HK1228852B - Rubber compound - Google Patents

Description

The invention relates to vulcanizable rubber compounds and vulcanized products thereof, suitable for the manufacture of tyres, tyre treads or tyre parts.

In the case of tyres or tyre treads, good adhesion to dry and wet surfaces, low rolling resistance and high abrasion resistance are important characteristics to be pursued. It is very difficult to improve the slip resistance of a tyre without at the same time deteriorating the rolling resistance and abrasion resistance. Low rolling resistance is important for low fuel consumption, and high abrasion resistance is the decisive factor for high tyre performance.

The wet slip resistance and rolling resistance of a tread are largely dependent on the dynamic-mechanical properties of the rubber used in the manufacture of the compound. To reduce rolling resistance, rubbers with a high bounce elasticity at higher temperatures (60°C to 100°C) are used for the tread. On the other hand, to improve wet slip resistance, rubbers with a high damping factor at low temperatures (0 to 23°C) and low return coefficients in the range 0°C to 23°C respectively are used. To meet this complex requirement, mixtures of different rubber compounds are used at medium and high bounce elasticities at higher temperatures (60°C to 100°C).

Dual-bonded anionic polymerized solvent rubbers, such as solvent polybutadiene and solvent styrene butadiene rubbers, have advantages over similar emulsion rubbers in the production of low rolling resistance tyre treads. The advantages include controllability of vinyl content and associated glass transition temperature and molecular branching. This in practical application results in particular advantages in the ratio of wet slip resistance to tyre rolling width. Significant contributions to tyre energy dissipation and thus rolling resistance in tyre tread networks result in free polymer and reverse-flow from the tread and the excess of the filler gas in the filler/exhaust balance (exhaust) and the exhaust emissions from the tyre.

The disadvantage of using functionalised solvent styrene butadiene rubber and silica as reinforcement for the production of tyres, tyre surfaces or tyre parts is that the rubber mixture becomes very elastic due to increased polymer-filler exchange and at the same time a reduced mixture of filler-filler-filler, which makes it difficult to operate the rubber mixture during extrusion or splitting. This is particularly evident in the evaluation of the roughness of the structure, which is demonstrated in the control of the heat loss.

For example, additives such as fatty acid esters, fatty acid salts or mineral oils have been proposed to improve the workability of silica-containing rubber mixtures. These additives have the disadvantage of increasing the flow capacity but at the same time reducing the strain values at higher stretch rates (e.g. 100% to 300%) or the hardness of the vulcanized rubber, so that the reinforcing effect of the filler is impaired.

US 2012/029114 A1 describes a tyre made of a rubber, which includes a component that has a silicon dioxide reinforced rubber composition including special polybutadiene rubbers, functionalised styrene/butadiene elastomers and cis-1,4-polyisoprene rubber.

EP 2 530 095 A1 describes a pneumatic tyre with a rim surface in the form of a cap/base with an outer rim surface rubber layer, comprising a tyre tread and a rim base rubber layer, where the rim base rubber layer is at least partially or completely below the outer rim surface rubber layer. The rubber composition of the outer rim cover covers the rubber, in terms of parts by weight per 100 parts by weight of the rim rubber (phruks), (A) 55 to 85 carbons, including cis-1,4-polybutadiene and (D) 45 to 45 carbons, including at least an additional E 60-1, a cis-1,4-polybutadiene-based fuel, a phosphorus-based fuel (C) 110 to 40 carbons, a phosphorus-based fuel, a phosphorus-based fuel, a phosphorus-based fuel, and a combination of hydrocarbon and phosphorus-rich compounds (1) containing a phosphorus-rich compound containing a phosphorus-rich compound of phosphorus and phosphorus-rich compounds.

US 2012/309891 A1 describes pneumatic tyres intended for high performance use and having a tread pattern with a special cis-1,4-polybutadiene rubber-rich tread pattern with a special cis-1,4-polybutadiene rubber-rich tread pattern based on the following parts per 100 parts by weight of tread pattern (phr), (A) approximately 55 to approximately 85 phr of specialised cis-1,4-polybutadiene rubber and (B) approximately 15 to approximately 45 parts of a specialised cis-1,4-polybutadiene rubber-rich tread pattern, including approximately 80 to approximately 60 percent of the cis-1,4-polybutadiene rubber, with a specialised cis-1,1-polybutadiene rubber-rich tread pattern based on the following parts by weight per 100 parts by weight of the tread pattern (phr), (A) approximately 55 to approximately 85 parts by weight of specialised cis-1,4-polybutadiene rubber and (B) approximately 15 to approximately 150 parts by weight of a specialised cis-1,4-polybutadiene rubber-rich tread pattern, including approximately 60 to approximately 60 parts by weight of specialised cis-1,1-polybutadiene rubber-rich treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted tread pattern (P1-polybutadiene rubber-rich treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted tread) and (P1-polybutadiene rubber-rich treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted treadjusted tread

US 2011/136956 A1 reveals 1,4-polybutadiene functionalized with an aromatic organo-sulfur compound. Improved machinability is achieved due to reduced Mooney viscosity and improved feel when striking and flying due to reduced compression and increased restitution in the manufacture of a golf ball core.

US 2009/156751 A1 concerns a manufacturing process for an aromatic 1,4-cis organosulfur-functionalised polybutadiene consisting of: polymerisation of 1,3-butadiene or butadiene derivative in the presence of a specific catalyst in an unpolar solvent to produce 1,4-cis polybutadiene; and conversion of the resulting polybutadiene to an aromatic organosulfur compound.

US 2010/186859 A1 describes pneumatic tyres with an outer tread consisting of a cis-1,4-polybutadiene-rich and silica-rich rubber compound containing specified elastomers with spatially defined glass transition temperatures in combination with silica and specified soot reinforcement.

US 2012/041129 A1 concerns rubber compounds containing silane with, where appropriate, functionalised service rubber and microgels, a process for their manufacture and use for the production of wet-resistant and low rolling resistant high abrasion resistant motor vehicle tyre tread surfaces, containing (A) at least one functional rubber compound, where applicable, with a polymer chain of repeating units based on at least one dien and one or more vinyl aromatic gears, where applicable, and (B) a styrene/butadiene monomer of rubber with a sourcing index in toluene of 1 to 25 and a particle size of 5 to 1000 nm and (C) a defined Silan.

US2011/282001 A1 concerns functional service rubbers and their manufacture, rubber compounds containing these functional service rubbers and their use in the manufacture of rubber vulcanisates, particularly for the manufacture of highly reinforced rubber moulds. In particular, the use of tyres with particularly low rolling resistance and particularly high wet and abrasion resistance is preferred. The functional service rubbers are obtained by polymerisation of dieners and, where appropriate, vinylaromatic monomers in a solvent and subsequent transformation with hydroxymercaptans of the following groups: HS-R-OH, R for a linear, branched or cyclic C1-C36 or alkyl group, or alkyl group, which may be on any of these groups, or by substitution of a hydroxy group and, where appropriate, by other sulphur groups.

US 2012/024441 A1 describes an air tyre having a rubber tread with a cap/base design consisting of an outer tread head layer with an outer tread and a base layer of tread below, the tread head layer consisting of several circular, longitudinal rubber tread cap zones with graded physical properties, the tread strip zones individually extending radially from the tread cap inside to the tread base layer, the tread strip base cap zones consisting of two primary tread caps and approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately approximately 90 to 100 TC of tread caps, the tread strip zones consisting of a central cylindrical poly (CaO) capsule with a cylindrical cylinder of approximately 40 to 40 C (CaO) or a cylindrical cylinder of approximately 40 to 100 C (CaO) per cent of the thermal expansion of a volcanic cylinder (CaO) comprising a cylinder of approximately 40 to 100 TC (CaO) of a cylinder of approximately 40 to 100 C (CaO) of a cylinder of approximately approximately 40 to 100 to 100 C (CaO) of a cylinder of approximately approximately approximately approximately approximately approximately 40 to 100 to 100 to 100 to 100 C (CaO) of a cylinder of approximately approximately approximately approximately approximately 40 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 1004-content of at least 90%, an average molecular weight (Mn) of more than 175.000 and a heterogeneity index (Mw/Mn) of less than 2.5; (A3) of about 50 to about 150 phr silicon dioxide; whereby the primary strip cap zones comprise a vulcanizable rubber composition based on 100 parts by weight of elastomer (phr) (B1) of about 60 to about 90 phr of a solution polymerized styrene butadiene rubber functionalized with an alkoxy group and comprising at least one functional group selected from the group consisting of primary and thiolene; (B2) 40 to about 10 phr polybutadiene with a cyclostructure of about 96-1,99% to about 0,4-amino cycloisomers,1 to about 1% trans-1,4-isomer units and about 1 to about 3% vinyl-1,2-isomer units; a mean molecular weight (Mn) in the range of about 75,000 to about 150,000 and a heterogeneity index (Mw/Mn) in the range of about 3/1 to about 5/1; and (B3) about 50 to about 150 phr silicon dioxide.

The purpose of the invention is therefore to provide vulcanizable rubber compounds which exhibit good handling characteristics in the manufacture of tyres, tyre treads or tyre parts, without any impairment of the dynamic-mechanical properties of the tyres, tyre treads or tyre parts, in particular in terms of rolling resistance, wet-slip resistance and/or mechanical strength.

Surprisingly, this target was found to be vulcanizable rubber compounds containing at least the following components: (b) at least one modified polybutadiene with a cis-1,4-unit content > 95% by weight and a 1,2-vinyl content < 1%, where the polybutadiene has been modified after polymerisation by sulphur chlorides, (c) at least one silica, (d) at least one other filler, (e) at least one vulcanizing agent, (f) at least one oil and (g) at least one other rubber additive, where applicable, including gum the modified polybutadiene has a leap-like increase in Mooney viscosity (ML 1+4 at 100 °C) of at least 50% compared to the Mooney viscosity (ML 1+4 at 100 °C) of the polybutadiene before the addition of the sulphur chloride, The Commission has already made a number of proposals.

Description of the figures

Figure 1 shows the graphical evaluation of the second heating thermogram by using three lines to determine the glass transition temperature of the rubber. The glass transition temperature Tg is obtained as the centre temperature of the interfaces Y and Z. The experimental implementation of the DSC method is described in detail later in this application.Figure 2 includes a graphical representation of the values for the stiffness index (SI) and rolling resistance index (RRI) which were determined for examples 1 to 10.Figure 3 shows the Garvey ExtrusionThe profiles of the extrudate from volcanoes as described in examples 1 to 4 (numbers as shown in Table 6 of the examples) are produced at 100°C.Figure 4 shows the experimental implementation of the DSC method in detail in the course of this application.Figure 5 shows the extrudate profiles of the volcanoes as described in Extrudate at 120°C (numbers as shown in Table 6 of the Examples) and examples as shown in Extrudate at 120°C (numbers as shown in Table 6 of the Extrudate Table 1 to 6 of the Extrudate Table 8 to 6 of the Extrudate) and shows the Garvey Extrudate profiles as described in Examples 6 to 6 of the Extrudate at 120°C.

It was found that the addition of modified polybutadiene (component b) has a positive effect on the fluidity of rubber compounds and results in vulcanizates with good dynamic behaviour and significantly increased hardness/stiffness, which is particularly important for the workability of tyres, tyre treads or tyre parts.

Component (a) is as follows:

The functionalised polymer is preferably functionalised dien polymers or dien copolymers obtained by copolymerisation of dien with vinyl aromatic monomers, and the functionalised polymer is preferably a polybutadiene, polyisoprene, butadiene isoprene copolymer, butadiene styrene copolymer (SSBR), isoprene styrene copolymer or butadiene isoprene styrene terpolymer.

In the case of a functionalised polymer used as component (a) which is a modified polybutadiene, it shall be different from component (b).

In particular, a) at least one butadiene styrene copolymer (SSBR) is used as a preferred component. SSBR is understood to mean rubber produced in a solution process based on vinyl aromatics and dyes, preferably conjugated dyes (H. L. Hsieh, R. P. Quirk, Marcel Dekker Inc. New York-Basel 1996, pp. 447-469; Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, 1987, Vol. E 20, pp. 114 to 134; Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Rubber 3. Synthetic, Vlagsgesellschaft mbH, D-69451 Weinheim, 1993, pp. 240-364).

The content of a polymerized vinyl aromatic is preferably in the range of 5 to 50% by weight, preferably in the range of 10 to 40 by weight. Diolefins are 1,3-butadiene, p-tert-butyl styrene, α-methyl styrene, p-methoxystyrene, vinyl naphthalene, divinyl benzene, trivinyl benzole and divinyl naphthalene. Preferably, the content of a polymerized vinyl aromatic is styrene. The content of a polymerized vinyl aromatic is preferably in the range of 5 to 50% by weight, preferably in the range of 10 to 40 by weight. Diolefins are 1,3-butadiene, p-tert-butyl styrene, α-methyl styrene, p-methyl styrene, p-methoxystyrene, 1,3-butadiene and 1,4-butadiene. The content of the total polymerized is 1,3-butadiene is 1,3-butadiene. The content of a double-butadiene is usually in the range of 90 to 10%, and the content of the double-butadiene is in the range of 90 to 10%, and the total polymerized is in the range of 90 to 10 to 10 to 10%, respectively.

Normally, the polymerized monomers and the different dien configurations are statistically distributed in the polymer.

(a) for the rubber mixtures of the invention, is produced in particular by anionic solution polymerisation, i.e. by means of an alkali or earth metal catalyst in an organic solvent.

The solution polymerized vinylaromate/diene rubbers have Mooney viscosities (ML 1+4 at 100°C) in the range of 20 to 150 Mooney units (MU), preferably in the range of 30 to 100 Mooney units. In particular, the high molecular weight SSBR types with Mooney viscosities > 80 MU may contain oils in amounts of 30 to 100 parts by weight relative to 100 parts by weight of rubber. Oil-free SSBR rubbers have glass transition temperatures in the range of -70°C to -10°C as determined by differential thermoanalysis (DSC).

SSBR can be linear, branched or end-group modified, for example, such types are listed in DE 2 034 989 C2 and JP-A-56-104 906.

The introduction of functional groups at the ends and/or the ends of the polymer chain allows the physical or chemical attachment of these polymer chain ends or ends to the filling surface, thereby limiting their mobility and thus reducing energy dissipation when dynamically applying the tyre tread surface. At the same time, these functional groups can improve the dispersion of the filling material in the tyre tread surface, which can lead to a weakening of the filling network and thus a further reduction in rolling resistance.

For this purpose, numerous end-group modification methods have been developed. For example, EP0180141A1 describes the use of 4,4'-bis ((dimethyl-amino) benzophenone or N-methylcaprolactam as functionalization reagents. The use of ethylene oxide and N-vinylpyrrolidone is also known from EP0864606A1. A number of other possible functionalization reagents are listed in US4417029. Methods for introducing functional groups at the beginning of the polymer chain by means of functional anionic polymerization initiators are described, for example, in EP0513217A1 and EP0675A1401 (initiators with protected hydroxyl group), US0520808A801 (Thio-A204A020), and in EP05289A901 (A205A0904 and EP05904A0904 as secondary initiators of polymerization.

The carboxy group as a highly polar, bi-toothed ligand can interact particularly well with the surface of the silica filler in the rubber mixture.

EP1000971A1,EP1050545A1,WO2009034001A1. The introduction of carboxy groups at the ends of the chains of service rubbers is also described, for example in US3242129 or US4465809 by translating the anionic polymer chains with CO_{2 and}- I 'm not .

In particular, silanes and cyclosiloxanes with a total of at least two silicon halogen and/or alkoxy and/or aryloxys substituents are well suited for end-group functionalization of servicing rubbers, as one of the said substituents at the Si atom can be easily replaced by an anionic servicing polymer chain end in a rapid substitution reaction and the other of the said substituents is available to Si as a functional group which, if necessary after hydrolysis, can interact with the tyre tread mixture filler.

WO2012/065908A1 describes 1-Oxa-2-silicacycloalkanes as functionalization reagents for introducing hydroxy end groups to dienopolymers. These 1-Oxa-2-silicacycloalkanes do not have the disadvantages of the silanes described in the previous paragraph, such as reaction of multiple anionic polymer chains per silane molecule, cleavage of disruptive components and coupling by formation of Si-O-Si bonds during processing and storage.

All functional polymers known from the state of the art can be used for the rubber composition of the invention.

The functional group is preferably hydroxyl and/or carboxyl, siloxy groups, and in one embodiment the functional group is hydroxyl and/or carboxyl and/or siloxy groups.

Preferably, the butadiene-styrol copolymer functionalised by the end-group for the rubber composition of the invention has Mooney viscosities (ML 1+4 at 100°C) of 10 to 200, preferably 30 to 150 Mooney units and medium molar weights (numerical means, M_nThe maximum concentration of the active substance in the foodstuff is 10 to 2 million g/mol, preferably 100 to 1 million g/mol.

For the vulcanizable rubber composition of the invention, the butadiene-styrene copolymer functionalised by the end-group preferably has glass transition temperatures of -110°C to +20°C, preferably -110°C to 0°C.

Polybutadiene is used as an important component of rubber compounds in the tyre industry, with the aim of improving the final properties, such as reducing rolling resistance and abrasion. Another field of application is golf ball cores or shoe soles, with a high bounce elasticity in particular. Polybutadiene with a high percentage of cis-1,4-units has long been produced on a large technical scale and used in the manufacture of tyres and other rubber products and for the modification of polystyrene impact.

To obtain high percentages of cis-1,4-units, catalysts based on rare earth compounds are currently used almost exclusively, as described in EP-A 1 0 011 184 and EP-A 1 0 007 027.

It is known from the state of the art that neodymium catalyzed polybutadiene in particular in the high cis polybutadiene group has particularly advantageous properties in terms of rolling resistance, abrasion and recoil elasticity.

The technical use of a neodymium catalyst is, for example, a Ziegler/Natta system, which is formed from several catalyst components. In the process of catalyst formation, usually different catalyst centers are formed, which can be detected in the polymer by a minimum bimodal mole mass distribution. In the Ziegler/Natta catalyst system, the three known catalyst components, usually consisting of a neodymium source, a chloride source and an aluminium organic compound, are mixed in various ways under certain temperature conditions, with or without aging, and the catalyst system is prepared for polymerization.

Several manufacturing processes for Ziegler/Natta catalytic conversion systems are known from the state of the art, which are used to produce polybutadiene.

For example, EP 0 127 236 describes a process in which the catalyst is produced by mixing neodymoxides, neodymal alcohols and carboxylates with organometallic halides and an organic compound at a temperature of 20°C to 25°C. It is also possible to mix these four components at 50°C to 80°C. In this variant the mixture is cooled to 20°C to 25°C and then DIBAH is added.

EP 1 176 157 B1 describes a process for the production of polybutadiene with a reduced viscosity/Mooney viscosity ratio, where the catalyst is made by preforming the catalyst, first mixing the neodymium versate with DIBAH and isoprene at 50°C, then cooling the mixture to 5°C, then adding ethyl aluminium eschloride (EASC). The aging process can take from several minutes to several days at a temperature between 10°C and -80°C. During the polymerisation, compounds such as ketones are added to increase the degree of branching of the polymer and thus also the polymer maintains a close ratio of solvent to Mooney. The Mooney is obtained by freezing only about 2 copies of the molecule.

The number of chain ends in the polymer is responsible for the energy dissipation. The higher the number of free chain ends, the higher the energy dissipation by the polymer. However, the lower the energy dissipation of the polymer, the lower the rolling resistance, and the better the rebound elasticity of the polymer. Accordingly, the end properties of a linear polymer with only 2 chain ends per molecule are always better than those of a branched polymer at the same molecule mass.

Preferably, Ziegler-Natta catalysts based on rare earth compounds such as cer, lanthanum, praseodymium, gadolinium or neodymium compounds soluble in hydrocarbons, and in particular the corresponding salts of rare earth metals used as Ziegler-Natta catalysts, such as neodymium phosphonates, neodymium carboxylates, in particular neodymium neodecanoate, neodymoctanoate, neodymium naphthenate, neodymium-2,2-diethyl hexanoate or neodymium-2,2-diethyl heptanoate, and the corresponding salts of lanthanum or praseodymium. Furthermore, the Ziegler-Natta catalysts based on metallocyanates are also described in EP 107139A, EP 107136A and EP 107136A.

Commercially produced polymers are known to have a statistical mole mass distribution, with the width of the mole mass distribution being affected by catalyst manufacturing.

Err1:Expecting ',' delimiter: line 1 column 240 (char 239)

It is further known that low cold-flow polydienes can be produced by treating the diene polymers after polymerisation with disulphur dichloride, sulphur dichloride, thionyl chloride, disulphur dibromide or thionyl bromide (DE-AS 12 60 794).

DE 44 36 059 A1 also describes a method for the jump-start increase in the molecular weight of Nd-catalyzed service rubbers, reducing the polymer's specific odor by a relaxation step after polymerisation to remove all low-boiling components from the reaction mixture.

Component b) is as follows:

Err1:Expecting ',' delimiter: line 1 column 381 (char 380)

This modification is typically achieved by transposition with sulphur chlorides.

Err1:Expecting ',' delimiter: line 1 column 59 (char 58)_{2 and}Cl_{2 and}Err1:Expecting ',' delimiter: line 1 column 304 (char 303)

For the purposes of clarification, the following definitions shall apply: Other

Ausgangsmooney-Viskosität:	Mooney-Viskosität (ML 1+4 100°C) nach der Polymerisation des Polymers.
Endmooney-Viskosität:	Mooney-Viskosität (ML 1+4 100°C) nach der Modifizierung bzw. Mooney-Sprung oder Sprung-Reaktion des Polymers (Sprung-Polymer).
Sprung-Polymer:	Polybutadien nach der Modifizierung, nach dem Mooney-Sprung oder nach der Sprung-Reaktion

Other Preferably, the modified polybutadiene is polymerized by solution polymerization in the presence of at least one inert organic solvent and at least one catalyst based on neodymium compounds in a temperature range of - 20 to 150 °C, polymerization is stopped by the addition of protonic compounds and the polymerisate is modified by sulphur chlorides.

Preferably, the sulphur chlorides are treated with a carbonic acid, fatty acid and/or fatty acid ester before addition.

The preferred sulphur chlorides are disulphur dichloride, sulphur chloride, sulphur bromide, sulphur dichloride, thionyl chloride, disulphur dibromide and/or thionyl bromide.

In particular, a modified polybutadiene (ML 1+4 at 100 °C) is preferred as component (b) in the vulcanizable rubber compound, the Mooney viscosity (ML 1+4 at 100 °C) of which has been increased by at least 50% in the previous modification reaction by conversion of the polybutadiene with sulphur chlorides, relative to the Mooney viscosity (ML 1+4 at 100 °C) of the polybutadiene before the addition of the sulphur chlorides.

Preferably, the modified polybutadiene after polymerisation has a Mooney viscosity (ML 1+4 at 100 °C) (starting Mooney viscosity) of at least 20 MU, preferably 20-25 MU, preferably at least 40 MU and after addition of sulphur chlorides a Mooney viscosity (ML 1+4 at 100 °C) (endmooney viscosity) of at least 30 MU, preferably 40-50 MU, preferably 60-80 MU, with a gel content of less than 1% by weight.

Preferably, high molecular Neodymium Catalyzed Polybutadiene (NdBR) with a cis-1,4-unit content of > 95% by weight and a 1,2-vinyl content of < 1% by weight is used for the inventive vulcanizable rubber composition, with NdBRs modified to increase their Mooney viscosity (ML 1+4 at 100 °C) after polymerisation.

Preferably, the NdBR is modified after polymerisation with sulphur chlorides.

A preferred embodiment of the vulcanizable rubber composition of the invention is: (a) 50 to 90 parts, preferably 60 to 70 parts, of at least one functionalised solution butadiene styrene copolymer (SSBR) (oil free) with a glass transition temperature (Tg) in the range of -110°C to +20°C relative to the oil free SSBR; (b) 10 to 50 parts, preferably 20 to 40 parts, of at least one modified neodymium catalyzed polybutadiene (NdBR) with a mooney viscosity (ML 1+4 at 100 °C) of at least 30 MU; (c) 50 to 120 parts, preferably 60 to 100 parts, of at least one silica acid; (d) 2 to 25 parts, preferably 5 to 10 parts, of at least one other filler; (e) at least 1 to 5 parts, preferably 1 to 4 parts, of a pre-vulcanized liquid; (f) at least 2 to 5 parts, preferably 2 to 5 parts, of a pre-vulcanized liquid; (g) at least 10 to 5 parts, preferably 50 to 5 parts, of a pre-vulcanized liquid; (i) at least 2 to 5 parts, preferably 5 to 10 parts, of a pre-vulcanized liquid; (i) at least 2 to 5 parts, pre-vulcanized liquid, pre-conditioned liquid, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, pre-conditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned, preconditioned where the weight of the components (c) to (g) is expressed as 100 parts by weight of total rubber, i.e. the sum of components (a) and (b).

The glass transition temperatures of the rubber used as a component (a) are determined by means of DSC (Differential Scanning Calorimetry) in accordance with DIN EN ISO 11357-1 and DIN EN 61006. The temperature calibration is carried out by means of the initial temperatures of the solid-liquid transition (deviations from the initial baseline and the rising melting curve) of indium (156.6°C) and lead (328°C). At the beginning of the first preheating cycle, the sample is cooled with liquid nitrogen at a cooling rate of 320 K/min to -130 °C. The subsequent heating is carried out by rinsing with liquid nitrogen at a heating point of 20 K/min to a temperature of 150 °C. The liquid nitrogen is then evaluated at a temperature of 20 °C and the average temperature is obtained by heating the glass at a temperature of -130 °C. The sample is then evaluated at a temperature of 20 K/min to -130 °C. The average temperature is obtained by heating the glass and the average temperature is obtained by taking the sample to a temperature of 20 K/min.

The oil must be removed from the rubber by means of a method called exhaustive extraction with methanol in a Soxhlet extractor, whereby the adhesive acetone is removed under vacuum until the weight constant before the glass transition temperature is determined. Alternatively, the oil can also be removed by enveloping a toluene rubber solution with methanol. For this purpose, the oil-coated rubber is cut and dissolved in toluene tube at room temperature (1 rubber solution in 50 g of Tpresol).

Component c)

Err1:Expecting ',' delimiter: line 1 column 228 (char 227)_{2 and}(Al) or aluminium oxide (Al)_{2 and}O₃) or mixtures thereof.

Err1:Expecting ',' delimiter: line 1 column 65 (char 64)^{2 and}/g, preferably from 20 to 400 m^{2 and}Err1:Expecting ',' delimiter: line 1 column 566 (char 565)

Aluminium oxide can also be used, for example as a highly dispersible aluminium oxide as described in EP-A-0 810 258.Examples include AI25 or CR125 (Baikowski), APA-1OORDX (Condea), Aluminium oxide C (Degussa) and ACP-GO 15 (Sumitomo Chemicals).

The light reinforcing filler can be in the form of powders, micropereles, granules or balls. In a preferred embodiment, silica and/or aluminium oxides are used.

The total content of hydroxyl group-containing oxidizing filler is usually in the range of 50 to 120 parts per w, preferably in the range of 60 to 100 parts per w, and particularly preferably 25 to 90 parts per w per 100 parts per w of total oil-free rubber (sum of (a) and (b)).

It has also been shown to be appropriate to use at least one light filler (component c) together with at least one polysulphide alcoholsylane, so-called clutch agents for dispersing and incorporating the strengthening filler into the elastomer matrix, which, as the expert knows, have two types of functional groups, the alcoholsylyl group binding to the light filler and the sulphide group binding to the elastomer.

As polysulphide-containing alkoxysilans, those of formulae I and II are particularly suitable, without the following definitions being restrictive; those of formula I are those which have a silyl group substituted on both sides of the central sulphur, whereas in formula II this is only the case on one side.

Err1:Expecting ',' delimiter: line 1 column 306 (char 305)^{1 and}The following are the main features of the new system:_{1 and}-C₁₈Alkyl group, one C₅-C₁₈Cycloalkyl group or C₆-C₁₈Aryl group and R^{2 and}The following are the main features of the new system:_{1 and}-C₁₈Alkoxy group, a C₅-C₁₈Cycloalcoxy group or C₆-C₁₈represent the aryloxy group, and R³Hydrogen, straight-chain or branched-chain alkyl, where the alkyl chain may optionally be interrupted by one or more, preferably up to five heteroatoms, in particular oxygen, sulphur or N (H), aryl, preferably C₆-C₂₀- means an aryl and/or a residue with subsequent structures -CN Other Other In which R⁴means an aliphatic, hetero-aliphatic, cyclo-aliphatic, aromatic or hetero-aromatic residue with 1 to 20, preferably 1 to 10, carbon atoms and optionally 1 to 3 hetero-atoms, preferably oxygen, nitrogen or sulphur.

Err1:Expecting ',' delimiter: line 1 column 343 (char 342)

In polysulphide alcohols of general formulae (I) and (II), the substituted or unsubstituted groups A are the same or different and preferably represent a two-value aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon group which is saturated or monounsaturated or monounsaturated and has 1 to 20, preferably 1 to 18 carbon atoms and optionally 1 to 3 heteroatoms, in particular oxygen, sulphur or nitrogen._{1 and}-C₁₈Alkyl groups or C₆-C₁₂Aryl groups are suitable, particularly preferred_{1 and}-C₁₀Alkyl groups, in particular C_{2 and}-C₄Alkyl groups and especially preferably propylene.

In the polysulphide alcohols of the general formulae (I) and (II), R is^{1 and}equal or different and preferably signify C_{1 and}-C₆Alkyl, cyclohexyl or phenyl, preferably C_{1 and}-C₄Alkyl and in particular methyl and/or ethyl.

In the polysulphide alcohols of the general formulae (I) and (II), R is^{2 and}equal or different and preferably signify C_{1 and}-C₁₀- Alkoxy, especially preferably C_{1 and}-C₈-Alkoxy, especially methoxy and/or ethoxy, C₅-C₈Cycloalcoxy, preferably cyclohexyloxy, or C₆-C₁₄Aryloxy, especially preferably phenoxy.

Err1:Expecting ',' delimiter: line 1 column 61 (char 60)

The polysulphide-containing alkoxylan is preferably a polysulfide, in particular a disulfide or tetrasulfide of Bis ((C_{1 and}-C₄(trialcoxysilylpropyl, preferably bis (C)_{1 and}-C₄The disulphide of bis (triethoxysilylpropyl) or TESPD of the formula [C]_{2 and}H₅O)₃Other_{2 and}(b)₃S]_{2 and}is commercially available, for example, from Evonik Degussa under the names Si266 or Si75 (in the latter case in the form of a mixture of disulfide and polysulfide) or from Witco under the name Silquest A 1589._{2 and}H₅O)₃Other_{2 and}(b)₃S_{2 and}[ Other ]_{2 and}It is available, for example, from Evonik Degussa under the name SI 69 (or X-50S with 50% by weight of Russ as carrier) or from Witco under the name Silquest A 1289 (both commercial polysulfide mixtures with a mean value of x close to 4).

The polysulphide alkoxysilans are used in the rubber mixtures according to the invention with 6 to 12% by weight, preferably 1 to 10% by weight, based on 100% by weight of silica.

Component d:

The vulcanizable composition of the invention contains at least one other filler as component (d). For example, soot, barium sulphate, titanium dioxide, zinc oxide, calcium oxide, calcium carbonate, magnesium oxide, aluminium oxide, iron oxide, aluminium hydroxide, magnesium hydroxide, aluminium silicates, diatomaceous earths, talc, kaolin, bentonite, carbon nanotubes, teflon (preferably in powder form) or silicates may be used as fillers. Soot is preferred.

The Russian authorities have proven that HAF, ISAF and SAF are the most commonly used soot in pneumatic tyres, and in particular in the tread of pneumatic tyres.

However, if soot is used as a further filler, the proportion of silica (component c) is more than 50% by weight, preferably more than 75% by weight, in relation to the total amount of fillers used in the form of components c) and d). The proportion of soot is then less than 50% by weight and preferably less than 40% by weight. In a preferred embodiment, soot is added to the rubber compounds of the invention in quantities of 2 to 25 parts by weight, preferably 5 to 10 parts by weight, in relation to 100 parts by weight of oil-free total rubber.

Component (e) is as follows:

The invention provides that at least one vulcanizing agent is used as component (e). Several vulcanizing agents may also be used.

The rubber compound of the invention is suitable for interconnection with either elemental sulphur or a sulphur donor.

Soluble sulphur is the only stable form at normal temperatures, yellow cycloacetate sulphur (S).₈The solution is obtained by the reaction of a mixture of the two hydrocarbons, which are the hydrocarbons of the hydrocarbon, which are the hydrocarbons of the hydrocarbon, which are the hydrocarbons of the hydrocarbon._{2 and}Err1:Expecting ',' delimiter: line 1 column 63 (char 62)

Insoluble sulphur is a sulphur modification which is not prone to so-called bloom on the surface of rubber compounds.

Err1:Expecting ',' delimiter: line 1 column 188 (char 187)

Sulphur and/or sulphur donors are used in the rubber mixture according to the invention in a quantity in the range of 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, in relation to 100 parts by weight of total oil-free rubber.

The rubber mixture of the invention may also contain one or more vulcanization accelerators suitable for sulphur vulcanization.

Err1:Expecting ',' delimiter: line 1 column 106 (char 105)

For the purpose of the present invention, such vulcanization accelerators may be selected from the group of xanthogenates, diithiocarbamates, tetramethylthiuramdisulfides, thiurame, thiazole, thio-carbamate derivatives, amines such as tetramine, sulfenimides, piperazine, aminescarbamate, sulfenamides, bisphenol and triazine derivatives, and polythiophosphorus compounds of general formula (III) or (IV). Other In which R⁵, R⁶, R⁷and R⁸are equal or different and for aliphatic, hetero-aliphatic, aromatic or hetero-aromatic residues of 1 to 24, preferably 1 to 18 carbon atoms, and optionally 1 to 4 hetero-atoms, in particular N, S or O,t represents an integer from 1 to 8, preferably 3 to 6,preferably 1 to 3, preferably 1 to 2, andM^z+means a metal cation with charge z+, where z+ is 1 to 3, preferably 1 and 2, or a cation of formula N(R⁹(b)₄ ⁺means where R⁹are equal or different and hydrogen and/or the meanings R⁵The Commission has already made a number of proposals.

The compounds of general formula (III) are phosphoryl polysulfides and the compounds of general formula (IV) are dithiophosphates.

The following metal cations are given for M^z+In the case of the following, the preferred are: Na, K, Zn and Cu.^z+for NH₄ ⁺- I 'm not .

The following metal diethiophosphates are of particular interest: Other In which equal to 2 is R⁵and R⁶are the same or different and contain hydrogen or a straight or branched, substituted or unsubstituted alkyl group or cycloalkyl group with 1 to 12 carbon atoms, preferably a C_{2 and}-C₁₂Alkyl group or a C₅-C₁₂Cycloalkyl group and in particular ethyl, propyl, isopropyl, butyl, isobutyl, cyclohexyl, ethylhexyl or dodecyl.

Such compounds of general formula (III) or (IV) may also be used optionally in a carrier or polymer-bound form.

The following substances are suitable accelerators of vulcanization: benzodiazyl-2-cyclohexyl sulfenamide (CBS), benzodiazyl-2-dihydydihydydihydydihydydihydydihydydihydydihydydihydydihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddihyddi Other with t = 2 to 4 (Rhenocure® SDT/S bound to 30% by weight of high-acid silica from Rhein Chemie Rheinau GmbH) and zinc dithiophosphate, such as Rhenocure® ZDT/G bound to 30% by weight of high-acid silica and 20% by weight of polymer binder from Rhein Chemie Rheinau GmbH with the formula The Commission is

The vulcanization accelerators are preferably used in a quantity in the range of 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of oil-free total rubber.

The mixture of the invention may also contain zinc oxide as an activator for sulphur vulcanization. The selection of an appropriate quantity is possible without great effort to the professional.

Component f:

(f) Process oils familiar to the professional and commonly used are used as a component. Preferably a naphthenic oil with a gas transition temperature (Tg) between -80°C and -40°C, a quantity less than 3% by weight extractable with DMSO according to the IP 346 method, of which the sum of the polycyclic aromatics < 10 ppm and the quantity of alpha-benzopyrene < 1 ppm, measured according to the Grimm test, is the analytical value. The Grimm test according to the method of Prof. Grimmer, Hamburg-Ahrensburg, is published in Fresenius, Bandytische Chemie, 1983, 314, pp. 29-36.

Components g)

The rubber composition of the invention may contain one or more additional rubber additives.

For example, stearic acid (octadecansic acid) may be present, which is known to the professional for its wide range of effects in rubber technology, and one of its effects is to improve the dispersion of zinc oxide and the accelerator of vulcanization.

Zinc oxide can also be present in the composition of the invention, and has been shown to be present in amounts of 0.5 to 15 parts by weight, preferably 1 to 7.5 parts by weight, and particularly 1 to 5 parts by weight, per 100 parts by weight of total oil-free rubber.

Stearic acid is preferably used in the composition according to the invention in a quantity of 0.1 to 7, preferably 0.25 to 7 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of oil-free total rubber.

Alternatively or in addition to the combination of zinc oxide and stearic acid, zinc tar can be used, in which case a quantity of 0.25 to 5 parts by weight, preferably 1 to 3 parts by weight, is usually used, each per 100 parts by weight of total oil-free rubber.

Err1:Expecting ',' delimiter: line 1 column 747 (char 746)

Err1:Expecting ',' delimiter: line 1 column 595 (char 594)

Err1:Expecting ',' delimiter: line 1 column 584 (char 583)

In addition, anti-aging agents may also be used, for example in the form of anti-aging colouring agents with fatigue and ozone protection, e.g. N-Isopropyl-N'-phenyl-p-phenylenediamine (IPPD); N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine (7PPD), NN'-bis-(1,4-dimethylpentyl) -p-phenylenediamine (77PD), etc., anti-aging colouring agents with fatigue protection but without ozone protection, e.g. Polyphenyl-α-phenyl phenylenediamine (PAN), anti-aging colouring agents with no special effects, such as anti-aging agents (Oxyl, Hydroxycycline, Oxycycline, Hydroxybutyl, Oxycycline, Oxycycline, Oxycycline, Oxygen-Diphenyl and Oxycycline), non-protective anti-aging agents (Oxycycline, Oxycycline, Oxygen-Diphenyl and Oxygen-Diphenyl); and non-protective anti-aging agents (Oxycycline, Oxycycline, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxygen, Oxy

Furthermore, chewing chemicals may be added to the rubber compounds of the invention, preferably selected from the group consisting of thiophenols, thiophenol zinc salts, substituted aromatic disulfides, derivatives of thiocarbon acids, hydrazine derivatives, nitrous compounds and metal complexes, particularly preferably iron hemiporphyralgin, iron phthalacyanin, iron acetonylac and its Zn salt. The chewing chemicals are used in particular to chew the natural rubber used in the mixture, with the chewing of the natural rubber being preferably carried out in a separate step-by-step process of preparation of the mixture.

The rubber additives used as components (n) (g) are used in standard quantities, depending on the intended use, for example, the standard quantities for individual rubber additives are between 0.1 and 50 phr, excluding oil used as a stretcher from rubbers in rubber compounds.

Err1:Expecting ',' delimiter: line 1 column 438 (char 437)

Suitable aggregates for the manufacture of the rubber compounds of the invention are known in themselves and include, for example, rollers, internal mixers or mixing extruders.

When using a two-stage internal blender or a three- or multi-stage blender, the first and/or second and subsequent blending steps, preferably the first and second blending steps, shall be worked at temperatures between 60°C and 180°C, preferably 120°C and 175°C, and preferably 125°C and 170°C, with mixing times in the range of 1 to 15 minutes at these temperatures, and selected so that no vulcanization (anvulcanization or scorch) starts already.

The temperature in the final mixing stage is 20 to 120 °C, preferably 30 to 110 °C.

The mixer is normally set up in a temperature range of 20 to 180 °C, preferably 50 to 170 °C, or on a roller at less than 110 °C. The choice of a suitable temperature can be made by the professional according to his expertise, it being noted that the silica is not silicalized and the silica is not scorched.

Vulcanization of the compositions of the invention is usually carried out at a temperature in the range of 100 to 250°C, preferably 130 to 180°C, either at normal pressure (1 bar) or optionally at a pressure of up to 200 bar.

The rubber compounds of the invention are suitable for the manufacture of vulcanized rubber and for the manufacture of pneumatic tyres, winter tyres, tyre components, in particular tyre treads, subtreads, carcasses, sidewalls, reinforced sidewalls for emergency tyres and apex compounds, and for the manufacture of technical rubber articles, preferably cushioning elements, roller coatings, tread liners, belts, spindle heads, seals, golf ball cores and shoe soles.

The following examples illustrate the rubber compositions of the invention:

Examples: I. Rubber

The rubber compounds of the invention are made of various polybutadienes and SSBRs, all of which are products of Lanxess Deutschland GmbH.

Table 1 shows the polybutadienes used, with Buna PBR 4065 (trade name Buna® Nd 24 EZ) and Buna PBR 4076 (trade name Buna® 22 EZ) being modified polybutadienes. Other Eingesetzte Polybutadiene

Buna CB 1203	CoBR	nein	43	0,41	145	3,0	145	395	2,7
Buna CB 24	NdBR	nein	43	0,68	230	1,9	205	420	2,0
Buna CB 22	NdBR	nein	63	0,74	350	1,8	238	466	2,0
Buna PBR 4065	NdBR	ja	44	0,45	150	2,9	171	375	2,2
Buna PBR 4076	NdBR	ja	63	0,45	280	2,3	212	462	2,2

Eingesetzte Polybutadiene

Table 2 shows the SSBRs used, with PBR 4078 and PBR 4070 being end-group functionalised SSBRs. PBR 4088 is a functionalised SSBR in the polymer chain. VSL 5025-2 is not functionalised. Furthermore, Table 2 summarises the important properties. Other Eingesetzte SSBR

VSL 5025-2	nein	nein	51	25	48	27	-29
VSL 5025-0 HM	nein	nein	50	25	65	0	-22
PBR 4088	ja	nein	40	26	54	27	-31
PBR 4078	nein	ja	49	23	65	20	-27
PBR 4070	nein	ja	32	34	81	27	-29

Eingesetzte SSBR

1: MV bedeutet die Mooney Viskosität ML1+4 @100°C in Mooney Units [MU].

The Commission has not yet adopted a decision.

The substances listed in Table 3 were used in the mixing studies: Other

VULCAN J/N375 als Ruß	Cabot Corporation
TDAE oil, Öl	Hansen und Rosenthal KG
ZINKWEISS ROTSIEGEL als Zinkoxid	Grillo Zinkoxid GmbH
EDENOR C 18 98-100 als Stearinsäure	Caldic Deutschland GmbH
VULKANOX 4020/LG als Stabilisator	Lanxess Deutschland GmbH
VULKANOX HS/LG als Stabilisator	Lanxess Deutschland GmbH
VULKACIT® NZ/EGC als Beschleuniger	Lanxess Deutschland GmbH
MAHLSCHWEFEL 90/95 CHANCEL, Schwefel	Solvay Barium Strontium
ANTILUX 654, Wachs	RheinChemie Rheinau GmbH
Si 69 , Silan	Evonic Degussa GmbH
RHENOGRAN DPG-(80), Diphenylguanidin	RheinChemie Rheinau GmbH
VULKALENT E/C, Sulfonamid	Lanxess Deutschland GmbH
ULTRASIL 7000 GR, Silica	Evonic Degussa GmbH

Table 4 lists the formulae of the rubber compounds of the invention.

Err1:Expecting ',' delimiter: line 1 column 47 (char 46)

SSBR (Berechnung ohne Öl)	70
Hoch-cis-Nd BR	30
Silica (ULTRASIL 7000 GR)	90
Si 69, Silan	7,2
VULCAN J/N375 als Ruß	7
TDAE oil, Öl	36,3
AFLUX 37, GE 1837 als Verarbeitungshilfsmittel	3
ZINKWEISS ROTSIEGEL als Zinkoxid	3
EDENOR C 18 98-100 als Stearinsäure	1
VULKACIT® NZ/EGC als Beschleuniger	1,6
VULKANOX 4020/LG als Stabilisator	2
VULKANOX HS/LG als Stabilisator	2
ANTILUX 654 , Wachs	2
MAHLSCHWEFEL 90/95 CHANCEL, Schwefel	1,6
RHENOGRAN DPG-(80), Diphenylguanidin	2,75
VULKALENT E/C, Sulfonamid	0,2

Manufacture of vulcanized products

For the manufacture of the vulcanizates, the components were mixed and treated as follows:

The first stage of mixing: 1.5 litres of interlocking knot, 60 rpm, starting temperature 60°C

0 sec -	Zugabe aller Polymere
30 sec -	Zugabe 2/3 Silica, 2/3 Silan, Russ, Öl, Stearinsäure, Wachse und Stabilisatoren
90 sec -	Zugabe restliches Silica und Silan
150 sec -	Zugabe Zinkoxid
210 sec -	Fegen
240 sec -	Erreichen der Temperatur von 150°C und Halten für 3 Minuten
420 sec -	Auswurf

Roll out to the skin on the cold roll, allow to cool and store for at least 8 hours before stage 2

The second stage of mixing: 1.5 litres of interlocking knot, 60 rpm, starting temperature 60°C

0 sec -	Zugabe der gesamten Mischung der ersten Mischstufe
120 sec -	Erreichen der Temperatur von 150°C und Halten von 150°C für 3 Minuten
300 c -	Auswurf

The following shall be added to the list of products:

Mix all remaining mesh chemicals on a roll, keeping the temperature below 110°C.

The following is a list of the main characteristics of the volcanic activity:

The vulcanizing properties of the mixtures produced in accordance with paragraph III are shown in Table 5. Other Vulkanisateigenschaften der Mischungen

	1	2	3	4	5	6	7	8	9	10
SSBR Typ	VSL 5025-2	VSL 5025-2	PBR 4088	PBR 4088	PBR 4070	PBR 4070	PBR 4078	PBR 4078	VSL 5025-0HM	VSL 5025-0HM
NdBR Typ	CB 24	PBR 4065	CB 24	PBR 4065	CB 24	PBR 4065	CB 24	PBR 4065	CB 22	PBR 4076
Shore A Härte 23°C	63	62	60	60	65	65	61	63	60	60
Shore A Härte 60°C	60	59	57	55			57	57	57	57
Rebound 23°C (%)	28	28	38	36	28	28	33	32	33	31
Rebound 60°C (%)	52	53	61	60	54	54	58	56	51	53
G*(15%) @ 60°C (MPa)	1,07	1,09	0,94	0,94	1,27	1,24	1,17	1,05	1,11	1,06
tan δ (max) 60°C	0,166	0,17	0,131	0,136	0,171	0,172	0,157	0,15	0,172	0,172
Eplexor tan δ 60°C	0,105	0,111	0,079	0,087	0,096	0,095	0,092	0,096	0,116	0,104
12,8	11,8	14,6	13,5	13,7	13,8	11,8	10,6	11,4	11,8
Mooney Viskosität ML1+4@100°C	66	58	68	64	87	81	75	69	73	66

The measurement methods used to determine the properties given in Table 5 are given below.

It appears that the dynamic properties of the vulcanizates have remained approximately the same when using PBR 4065 and PBR 4076 respectively and vulcanizates with CB 24 and CB 22 respectively, except that the Mooney viscosity is lower in the rubber compounds with modified polybutadiene.

The stiffness index (SI) and rolling resistance index (RRI) for examples 1-10 are given in Table 6 and are also illustrated in Figure 2. Other 6: Steifigkeitsindex (SI) und Rollwiderstandsindex (RRI)

1	VSL 5025-2/CB24	100	100
2	VSL 5025-2/PBR 4065	92	94
3	PBR 4088 / CB 24	95	198
4	PBR 4088 / PBR 4065	88	170
5	PBR 4070 / CB24	131	110
6	PBR 4070 / PBR 4065	129	111
7	PBR 4078 / CB 24	98	135
8	PBR 4078 / PBR 4065	81	130
9	VSL 5025-0HM / CB 22	88	86
10	VSL 5025-0HM / PBR 4076	87	99

6: Steifigkeitsindex (SI) und Rollwiderstandsindex (RRI)

For the above measurements, mixture 1 consisting of VSL 5025-2 and CB 24 is normalised to 100 as neither the SSBR nor the polybutadiene is functionalised or modified.

It can be seen from Table 6 and Figure 2 that the vulcanizates with modified polybutadiene 2, 4, 6, 8, 10 have always lower stiffness indices and lower rolling resistance indices than the vulcanizates without modified polybutadiene 1, 3, 5, 7, 9. Thus, the vulcanizates according to the invention not only have an improved processing behaviour (stiffness index) but also an improved rolling resistance.

V. Methods/Din standards used in the volcanic test

The volcanic products were characterised by the following standards, as shown in Table 5: Other

(für Kautschukzusammensetzung): Mooneyviskosität und Mooney-Stress-Relaxation

Shore A-Härte bei 60°C

Rückprallelastizität bei 60°C

Abrieb

Determination of the dynamic properties (temperature dependence of the storage module E' in the temperature range -60°C to 0°C and tan δ at 60°C):

For the determination of the dynamic properties (temperature dependence of the storage module E' in the temperature range -60°C to 0°C and tan δ at 60°C) an Eplexor apparatus (Eplexor 500 N) from Gabo-Testanlagen GmbH, Ahlden, Germany was used.

The method obtained the following values, which are given in accordance with ASTM 5992-96: Other

Speichermodul bei 60°C

Speichermodul bei 23°C

Speichermodul bei 0°C

Other and Other

Verlustfaktor (E"/E') bei 60°C

Verlustfaktor (E"/E') bei 23°C

Verlustfaktor (E"/E') bei 0°C.

The lower the E' the better the grip.

The lower the tan δ (60°C), the lower the rolling resistance of the tyre.

DIN 53513-1990: Elastic properties - The elastic properties were determined using the MTS elastomer test system (MTS Flex Test) of MTS, measured according to DIN 53513-1990 on cylinder samples (2 samples of 20 x 6 mm each) compressed to a total of 2 mm at a temperature of 60°C and a measuring frequency of 1 Hz in the range of 0.1 to 40% of the amplitude range.

The method obtained the following values, which are given in accordance with ASTM 5992-96: Other

dynamischer Modul bei 0,5% Amplitudensweep

dynamischer Modul bei 15% Amplitudensweep

Differenz des dynamischen Moduls bei 0,5% zu 15 % Amplitudensweep

Err1:Expecting ',' delimiter: line 1 column 97 (char 96)

G* (0.5%) - (15%) gives an index of the Payne effect of the mixture, where a low value indicates good filler distribution and thus low rolling resistance.

The lower the tan δ (max), the lower the rolling resistance of the tyre.

VI. Surface characteristics of the extruded product

In addition, various extrudates were produced by means of an extruder (Brabender Plasticorders) at 90°C, 100°C and 120°C at a speed of 50 rpm (rotation per minute) according to ASTM D 2230.

Figure 3 shows the Garvey-Di profiles of the extrudates from examples 1-4 (numbered according to Table 6 of the examples) produced at 100°C. The profiles of the vulcanized based on modified NdBR (PBR 4065) show a smoother structure than the comparison extrudate based on unmodified NdBR (CB 24), indicating improved processing performance.

Figure 4 shows the Garvey-Di profiles of the extrudates from examples 1-4 (numbering according to Table 6 of the examples) produced at 120°C. Here again, the profiles of the volcanized products based on modified NdBR (PBR 4065) show a smoother surface structure than the comparison extrudates based on unmodified NdBR (CB24).

Figure 5 shows various Garvey-Di profiles of extrudates based on volcanized 1, 2, 5 and 6 (numbering according to Table 6 of the examples) produced at 90°C.

Again, it can be seen that the vulcanizates based on the component b) of the invention (PBR 4065) have a smoother structure than the vulcanizates based on a non-component b) of the invention (Buna CB 24).

Figure 6 shows various Garvey-Di profiles of extrudates based on vulcanizates 7 and 8 (numbering according to Table 6 of the examples) produced at 100°C and 120°C respectively. The smoother structure of the Garvey profiles also shows an improvement in machinability by using the component of the invention (b) in the form of modified NdBR PBR 4065 (instead of non-invention Buna CB 24) in combination with the component of the invention (a) in the form of end-group functionalised SSBR PBR 4078.

Claims (18)

1. Vulcanizable rubber composition comprising at least the following components:

   a) at least one functionalized polymer,

   b) at least one modified polybutadiene having a proportion of cis-1,4 units of > 95% by weight and a 1,2-vinyl content of < 1% by weight, the polybutadiene having been modified by means of sulphur chlorides after the polymerization,

   c) at least one silica,

   d) at least one further filler,

   e) at least one vulcanizing agent,

   f) at least one oil and

   g) optionally at least one further rubber additive, where

   the modified polybutadiene has an abrupt increase in the Mooney viscosity (ML 1+4 at 100°C) by at least 50%, based on the Mooney viscosity (ML 1+4 at 100°C) of the polybutadiene prior to addition of the sulphur chlorides.
2. Vulcanizable rubber composition according to Claim 1, characterized in that the functionalized polymer comprises functionalized diene polymers, or diene copolymers obtainable by copolymerization of dienes with vinylaromatic monomers.
3. Vulcanizable rubber composition according to Claim 1, characterized in that the functionalized polymer is a polybutadiene, a polyisoprene, a butadiene-isoprene copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer or a butadiene-isoprene-styrene terpolymer.
4. Vulcanizable rubber composition according to Claim 1, characterized in that the functionalized polymer comprises end group-functionalized butadiene-styrene copolymers prepared by solution polymerization.
5. Vulcanizable rubber composition according to Claim 4, characterized in that the end group-functionalized butadiene-styrene copolymer has Mooney viscosities (ML 1+4 (100°C)) of 10 to 200, preferably 30 to 150 Mooney units.
6. Vulcanizable rubber composition according to Claim 5, characterized in that the end group-functionalized butadiene-styrene copolymer has mean molar masses (number-average, Mn) of 10 000 to 2 000 000 g/mol, preferably of 100 000 to 1 000 000 g/mol.
7. Vulcanizable rubber composition according to Claim 6, characterized in that the end group-functionalized butadiene-styrene copolymer has a glass transition temperatures of -110°C to +20°C, preferably -110°C to 0°C.
8. Vulcanizable rubber composition according to Claim 7, characterized in that the modified polybutadiene is polymerized by solution polymerization in the presence of at least one inert organic solvent and in the presence of at least one catalyst based on neodymium compounds within a temperature range from -20°C to 150°C, the polymerization is stopped by adding protic compounds and the polymer is modified by means of sulphur chlorides.
9. Vulcanizable rubber composition according to Claim 8, characterized in that the sulphur chlorides, prior to addition, are treated with a carboxylic acid, fatty acid and/or fatty acid ester.
10. Vulcanizable rubber composition according to Claim 9, characterized in that the sulphur chlorides are disulphur dichloride, sulphur chloride, sulphur bromide, sulphur dichloride, thionyl chloride, disulphur dibromide and/or thionyl bromide.
11. Vulcanizable rubber composition according to Claim 1, characterized in that the modified polybutadiene after the polymerization has a Mooney viscosity (ML 1+4 at 100°C) (starting Mooney viscosity) of at least 20 MU, preferably 20-25 MU, more preferably at least 40 MU, and after the addition of sulphur chlorides has a Mooney viscosity (ML 1+4 at 100°C) (final Mooney viscosity) of at least 30 MU, preferably 40-50 MU, more preferably 60-80 MU, where the gel content is less than 1% by weight.
12. Vulcanizable rubber composition according to any of the preceding Claims 1-11, comprising

    a) 50 to 90 parts by weight, preferably 60 to 70 parts by weight, of at least one functionalized solution butadiene-styrene copolymer (SSBR) (oil-free) having a glass transition temperature (Tg) between -110°C to +20°C, based on the oil-free SSBR,

    b) 10-50 parts by weight, preferably 20 to 40 parts by weight, of at least one modified neodymium-catalysed polybutadiene (NdBR) having a Mooney viscosity (ML 1+4 at 100°C) of at least 30 MU,

    c) 50-120 parts by weight, preferably 60-100 parts by weight, of at least one silica,

    d) 2-25 parts by weight, preferably 5-10 parts by weight, of at least one further filler,

    e) 1-5 parts by weight, preferably 2-4 parts by weight, of at least one vulcanizing agent,

    f) 5-50 parts by weight, preferably 10-40 parts by weight, of at least one oil,

    g) optionally 1-7 parts by weight, preferably 2-5 parts by weight, of at least one rubber additive,

    where the parts by weight figures for components c)-g) are each based on 100 parts by weight of rubber (sum total of a) and b)).
13. Vulcanizable rubber composition according to Claim 12, characterized in that the further filler is carbon black.
14. Process for producing vulcanizable rubber compositions according to any of Claims 1 to 13, characterized in that components a) to f) and optionally g) are mixed with one another in one or more stages, preferably either by a three-stage mixing operation with two mixing stages in an internal mixer and a final mixing stage on a roller, or by a two-stage mixing operation in which the 1st mixing stage is effected in an internal mixer and the 2nd mixing stage on a roller, or by a two-stage mixing operation in which both mixing stages are effected in an internal mixer, with cooling of the mixture to temperatures of < 120°C, preferably < 110°C, prior to addition of those components which are added on the roller in a three-stage mixing operation.
15. Process for producing vulcanizates, characterized in that vulcanizable rubber compositions according to any of Claims 1 to 14 are subjected to a crosslinking reaction, preferably at a temperature in the range from 100 to 250°C, especially from 130 to 180°C, under a pressure in the range from 1 to 200 bar.
16. Process according to Claim 15, characterized in that the crosslinking takes place in the course of a shaping operation.
17. Vulcanizates obtainable by the process according to any of Claims 14 to 16.
18. Use of vulcanizable rubber composition according to any of Claims 1 to 13 for production of pneumatic tyres, especially winter tyres, tyre components, especially tyre treads, subtreads, carcasses, sidewalls, reinforced sidewalls for runflat tyres and apex mixtures, and for the production of industrial rubber articles, preferably damping elements, roll coverings, conveyor belt coverings, drive belts, spinning cops, seals, golfball cores and shoe soles.