the cured according to the invention Rubber mixture is coated, the carcass a  increased impermeability to gases, especially air having. For tires that can include such a carcass the inner plate can be completely dispensed with or it has at least a reduced thickness compared to Inner layers, which are necessary for tires, the usual Carcass have the usual composition. The textile car Cash register usually consists of 1 to 2 car for car tires checkout locations.

The material of the reinforcement (fabric, cord) is made of selected from rayon, polyester, polyamide, polyaramid or Stole. The cured rubber compounds can also in conveyor belts, seals, V-belts, hoses and Find shoe soles.

The rubber compositions according to the invention can, such as shown in the examples below for the preparation of Carcasses are used for pneumatic tires that not just increased impermeability against gases and especially against air, but also a reduced rolling resistance have compared to a tire of a conventional design, the a carcass made from a rubber composition of the prior art of technology (GB-A-2 189 138).

The present invention is illustrated by the following Examples explained, but not limited to them.

Examples

The table below shows the Examples A and B for rubber compositions according to the State of the art (GB-A-2 198 138). Examples C and D are examples according to the invention, wherein Example C with Example A and Example D with Example B of the prior art Technology is comparable.  

Ultrasil VN3 (commercial product of the company DEGUSSA, Germany) used, the soot is the quality (GPF) N 660 (DBPA number = 90 cm³ / 100 g, Iodine number = 38 g / kg, CTAB number = 35 m³ / g).

The styrene-butadiene copolymer SBR 1500 is an emulsion copolymer with 23.5% by weight of styrene, at SBR 1013 is an emulsion copolymer with 43% by weight styrene Proportion of. Bis (3-triethoxysilyl propyl) tetrasulfide (Si 69, commercial product from DEGUSSA, Germany) used.

The silicas usable according to the invention with be special morphology can be according to the following play 1 to 3 are made:

example 1 Production of a silica in N₂ Surface area of 100 m² / g

43.5 m³ of hot water are stirred into a tub and so much commercial soda water glass (weight module 3.42, density 1348) until pH 8.5 is reached. Maintaining a fall temperature of 88 ° C and pH 8.5 are now 16.8 m³ of the same water glass and Schwe rock acid (96%) in 150 minutes at the same time against overlying points added. There is a feast content of 100 g / l. After that, sulfur continues acid added until pH <5 is reached. The solid is separated on filter presses, washed and the Press dough for spray drying or rotary kiln drying subjected and ground or not ground.

The product obtained has an N₂ surface area of 80 m² / g, an aggregate size of 1320 nm and a grindability of 10 µm. The Sears number (V₂) is 9.0 and the mercury poro simetry 2.7 ml / g.  

Example 2 Production of a silica in N₂ Surface level of 100-150 m² / g

The procedure is as in Example 1, with the exception that in a pH value of 9.0 during the precipitation template and during the precipitation is kept constant. After 135 minutes it appears Solids content in the precipitation suspension of 93 g / l.

The silica has an N₂ surface area of 120 m² / g, one Grindability of 8.8 µm, a Sears number of 9.1 for one Aggregate size of 490 nm and an Hg pore volume of 2.85 ml / g.

Example 3 Production of a silica in N₂ Surface level of 150-200 m² / g

The procedure is as in Example 1, with the exception that in a pH value of 9.5 during the precipitation template and during the precipitation is kept constant. After 135 minutes it appears Solids content in the precipitation suspension of 93 g / l.

The silica has an N₂ surface area of 184 m² / g, one Grindability of 8.7 µm, a Sears number of 15.7 an aggregate size of 381 nm and an Hg pore volume of 2.26 ml / g.  

table

The values can be adjusted by using pebbles acidity with the special morphology improved even further will.

Claims (21)

1. comprising rubber vulcanizable rubber mixture
20 to 60 parts by weight of natural rubber and / or synthetic rubber,
20 to 80 parts by weight of at least one copolymer of a conjugated diene and styrene,
up to 70 parts by weight of at least one diene elastomer as a further polymer,
20 to 150 parts by weight, based on 100 parts by weight of the total amount of polymer, filler
and optionally further conventional additives, characterized in that the copolymer of the conjugated diene and the styrene contains at least 30 parts by weight, based on the copolymer, of styrene, the copolymer is present in the rubber mixture at least 20% by weight and that Filling material is finely divided, precipitated silica alone or a combination of finely divided silica with soot. 2. Rubber mixture according to claim 1, characterized records that the proportion of natural rubber and / or Synthetic rubber 30 to 50 parts by weight, the proportion of Copolymer is 30 to 70 parts by weight. 3. Rubber mixture according to claim 1 or 2, characterized characterized in that the conjugated diene is selected from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, chloro pren, 1,3-pentadiene, hexadiene or mixtures thereof. 4. Rubber mixture according to one or more of the Claims 1 to 3, characterized in that the copoly mer of the conjugated diene and the styrene by solution polymerization or emulsion polymerization is available.   5. Rubber mixture according to one or more of the Claims 1 to 4, characterized in that two copoly with a difference between conjugated diene and styrene Lich styrene content can be used. 6. Rubber mixture according to claim 5, characterized records that the weight ratio of the copolymers under different styrene content is 2: 1 to 1: 2. 7. Rubber mixture according to one or more of the Claims 1 to 6, characterized in that the copolymer a conjugated diene and styrene a styrene-butadiene Is copolymer. 8. Rubber mixture according to one or more of the Claims 1 to 7, characterized in that they are fine distributed, precipitated silica that has a BET area from 40 to 350 m² / g, a CTAB area of 50 to 350 m² / g, an average particle diameter of 10 to 150 microns as well has a DBP number of 50 to 350 ml / 100 g. 9. Rubber mixture according to one or more of claims 1 to 8, characterized in that it contains silica of a special morphology which has an N₂ surface of 35 m² / g to 350 m² / g, with a BET / CTAB ratio of 0 , 8 to 1.2 and at the same time, as indicated below, have a pore volume, measured by means of mercury porosimetry (DIN 66 133), silanol group densities, measured in the form of the Sears numbers and an average aggregate size, measured by means of photon correlation spectroscopy, depending on the surface area: 10. Rubber mixture according to one or more of the Claims 1 to 9, characterized in that the pebbles good grindability, represented by the mean particle size after Malvern laser diffraction [D (4,3)] of 11 µm, in particular 10 µm, measured after grinding on an Alpine-Kolloplex impact pin mill (Z 160) at one Throughput of 6 kg / h. 11. Rubber mixture according to one or more of the Claims 1 to 10, characterized in that the soot is a Dibutyl phthalate absorption (DBPA number) from 30 to 180 cm³ / 100 g (ASTM D 2414), an iodine value of 10 to 250 g / kg (ASTM D 1510) and a CTAB number of 5 to 150 m³ / g (ASTM D 3765) owns. 12. Rubber mixture according to one or more of the Claims 1 to 11, characterized in that the Volume ratio of silica to the carbon black 1: 4 to 5: 1 is. 13. Rubber mixture according to one or more of claims 1 to 12, characterized in that the surfaces of the silicas are additionally coupled with silane coupling agents of the formulas I to III [R _n ¹ (RO) _3-n Si (alk) _m - (Ar) _p ] _q [B] (I), R _n 1 (RO) _3-n Si (alkyl) (II) or R _n 1 (RO) _3-n Si (alkenyl) (III), in which mean
B: -SCN, -SH, -Cl, -NH₂ (if q = 1) or
-S _x (if q = 2),
R and R¹: an alkyl group with 1 to 4 carbon atoms, the phenyl radical, where all radicals R and R ′ can each have the same or a different meaning,
R: a C₁-C₄-alkyl, C₁-C₄-alkoxy group,
n: 0.1 or 2,
Alk: a divalent straight or branched hydrocarbon residue with 1 to 6 carbon atoms,
m: 0 or 1,
Ar: an arylene radical with 6 to 12 C atoms, preferably 6 C atoms,
p: 0 or 1 with the proviso that p and n do not simultaneously mean 0,
x: a number from 2 to 8,
Alkyl: a monovalent straight or branched unsaturated hydrocarbon radical with 1 to 20 carbon atoms,
Alkenyl: a monovalent straight or branched unsaturated hydrocarbon radical with 2 to 20 carbon atoms. 14. Rubber mixture according to one or more of the Claims 1 to 13, characterized in that the silane coupling agent is selected from bis (3-triethoxysilyl propyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, Bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxy silylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3- Mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxy silane, 2-mercaptoethyltriethoxysilane, 3-nitropropyltri methoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropyl trimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloro ethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3- TrimethoxysilylpropylN, N-dimethylthiocarbamoyltetrasulfid, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfid, 2-triethoxysilyl-N, N-dimethylthiocarbamoyltetrasulfid, 3- Trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxy silylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3- Mercaptopropyldimethoxymethylsilane, 3-nitropropyldimethoxy methylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxy methylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfid, Dimethoxymethylsilylpropylbenzothiazoltetrasulfid, 3-thio cyanatopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxy silane, triinethoxy vinyl silane, triethoxy vinyl silane. 15. Rubber mixture according to claim 13 or 14, characterized characterized in that with the silane coupling agents modified silicas are obtainable by reaction from 0.2 to 30 parts by weight of the silane coupling agent to 100 parts by weight of the silica, the reaction between silica and silane coupling agent during the  Mixture production (in situ) or outside (pre-modifi adorned) can be carried out. 16. A process for the preparation of the rubber mixture as defined in one or more of claims 1 to 15, by

• 1) Mixing 20 to 60 parts by weight of natural rubber and / or synthetic rubber, 20 to 80 parts by weight of at least one copolymer of a conjugated diene and styrene, the copolymer having a styrene content of at least 30% by weight and in the rubber mixture is contained in a proportion of at least 20% by weight, 20 to 150 parts by weight, based on 100 parts by weight of the total amount of polymer of a filler material, which is selected from finely divided, precipitated silica and a combination of finely divided, precipitated silica with carbon black and optionally up to 70 parts by weight of a diene elastomer as a further polymer and optionally other customary additives with the exception of the vulcanization system while simultaneously heating the composition to a temperature of up to 180 ° C.,
• 2) admixing the vulcanization system at a temperature below the vulcanization temperature.

17. The method according to claim 16, characterized in that mixing at least one consecutive heat cooling and cooling cycle. 18. Shaped body comprising those made with sulfur cured rubber compound, as in one or more of the Claims 1 to 15 defined. 19. Shaped body according to claim 18, characterized records that it is a carcass comprising a textile and / or metallic fabric, which with the hardened Rubber mixture is coated.   20. The method of manufacturing the molded body according to Claim 18 or 19 by informing the rubber mixture as defined in claims 1 to 15 a temperature below the vulcanization temperature and subsequent vulcanization of the rubber mixture at the Vulcanization temperature or above. 21. Pneumatic tire encompassing the carcass, as in Claim 19 defined, wherein the tire has no inner plate having.