DE102024203747A1 - Sulphur-curable rubber compound, vulcanizate of the rubber compound and vehicle tires - Google Patents

Abstract

The invention relates to a sulfur-crosslinkable rubber mixture, the vulcanizate of the rubber mixture, and a vehicle tire. The rubber mixture contains at least the following components: a) 50 to 100 phr of at least one polyisoprene, b) 0 to 50 phr of at least one butadiene rubber, wherein the butadiene rubber is functionalized for the attachment of silica, c) 20 to 100 phr of at least one high-surface-area silicon dioxide, d) 1 to 30 phr of silanes selected from at least two organosilicon compounds.

Description

The invention relates to a sulfur-crosslinkable rubber mixture, its vulcanizate, and a vehicle tire. Furthermore, the invention relates to the use of the sulfur-crosslinkable rubber mixture.

The rubber composition of the tread largely determines the driving characteristics of a vehicle tire, especially a pneumatic tire. Likewise, the rubber compounds used in belts, hoses, and straps—especially in areas subject to high mechanical stress—are largely responsible for the stability and durability of these rubber products. Therefore, very stringent requirements are placed on these rubber compounds for pneumatic tires, belts, and hoses.

There are conflicting objectives between most of the known tire properties such as wet grip, braking, handling, rolling resistance, winter properties, abrasion and wet braking properties, especially tear properties.

The object of the present invention was to provide a rubber mixture which, in comparison with the prior art, as described for example in the document DE 10 2017 221 232 A1 or in print WO 2023 104 252 A1 published, shows an overall improvement in the property profile comprising rolling resistance behavior, abrasion behavior, in particular abrasion resistance, and wet braking properties.

Surprisingly, the rubber mixture according to the invention, the vulcanizate according to the invention, and the vehicle tire according to the invention achieve an improvement in the conflicting objectives of rolling resistance behavior, abrasion behavior, in particular abrasion resistance, and wet braking behavior, in particular wet grip. In particular, the rolling resistance behavior is improved.

At the same time, the rubber mixture according to the invention has good processability, in particular miscibility and extrudability, so that the vulcanizate according to the invention and the vehicle tire according to the invention are also easy to process.

Thus, with the rubber mixture according to the invention, the vulcanizate according to the invention and the vehicle tire according to the invention, an improvement is also achieved in the conflict of objectives between processability and the aforementioned properties, in particular the rolling resistance behavior, the abrasion behavior and the wet braking behavior.

The invention encompasses all advantageous embodiments, which are reflected, inter alia, in the patent claims. In particular, the invention also encompasses embodiments that result from the combination of different features, for example, components of the rubber mixture, with varying degrees of preference for these features, so that a combination of a first feature designated as "preferred" or described within the scope of an advantageous embodiment with another feature designated, for example, as "particularly preferred" is also encompassed by the invention.

The components of the sulfur-crosslinkable rubber mixture according to the invention are described in more detail below. All information regarding the components of the rubber mixture according to the invention, regardless of the degree of preference given to these features, also applies accordingly to the vulcanizate according to the invention, the vehicle tire according to the invention, and the use according to the invention.

The term phr (parts per hundred parts of rubber by weight) used in this document is the standard quantity used in the rubber industry for compound formulations. The dosage of the parts by weight of the individual substances in this document is based on 100 parts by weight of the total mass of all rubbers present in the compound with a molecular weight Mw of greater than 20,000 g/mol, measured by GPC (gel permeation chromatography) in accordance with ISO 13885-1.

According to the invention, the rubber mixture contains at least one diene rubber from the group consisting of natural polyisoprene (NR) and synthetic polyisoprene (IR).

Diene rubbers are rubbers that are produced by polymerization or copolymerization of dienes and/or cycloalkenes and thus have C=C double bonds either in the main chain or in the side groups.

According to the invention, the rubber mixture further contains at least one diene rubber which is a butadiene rubber (synonyms: BR, BR rubber, polybutadiene).

The butadiene rubber according to the invention is explicitly none of the following dienes rubbers such as butadiene-isoprene rubber or styrene-butadiene rubber.

Other possible diene rubbers which may be present in the mixture according to the invention in smaller amounts are butadiene-isoprene rubber, styrene-butadiene rubber (SBR), in particular solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), styrene-isoprene rubber, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, nitrile rubber, chloroprene rubber, acrylate rubber, fluorine rubber, silicone rubber, polysulfide rubber, epichlorohydrin rubber, styrene-isoprene-butadiene terpolymer, hydrogenated Acrylonitrile butadiene rubber and hydrogenated styrene butadiene rubber.

The mixture preferably does not comprise any liquid rubbers, i.e. in particular no rubbers that are liquid at room temperature and ambient pressure.

In particular, nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber, or ethylene-propylene-diene rubber are used in the production of technical rubber articles, such as belts, straps, and hoses, and/or shoe soles. The preferred blend compositions for these rubbers—specific with regard to fillers, plasticizers, vulcanization systems, and additives—are known to those skilled in the art.

The diene rubber according to the invention comprises 50 to 100 phr of polyisoprene, preferably 55 to 85 phr of polyisoprene, particularly preferably 60 to 80 phr, which is preferably natural polyisoprene (NR).

The diene rubber according to the invention further comprises 0 to 50 phr of butadiene rubber (BR), preferably 10 to 40 phr, particularly preferably 15 to 25 phr of butadiene rubber.

With the combination of 50 to 100, preferably 55 to 85 phr, particularly preferably 60 to 80 phr of polyisoprene, preferably natural polyisoprene (NR), and 0 to 50 phr, preferably 10 to 40 phr, particularly preferably 15 to 25 phr of butadiene rubber (BR), the object underlying the invention is achieved particularly well and the rubber mixture has particularly optimal processability.

Preferably, the proportions of NR and BR add up to approximately 100 phr or exactly 100.00 phr.

In the event that the rubber mixture contains less than 100 phr of NR and BR, at least one further rubber, preferably at least one further diene rubber selected from the above list, is contained, so that the sum of the rubbers contained is, by definition, 100 phr.

The butadiene rubber (polybutadiene, BR) contained in the rubber mixture according to the invention is preferably of the low-cis type. The so-called high-cis and low-cis types are understood to mean polybutadienes with a cis content greater than or equal to 90 wt.% (high-cis type) or polybutadienes with a cis content less than 90 wt.% (low-cis type).

The polybutadienes used can be end-group modified with modifications and functionalizations and/or functionalized along the polymer chains. The polybutadienes can be modified once or multiple times. The modifications can be those with hydroxyl groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxyl groups and/or phthalocyanine groups and/or silane sulfide groups. However, other modifications known to the person skilled in the art, also referred to as functionalizations, are also possible. Metal atoms can be part of such functionalizations.

The BR rubber used in the present rubber mixture is a BR specifically functionalized for the bonding of silicon dioxide or silica, which preferably has a glass transition temperature Tg below -70°C, preferably below -75°C. The glass transition temperature Tg is preferably not colder than -110°C, preferably not colder than -100°C, and more preferably not below -95°C. A preferred glass transition temperature is between -85°C and -95°C or between -75°C and -85°C.

The BR rubber used in the present rubber mixture is preferably of the low-cis type.

The chain ends of the BR rubber used in the present rubber mixture are preferably functionalized for the attachment of silicas.

The BR rubber used in the present rubber compound is preferably not oil extended.

The BR rubber used in the present rubber mixture preferably has a weight-average molecular weight Mw, measured by means of GPC (based on ISO 13885-1 ), in the range from 200,000 to 2,000,000 g/mol, preferably in the range from 250,000 to 1,000,000 g/mol, particularly preferably in the range from 300,000 to 750,000 g/mol, particularly preferably between 300,000 and 600,000 g/mol.

Several of the aforementioned BR rubbers can also be blended. However, liquid BR rubbers are preferably avoided in this rubber mixture.

The terms “silica”, “silica” and “silicon dioxide” are used synonymously in the present invention.

In the present rubber mixture, the silica-functionalized BR rubber is preferably blended with a high-surface area silicon dioxide, as specified in more detail later.

The functionalized BR rubber can have multiple functionalizations and, for example, can also be functionalized for interaction with carbon black.

The combination enables an unexpectedly significant performance advantage of the rubber compound. It shows a significant improvement in rolling resistance, as well as unexpectedly improved wet braking performance and unexpectedly good abrasion behavior.

Examples of BR rubbers used in the present invention include BR511 from Eneos (Tg = -78 °C, functionalized, Mw = 361,000 g/mol, 37% trans content and 30% cis content and 30% vinyl content, high silicon dioxide affinity) or KBR820 from KKPC (Tg = -92 °C, functionalized, 40.5% cis content and 12% vinyl content, high silicon dioxide affinity). The percentages are in each case by weight.

According to the invention, the rubber mixture contains as a further component 20 to 100 phr, preferably 30 to 70 phr, particularly preferably 40 to 60 phr, more preferably 45 to 55 phr of at least one silicon dioxide.

The at least one silicon dioxide has an average nitrogen surface area (BET surface area) according to DIN ISO 9277 of at least 210 m2/g (square meters per gram), preferably 210 to 425 m2/g, more preferably 210 to 320 m2/g, more preferably 265 to 320 m2/g.

The at least one silicon dioxide preferably further has an average CTAB surface area according to ASTM D 3765 of more than 200 m2/g, preferably 200 to 400 m2/g, more preferably 200 to 300 m2/g, particularly preferably 245 to 300 m2/g.

The at least one silicon dioxide is preferably amorphous silicon dioxide, preferably precipitated silica, which is also referred to as precipitated silicon dioxide.

With the described CTAB surface, the silicon dioxide used has an extremely high specific surface area and is classified as ultra-high surface silicon dioxide.

The associated increased reinforcing effect in rubber compounds results in advantageous abrasion properties.

With the present invention, it has surprisingly been possible to achieve good abrasion behavior, while at the same time offering good processability and surprisingly improved rolling resistance properties.

Surprisingly, an improvement in the conflicting objectives of rolling resistance, abrasion and wet braking performance as well as an improvement in the conflicting objectives of the aforementioned properties and processability was achieved.

A suitable silicon dioxide with an average BET surface area of 275 m2/g and an average CTAB surface area of 250 m2/g is available, for example, under the trade name Premium SW from Solvay Silica Korea Co., Ltd.

It has also surprisingly been found that particularly good properties, especially in the conflicting objectives of rolling resistance, abrasion behavior, wet braking and processability of the rubber compound, are achieved when a targeted selection of the type and quantity of diene rubber, in particular NR and BR, as well as silicon dioxide, is made.

The rubber mixture of these aforementioned embodiments preferably also contains comparatively small amounts of plasticizers, preferably in amounts of 0 to 20 phr, preferably 0 to 10 phr, particularly preferably 1 to 5 phr. The plasticizer(s) contained are preferably selected from the substances mentioned below.

The rubber mixture according to the invention, including all embodiments, may also contain at least one further filler which has a reinforcing effect or which does not have a reinforcing effect.

Further reinforcing fillers are in particular carbon blacks, preferably selected from industrial carbon blacks and pyrolysis carbon blacks, with industrial carbon blacks being more preferred, and further silicon dioxides, which have a CTAB surface area according to ASTM D 3765 of less than 190 m2/g.

Carbon blacks for rubber compounds known to those skilled in the art can be used. In one embodiment, the carbon black has an iodine number according to ASTM D 1510, also known as the iodine adsorption number, of between 30 and 250 g/kg, preferably 40 to 180 g/kg, more preferably 40 to 100 g/kg, and most preferably 60 to 90 kg/g.

The carbon blacks used preferably have a DBP number according to ASTM D 2414 of 80 to 200 ml/100 g, preferably 100 to 200 ml/100 g, and particularly preferably 110 to 180 ml/100 g. The DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light-colored filler using dibutyl phthalate. The carbon blacks used also include so-called "recovered" or recycled carbon blacks. The carbon blacks used can also be oxidized.

The total amount of carbon black contained corresponds to the usual amounts, preferably 0 to 50 phr.

Coal may optionally be included in the rubber mixture. This can be, for example, ground hard coal or lignite. However, HTC coal is preferably used as the coal, which is produced by hydrothermal carbonization of at least one starting substance. The abbreviation "HTC" stands for hydrothermal carbonization, which is well known in the art. In this process, at least one starting substance is heated together with water in a closed, pressure- and heat-resistant device, such as an autoclave. The starting mixture is thus a suspension and/or solution of the starting substance(s) in water. The heating and the resulting steam generate increased pressure, which depends in particular on the temperature and the filling level of the device. In hydrothermal carbonization, the process that naturally leads to the formation of lignite over many millions of years is imitated within a short period of time, usually a few hours. "HTC coal" refers to the solid that is the product of hydrothermal carbonization.

Soot and coal can also be used as a mixture.

According to advantageous embodiments of the invention, the rubber mixture contains at least one further reinforcing filler which is selected from the group consisting of carbon blacks, preferably selected from industrial carbon blacks and pyrolysis carbon blacks, with industrial carbon blacks being further preferred.

A carbon black of type N339 is particularly suitable and preferred.

The fillers preferably contain little or no other silicon dioxides that have a CTAB surface area according to ASTM D 3765 of less than 200 m2/g or a BET surface area of less than 210 m2/g. "Little" is understood here to mean a maximum amount of 5 phr, preferably a maximum of 1.5 phr.

Other (non-reinforcing) fillers within the scope of the present invention include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels as well as fibers (such as aramid fibers, glass fibers, carbon fibers, cellulose fibers).

Other potentially reinforcing fillers include carbon nanotubes (CNTs) including discrete CNTs, so-called hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups, such as hydroxyl, carboxy and carbonyl groups), graphite and graphene and so-called “carbon-silica dual-phase fillers”.

According to the invention, the rubber mixture further contains 1 to 30 phf of silanes in the form of at least two organosilicon compounds.

The term phf (parts per hundred parts of filler by weight) used in this document is the quantity commonly used in the rubber industry for coupling agents for fillers.

In the context of this application, phf refers to all silicon dioxides present, including those contained in the invention and other silicon dioxides. This means that any other fillers present, such as carbon black, are not included in the calculation of the silane quantity.

1. a) 1 bis 30 phf, bevorzugt 3 bis 30 phf, besonders bevorzugt 3 bis 20 phf, ganz besonders bevorzugt 5 bis 15 phf, wenigstens eines Silans A, welches ausgewählt ist aus den Silanen mit den allgemeinen Summenformeln A-I) und A-XI): A-I) (R¹)_oSi-R²⁰-(S-R³⁰)_m-S_x-(R³⁰-S)_m-R²⁰-Si(R¹)_o; A-XI) (R¹)_oSi-R²-(S-R³)_q-S-X; und optional b) 0,5 bis 30 phf, bevorzugt 2 bis 30 phf, besonders bevorzugt 3 bis 15 phf, ganz besonders bevorzugt 3 bis 10 phf, wenigstens eines Silans B, welches ausgewählt ist aus den Silanen mit den allgemeinen Summenformeln B-I), B-01) und B-02): B-I) (R¹)_oSi-R⁴-(S-R⁵)_u-S-R⁴-Si(R¹)_o; B-01) (R¹)_oSi-R¹⁰-Si(R¹)_o; B-02) (R¹)_oSi-R⁹;

wobei die Indizes o unabhängig voneinander gleich 1, 2 oder 3 sind;
und wobei die Reste R¹ gleich oder verschieden voneinander sind und ausgewählt sind aus C₁-C₂₀-Alkoxygruppen, C₆-C₂₀-Phenoxygruppen, C₂-C₁₀-cyclischen Dialkoxygruppen, C₂-C₂₀-Dialkoxygruppen, C₄-C₂₀-Cycloalkoxygruppen, C₆-C₂₀-Arylgruppen, C₁-C₂₀-Alkylgruppen, C₂-C₂₀-Alkenylgruppen, C₂-C₂₀-Alkinylgruppen, C₇-C₂₀-Aralkylgruppen, Halogeniden oder Alkylpolyethergruppen -O-(R⁶ -O)_r-R⁷, wobei die Reste R⁶ gleich oder verschieden sind und verzweigte oder unverzweigte, gesättigte oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische/aromatische zweibindige C₁-C₃₀-Kohlenwasserstoffgruppen sind, r eine ganze Zahl von 1 bis 30 ist und die Reste R⁷ unsubstituierte oder substituierte, verzweigte oder unverzweigte einbindige Alkyl-, Alkenyl-, Aryl- oder Aralkylgruppen sind,
oder zwei R¹ entsprechen einer Dialkoxygruppe mit 2 bis 10 Kohlenstoffatomen, wobei dann o < 3 ist,
oder es können zwei oder mehr Silane gemäß den Formeln A-I), A-XI), B-I), B-01) und/oder B-02) über Reste R¹ oder durch Kondensation verbrückt sein, wobei dann o pro Molekül < 3 ist; und wobei die Bedingung gilt, dass in den Formeln A-I), A-XI), B-I), B-01) und B-02) in jeder (R¹)_oSi-Gruppe wenigstens ein R¹ aus denjenigen oben genannten Möglichkeiten ausgewählt ist, bei der dieses R¹

• i) über ein Sauerstoffatom an das Siliziumatom gebunden ist oder
• ii) ii) ein Halogenid ist;

und wobei der Rest R⁹ ausgewählt ist aus C₆-C₂₀-Arylgruppen, C₁-C₂₀-Alkylgruppen, C₂-C₂₀-Alkenylgruppen, C₂-C₂₀-Alkinylgruppen, C₇-C₂₀-Aralkylgruppen;
und wobei die Reste R², R³, R⁴, R⁵, R^10, R²⁰, R³⁰ in jedem Molekül und innerhalb eines Moleküls gleich oder verschieden sind und verzweigte oder unverzweigte, gesättigte
oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische/aromatische zweibindige C₁-C₃₀-Kohlenwasserstoffgruppen sind;
und wobei x eine ganze Zahl von 2 bis 10 ist; und wobei m gleich 0 oder 1 oder 2 oder 3 ist; und q gleich 1 oder 2 oder 3 ist; und u gleich 1 oder 2 oder 3 ist;
und X ein Wasserstoffatom oder eine -C(=O)-R⁸ Gruppe ist, wobei R⁸ ausgewählt ist aus Wasserstoff, C₁-C₂₀-Alkylgruppen, C₆-C₂₀-Arylgruppen, C₂-C₂₀-Alkenylgruppen und C₇-C₂₀-Aralkylgruppen.The rubber mixture preferably contains as silanes at least

1. a) 1 to 30 phf, preferably 3 to 30 phf, particularly preferably 3 to 20 phf, very particularly preferably 5 to 15 phf, of at least one silane A, which is selected from the silanes having the general empirical formulas AI) and A-XI): AI) (R ¹ ) _o Si-R ²⁰ -(SR ³⁰ ) _m -S _x -(R ³⁰ -S) _m -R ²⁰ -Si(R ¹ ) _o ; A-XI) (R ¹ ) _o Si-R ² -(SR ³ ) _q -SX; and optionally b) 0.5 to 30 phf, preferably 2 to 30 phf, particularly preferably 3 to 15 phf, very particularly preferably 3 to 10 phf, of at least one silane B, which is selected from the silanes having the general empirical formulas BI), B-01) and B-02): BI) (R ¹ ) _o Si-R ⁴ -(SR ⁵ ) _u -SR ⁴ -Si(R ¹ ) _o ; B-01) (R ¹ ) _o Si-R ¹⁰ -Si(R ¹ ) _o ; B-02) (R ¹ ) _o Si-R ⁹ ;

where the indices o are independently equal to 1, 2 or 3;
and wherein the radicals R ¹ are identical or different from one another and are selected from C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₂₀ phenoxy groups, C ₂ -C ₁₀ cyclic dialkoxy groups, C ₂ -C ₂₀ dialkoxy groups, C ₄ -C ₂₀ cycloalkoxy groups, C ₆ -C ₂₀ aryl groups, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups, C ₇ -C ₂₀ aralkyl groups, halides or alkylpolyether groups -O-(R ⁶ -O) _r -R ⁷ , wherein the radicals R ⁶ are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C ₁ -C ₃₀ -hydrocarbon groups, r is an integer from 1 to 30 and the radicals R ⁷ are unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl groups,
or two R ¹ correspond to a dialkoxy group with 2 to 10 carbon atoms, where o is < 3,
or two or more silanes according to the formulas AI), A-XI), BI), B-01) and/or B-02) can be bridged via radicals R ¹ or by condensation, in which case o per molecule is <3; and the condition applies that in the formulas AI), A-XI), BI), B-01) and B-02) in each (R ¹ ) _o Si group at least one R ¹ is selected from those possibilities mentioned above, in which this R ¹

• i) is bonded to the silicon atom via an oxygen atom or
• ii) ii) is a halide;

and wherein the radical R ⁹ is selected from C ₆ -C ₂₀ aryl groups, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups, C ₇ -C ₂₀ aralkyl groups;
and wherein the radicals R ² , R ³ , R ⁴ , R ⁵ , R ^10, R ²⁰ , R ³⁰ are the same or different in each molecule and within a molecule and are branched or unbranched, saturated
or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C ₁ -C ₃₀ hydrocarbon groups;
and wherein x is an integer from 2 to 10; and wherein m is 0 or 1 or 2 or 3; and q is 1 or 2 or 3; and u is 1 or 2 or 3;
and X is a hydrogen atom or a -C(=O)-R ⁸ group, where R ⁸ is selected from hydrogen, C ₁ -C ₂₀ alkyl groups, C ₆ -C ₂₀ aryl groups, C ₂ -C ₂₀ alkenyl groups and C ₇ -C ₂₀ aralkyl groups.

The silane A contained as component a) according to the invention is a silane that can bind to polymers due to the S _x - group, where x is an integer from 2 to 10, or the SX group. In the case of the SX group, this is possible by removing X, i.e., the hydrogen atom or the -C(=O)-R ⁸ group.

In the case of the S _x grouping with x equal to 2 to 10, this is made possible by splitting the polysulfide group.

Different silanes of type A, i.e. with different S _x and/or SX groups, can also be present in the mixture.

The silane B contained according to the invention has no or only single sulfur atoms that cannot bond to the polymer chains of the diene rubber, since the chemical bond -C-S-C- does not usually open during vulcanization.

The silane B contained according to the invention is thus a so-called “non-binding silane”, which particularly means “non-binding to diene rubbers”.

Different silanes of type B) may also be present in the mixture.

Preferably, as silane A, at least 5 phf to 15 phf of the silane according to formula A-XII) are contained: A-XII) (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -SC(=O)-CH ₃

Preferably, as silane B, at least 3 phf to 10 phf of the silane according to formula B-II) are contained: B-II) (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -S-(CH ₂ ) ₃ -Si(OEt) ₃

With such a combination of silanes A and B, preferably the silanes according to formulas A-XII) and B-II), in combination with the other components contained according to the invention, the object underlying the invention is achieved particularly well.

The total amount of silanes A present, including all embodiments, is preferably 3 to 30 phf, particularly preferably 3 to 20 phf, very particularly preferably 5 to 15 phf.

The total amount of silanes B present, including all embodiments, is preferably 2 to 30 phf, particularly preferably 3 to 15 phf, very particularly preferably 3 to 10 phf.

Particularly with the preferred, particularly preferred, and very particularly preferred amounts and embodiments of silanes A and B, very good properties are achieved with regard to the conflicting objectives of abrasion, rolling resistance, wet braking properties, and processability of the rubber mixture. The molar ratio of silanes A to silanes B is particularly preferably 20:80 to 90:10, preferably 45:55 to 80:20.

• 1) Ozonschutzwachse und Alterungsschutzmittel, wie z. B. Diamine, wie N-Phenyl-N'-(1 ,3-dimethylbutyl)-p-phenylendiamin (6PPD), N,N'-Diphenyl-p-phenylendiamin (DPPD), N,N'-Ditolyl-p-phenylendiamin (DTPD), N-(1 ,4-dimethylpentyl)-N'-phenyl-p-phenylendiamin (7PPD), N-Isopropyl-N'-phenyl-p-phenylendiamin (IPPD), und/oder Dihydrochinoline, wie 2,2,4-Trimethyl-1 ,2-dihydrochinolin (TMQ), und/oder substituierte Bisphenole, wie 2,2'-Methylenbis(4-methyl-6-tert-butylphenol) (BPH), und/oder substituierte Phenole, wie Butylhydroxytoluol (BHT),
• 2) Aktivatoren, wie z. B. Zinkoxid und Fettsäuren (z. B. Stearinsäure) und/oder sonstige Aktivatoren, wie Zinkkomplexe wie z.B. Zinkethylhexanoat,
• 3) weitere Aktivatoren und/oder Agenzien für die Anbindung von Füllstoffen, insbesondere Ruß oder Siliziumdioxid, wie beispielsweise S-(3-Aminopropyl)-Thioschwefelsäure und/oder deren Metallsalze (Anbindung an Ruß) sowie weitere Silan-Kupplungsagenzien (Anbindung an Siliziumdioxid, insbesondere Kieselsäure) außer den erfindungsgemäß enthaltenen Silanen A und B,
• 4) Kohlenwasserstoffharze, wie insbesondere Phenolharze, insbesondere als Klebharze,
• 5) Mastikationshilfsmittel, wie z. B. 2,2'-Dibenzamidodiphenyldisulfid (DBD) und
• 6) Prozesshilfsmittel, wie insbesondere Fettsäureester und Metallseifen, wie z.B. Zinkseifen und/oder Calciumseifen,
• 7) Weichmacher, wie insbesondere wie aromatische, naphthenische oder paraffinische Mineralölweichmacher, wie z.B. MES (Mild Extraction Solvate) oder RAE (Residual Aromatic Extract) oder TDAE (Treated Distillate Aromatic Extract), oder Rubber-to-Liquid-Öle (RTL) oder Biomass-to-Liquid-Öle (BTL) bevorzugt mit einem Gehalt an polycyclischen Aromaten von weniger als 3 Gew.-% gemäß Methode IP 346 oder Triglyceride, wie z. B. Rapsöl, oder Faktisse oder Kohlenwasserstoffharze oder Flüssigkautschuk in Form von flüssigen Polymeren, deren mittleres Molekulargewicht (Bestimmung per GPC = gel permeation chromatography, in Anlehnung an ISO 11344) zwischen 500 und 20000 g/mol liegt.

Furthermore, the rubber mixture may contain conventional additives in the usual parts by weight, which are preferably added in at least one basic mixing stage during its production. These additives include

• 1) Ozone protection waxes and ageing inhibitors, such as diamines such as N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine (7PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), and/or dihydroquinolines such as 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), and/or substituted bisphenols such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (BPH), and/or substituted phenols such as butylhydroxytoluene (BHT),
• 2) Activators such as zinc oxide and fatty acids (e.g. stearic acid) and/or other activators such as zinc complexes such as zinc ethylhexanoate,
• 3) further activators and/or agents for the bonding of fillers, in particular carbon black or silicon dioxide, such as S-(3-aminopropyl)-thiosulphuric acid and/or its metal salts (bonding to carbon black) and further silane coupling agents (bonding to silicon dioxide, in particular silicic acid) in addition to the silanes A and B contained according to the invention,
• 4) Hydrocarbon resins, such as phenolic resins, in particular as adhesive resins,
• 5) Mastication aids, such as 2,2'-dibenzamidodiphenyl disulfide (DBD) and
• 6) Processing aids, such as fatty acid esters and metal soaps, such as zinc soaps and/or calcium soaps,
• 7) Plasticizers, in particular aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (Mild Extraction Solvate) or RAE (Residual Aromatic Extract) or TDAE (Treated Distillate Aromatic Extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL), preferably with a polycyclic aromatics content of less than 3% by weight according to method IP 346, or triglycerides, such as rapeseed oil, or factices or hydrocarbon resins or liquid rubber in the form of liquid polymers whose average molecular weight (determined by GPC = gel permeation chromatography, based on ISO 11344) is between 500 and 20,000 g/mol.

When using mineral oil, it is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts), RAE (Residual Aromatic Extract), TDAE (Treated Distilled Aromatic Extracts), MES (Mild Extracted Solvents) and naphthenic oils.

The proportion of the total amount of further additives is preferably 3 to 150 phr, particularly preferably 3 to 100 phr and most preferably 5 to 80 phr.

The rubber mixture according to the invention is preferably used in vulcanized form, in particular in vehicle tires or other vulcanized technical rubber articles.

The terms “vulcanized” and “crosslinked” are used synonymously in the context of the present invention.

The vulcanization of the rubber mixture according to the invention is preferably carried out in the presence of sulfur and/or sulfur donors using vulcanization accelerators, whereby some vulcanization accelerators can also act as sulfur donors. The accelerator is selected from the group consisting of thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators, and guanidine accelerators. Preference is given to using at least one sulfenamide accelerator selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS), N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS), benzothiazyl-2-sulfenemorpholide (MBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), N-tert-butyl-2-benzothiazolesulfenimide (TBSI), and/or at least one guanidine accelerator, such as diphenylguanidine (DPG).

In particular, two or more accelerators can be used.

All sulfur-donating substances known to the person skilled in the art can be used as sulfur-donating substances.

Furthermore, one or more reversion inhibitors, such as 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane, hexamethylene-1,6-bis(thiosulfate) disodium salt dihydrate, and/or tetrabenzylthiuram disulfide (TBzTD), can be used in the rubber mixture.

In addition, vulcanization retarders may be present in the rubber compound.

Otherwise, the rubber compound is produced according to the process commonly used in the rubber industry, in which a base compound containing all components except the vulcanization system (e.g., sulfur and vulcanization-influencing substances) is first prepared in one or more mixing stages. The finished compound is created by adding the vulcanization system in the mixing stages, preferably in the last mixing stage.

The finished mixture is further processed, for example, by extrusion or calendering, and formed into the appropriate shape. The rubber mixture according to the invention is particularly suitable for use in vehicle tires, especially pneumatic vehicle tires. Application in all tire components is conceivable in principle, in particular and preferably in the tread and/or sidewall, most preferably in the tread. In the case of a tread with a cap/base construction, the rubber mixture according to the invention is preferably used at least in the cap.

For use in vehicle tires, the mixture is formed as a ready-mix into the appropriate shape, preferably a sidewall and/or a tread, before vulcanization and is applied as known during the production of the green vehicle tire.

The rubber mixture according to the invention for use as a body compound in vehicle tires is produced as already described. The difference lies in the shaping after the extrusion process or calendering of the mixture. The resulting shapes of the still unvulcanized rubber mixture for one or more different body compounds are then used to construct a green tire.

The body compound refers to the rubber compounds for the other components of a tire, such as the horn profile, separator plate, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcement, bead profile and bandage.

For use of the rubber mixture according to the invention in belts and straps, especially conveyor belts, the extruded, still unvulcanized mixture is molded into the appropriate shape and, during or afterward, often provided with reinforcements, e.g., synthetic fibers or steel cords. Further processing then takes place by vulcanization.

As already stated at the outset, the present invention also provides a vulcanizate obtained by sulfur vulcanization of at least one rubber mixture according to the invention, including all of the preferred features. As already stated at the outset, the present invention also further provides a vehicle tire comprising at least one vulcanizate according to the invention, including all of the preferred features, in at least one component.

For the purposes of the present invention, vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, car and two-wheel tires.

A vehicle tire according to the invention is preferred which has at least one vulcanizate according to the invention including all preferred features at least in the tread and/or the sidewall, particularly preferably at least in the tread.

A further subject matter of the present invention, as already stated at the outset, is the use of the sulfur-crosslinkable rubber mixture according to the invention, including all preferred features, for the production of technical rubber articles, such as bellows, conveyor belts, air springs, belts, straps or hoses, as well as shoe soles.

The invention will now be explained in more detail using comparative and exemplary embodiments, which are summarized in Tables 1 and 3.

The inventive examples are designated E1 and E2, and the comparative examples are designated C1 and C2. Furthermore, Table 3 discloses the inventive examples E10 and E20.

Substances used: NR: NR TSR 20
SSBR: Sprintan SLR 3402, Trinseo, glass transition temperature Tg = -62 °C, functionalized, Mw = 470,000 g/mol,
Sprintan SLR 3402 is a solution-polymerized styrene-butadiene copolymer with 15% styrene and 30% vinyl content.

B1: BR500, Eneos (JSR), Tg = -88 °C, functionalized, Mw = 512,000 g/mol. BR500 is a butadiene rubber (BR) with a low cis content. BR500 has a 49% trans content, 35% cis content, and 15% vinyl content. BR500 is functionalized and exhibits a high carbon black (soot) affinity.

BR 2: BR511, Eneos (JSR), Tg = -78 °C, functionalized, Mw = 361,000 g/mol. BR511 is a butadiene rubber (BR) with a low cis content. BR511 has a 37% trans content, 30% cis content, and 30% vinyl content. BR511 is functionalized and exhibits a high affinity for silicon dioxide.

BR 3: KBR820, KKPC (Kumho), Tg = -92 °C, functionalized. KBR820 is a butadiene rubber (BR) with a low cis content. KBR820 has a 40.5% cis content and a 12% vinyl content. KBR820 is functionalized and exhibits a high affinity for silica.

• - in V1: BC2123, Fa. Birla Carbon,
• - ansonsten: BC2123 oder N220, Fa. Birla Carbon; oder N339, Fa. Orion Engineered Carbons.

Soot:

• - in V1: BC2123, Birla Carbon,
• - otherwise: BC2123 or N220, Birla Carbon; or N339, Orion Engineered Carbons.

Silica 1: Zeosil® 1165MP, Solvay, average CTAB surface area 157 m2/g, average BET surface area 161 m2/g,

Silica 2: Premium SW, Solvay, average CTAB surface area 250 m2/g, average BET surface area 275 m2/g,

Silane 1: Mixture of organosilicon compounds with at least two components having the following structure according to formulas A-XII): (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -SC(=O)-CH ₃
and B-II): (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -S-(CH ₂ ) ₃ -Si(OEt) ₃

Silane 2: Bis-[3-(triethoxysilyl)propyl] disulfide (TESPD, silane with 75% S ₂ ), from Evonik Industries

• 1) Sonstige Zusatzstoffe: Zinkoxid, Zinkseife, Stearinsäure, Weichmacher, Alterungsschutzmittel, Ozonschutzwachs, flüssiges Polybutadien
• 2) DPG und Vulkanisierungschemikalien (Vulkachemikalien): Sulfenamid-Beschleuniger und Schwefel

Silane 3: 3-Octanoylthio-1-propyltriethoxysilane, NXT, Momentive

• 1) Other additives: zinc oxide, zinc soap, stearic acid, plasticizer, anti-aging agent, ozone protection wax, liquid polybutadiene
• 2) DPG and vulcanization chemicals (vulcan chemicals): sulfenamide accelerators and sulfur

• Na₂CO₃ (59,78 g; 0,564 mol) und eine wässrige Lösung von NaSH (40% in Wasser; 79,04 g; 0,564 mol) wurden mit Wasser (97,52 g) vorgelegt. Dann wurde Tetrabutylphosphoniumbromid (TBPB) (50% in Wasser; 3,190 g; 0,005 mol) zugegeben und Acetylchlorid (40,58 g; 0,517 mol) über 1 h zugetropft wobei die Reaktionstemperatur bei 25-32 °C gehalten wurde. Nach vollständiger Zugabe des Acetylchlorids wurde 1 h bei Raumtemperatur gerührt. Dann wurde TBPB (50% in Wasser; 3,190 g; 0,005 mol) und 1 -Chlor-6-thiopropyltriethoxysilylhexan (s. oben; 167,8 g; 0,470 mol) zugegeben und 3-5 h am Rückfluss erhitzt. Der Reaktionsfortschritt wurde mittels Gaschromatographie verfolgt. Als das 1 -Chlor-6-thiopropyltriethoxy-silylhexan zu >96% abreagiert war wurde Wasser zugegeben bis sich alle Salze gelöst hatten und die Phasen wurden separiert. Die flüchtigen Bestandteile der organischen Phase wurden unter vermindertem Druck entfernt und S-(6-((3-(Triethoxysilyl)-propyl)thio)hexyl)thioacetat) als gelbe bis braune Flüssigkeit erhalten (Ausbeute: 90%, Molverhältnis: 97% S-(6-((3-(Triethoxysilyl)propyl)thio)hexyl)thioacetat (Silan A-XII), 3% Bis(thiopropyltriethoxysilyl)hexan (Silan B-II); Gew.-%: 96 Gew.-% S-(6-((3-(Triethoxysilyl)propyl)thio)hexyl)thioacetat (Silan A-XII), 4 Gew.-% 1,6-Bis(thiopropyltriethoxysilyl)hexan (Silan B-II)).

The silane according to formula A-XII) was prepared as follows:

• Na ₂ CO ₃ (59.78 g; 0.564 mol) and an aqueous solution of NaSH (40% in water; 79.04 g; 0.564 mol) were initially charged with water (97.52 g). Tetrabutylphosphonium bromide (TBPB) (50% in water; 3.190 g; 0.005 mol) was then added, and acetyl chloride (40.58 g; 0.517 mol) was added dropwise over 1 h, maintaining the reaction temperature at 25-32 °C. After complete addition of the acetyl chloride, the mixture was stirred at room temperature for 1 h. TBPB (50% in water; 3.190 g; 0.005 mol) and 1-chloro-6-thiopropyltriethoxysilylhexane (see above; 167.8 g; 0.470 mol) were then added and heated to reflux for 3-5 h. The reaction progress was monitored by gas chromatography. When the 1-chloro-6-thiopropyltriethoxysilylhexane had reacted to >96%, water was added until all salts had dissolved, and the phases were separated. The volatile components of the organic phase were removed under reduced pressure and S-(6-((3-(triethoxysilyl)propyl)thio)hexyl)thioacetate) was obtained as a yellow to brown liquid (yield: 90%, molar ratio: 97% S-(6-((3-(triethoxysilyl)propyl)thio)hexyl)thioacetate (silane A-XII), 3% bis(thiopropyltriethoxysilyl)hexane (silane B-II); wt%: 96 wt% S-(6-((3-(triethoxysilyl)propyl)thio)hexyl)thioacetate (silane A-XII), 4 wt% 1,6-bis(thiopropyltriethoxysilyl)hexane (silane B-II)).

• Zu Mercaptopropyltriethoxysilan (62,0 g; 0,260 mol; 2,10 eq) wird Natriumethanolat (21 % in EtOH; 82,3 g; 0,254 mol; 2,05 eq) so zudosiert, dass die Reaktionstemperatur nicht 35 °C übersteigt. Nach vollständiger Zugabe wird 2 h am Rückfluss erhitzt. Dann wird das Reaktionsgemisch zu 1,6-Dichlorhexan (19,2 g; 0,124 mol; 1 ,00 eq) über 1,5 h bei 80 °C zugegeben. Nach vollständiger Zugabe wird 3 h am Rückfluss erhitzt und anschließend auf Raumtemperatur erkalten gelassen. Ausgefallene Salze werden abfiltriert und das Produkt unter vermindertem Druck vom Lösungsmittel befreit. Das Produkt (Ausbeute: 88%, Reinheit: > 99% im13 C-NMR) wurde als klare Flüssigkeit erhalten.

The silane of formula B-II): 1,6-bis(thiopropyltriethoxysilyl)hexane) was prepared as follows:

• Sodium ethanolate (21% in EtOH; 82.3 g; 0.254 mol; 2.05 eq) was added to mercaptopropyltriethoxysilane (62.0 g; 0.260 mol; 2.10 eq) at a rate such that the reaction temperature did not exceed 35 °C. After the addition was complete, the mixture was heated at reflux for 2 h. The reaction mixture was then added to 1,6-dichlorohexane (19.2 g; 0.124 mol; 1.00 eq) over 1.5 h at 80 °C. After the addition was complete, the mixture was heated at reflux for 3 h and then allowed to cool to room temperature. Precipitated salts were filtered off, and the product was freed from the solvent under reduced pressure. The product (yield: 88%, purity: > 99% by 13 C NMR) was obtained as a clear liquid.

NMR method: The molar ratios and mass fractions given as analytical results in the above examples are derived from 13 C NMR measurements with the following parameters: 100.6 MHz, 1000 scans, solvent CDCb, internal standard for calibration: tetramethylsilane, relaxation aid Cr(acac)s, to determine the mass fraction in the product, a defined amount of dimethyl sulfone was added as an internal standard and the mass fraction was calculated from the molar ratios of the products.

The mass fractions are given in Table 1. Table 1: Components Unit V1 V2 E1 E2 NR phr 80 80 80 80 SSBR phr 20 BR 1 phr 20 BR 2 phr 20 BR 3 phr 20 soot phr 40 5 5 5 Silica 1 phr 15 60 Silica 2 phr 50 50 Silane 1 phf 17 17 Silane 2 phf 7 Silane 3 phf 10 Other additives 1) phr 11 21 14 14 Volcanic chemicals 2) phr 3 4 5 5

The compound was manufactured according to the process customary in the rubber industry under standard conditions in 2-5 stages.

• • Shore A Härte bei Raumtemperatur (RT) und bei 70 °C gemäß ISO 868,
• • Rückprallelastizität bei Raumtemperatur (RT) und bei 70 °C gemäß ISO 4662,
• • Spannungswert bei 300% Dehnung (M 300) bei RT und 70 °C, Zugfestigkeit sowie Bruchdehnung bei Raumtemperatur (RT), gemäß DIN 53 504.

Test specimens were prepared from all mixtures by vulcanization to t95 to t100 (measured on a Moving Die Rheometer according to ASTM D 5289-12/ ISO 6502 ) under pressure at 140-150 °C and using these test specimens, material properties typical for the rubber industry were determined using the test methods specified below.

• • Shore A hardness at room temperature (RT) and at 70 °C according to ISO 868,
• • Rebound resilience at room temperature (RT) and at 70 °C according to ISO 4662,
• • Tensile strength at 300% elongation (M 300) at RT and 70 °C, tensile strength and elongation at break at room temperature (RT), according to DIN 53 504.

• • Nassbremsen: ABS-Bremsen aus 80 km/h, nasser Beton, niedriges p (low p),
• • Rollwiderstand: gemäß ISO 28580
• • Abrieb: Relativer Gewichtsverlust der jeweiligen Reifen nach 15000 km bis 20000 km Straßenfahrt bei einer mittleren Temperatur von 5 bis 10 °C.

Furthermore, tire tests were conducted in Comparative Examples V1 and V2, as well as in Inventive Examples E1 and E2, each using the compound as a tread cap. The following test methods were used:

• • Wet braking: ABS braking from 80 km/h, wet concrete, low p,
• • Rolling resistance: according to ISO 28580
• • Wear: Relative weight loss of the respective tires after 15,000 km to 20,000 km of road travel at an average temperature of 5 to 10 °C.

The measured values are given in % relative to the measured values of the comparison example V1. A higher percentage indicates better tire performance. Table 2 Unit V1 V2 E1 E2 Properties of the rubber compound Shore hardness RT Shore A 62 62 69 68 Shore hardness 70 °C Shore A 60 57 66 64 Rebound RT % 63 53 57 57 Rebound 70 °C % 72 68 68 68 M 300 RT MPa 18 11 15 13 M 300 70 °C MPa 14 9 12 10 Tensile strength RT MPa 24 21 23 23 Elongation at break RT % 426 509 460 502 Tire properties Rolling resistance % 100 92 101 104 Wet braking % 100 112 115 110 Abrasion % 100 65 101 108

As can be seen in Table 2, the rubber mixtures according to the invention, in particular mixture E1, surprisingly achieve significantly improved wet braking performance in tires according to the invention, while still maintaining at least the same or even improved rolling resistance and abrasion performance compared to V1. Compared to V2, the rolling resistance and abrasion performance can be significantly improved, and the wet braking performance can be further improved.

The E2 tire has particularly advantageous abrasion and rolling resistance characteristics.

Furthermore, the rubber mixtures according to the invention exhibit optimal processability, in particular miscibility and extrudability. Thus, the conflicting objectives of the aforementioned properties are resolved at a higher level by the rubber mixture according to the invention.

Furthermore, modified examples of rubber compounds according to the invention, E10 and E20, were tested. E10 and E20 correspond to E1 and E2 (see Table 1), except that the BR content was increased from 20 phr to 40 phr and the NR content was reduced from 80 phr to 60 phr.

For E10 and E20, the measurement results described in Table 3 are analogous to those in Table 2. This shows that the inventive object is also achieved by a mixture according to Examples E10 or E20. Table 3 Unit E10 E20 Properties of the rubber compound Shore hardness RT Shore A 70 71 Shore hardness 70 °C Shore A 66 68 Rebound RT % 61 60 Rebound 70 °C % 68 70 M 300 RT MPa 12 12 M 300 70 °C MPa 9 10 Tensile strength RT MPa 21 21 Elongation at break RT % 506 487

QUOTES CONTAINED IN THE DESCRIPTION

This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 10 2017 221 232 A1 [0004]
• WO 2023 104 252 A1 [0004]

Cited non-patent literature

• ISO 13885-1 [0029]
• DIN ISO 9277 [0037]
• ISO 6502 [0112]

Claims (13)

A sulfur-crosslinkable rubber mixture comprising at least the following components: a) 50 to 100 phr of at least one polyisoprene, preferably a natural polyisoprene, b) 0 to 50 phr of at least one butadiene rubber, wherein the butadiene rubber is functionalized for the binding of silica and preferably has a glass transition temperature Tg between -70°C and -110°C, c) 20 to 100 phr, preferably 30 to 70 phr of at least one high-surface-area silicon dioxide with a BET surface area according to DIN ISO 9277 of at least 210 m²/g, preferably 265 to 320 m²/g, d) 1 to 30 phr of silanes selected from at least two organosilicon compounds. Sulphur-curable rubber compound according to Claim 1 , where the proportions of natural polyisoprene and butadiene rubber add up to exactly 100 phr, preferably 100.00 phr. Sulphur-curable rubber mixture according to one of the Claims 1 or 2 , wherein the butadiene rubber contained in the rubber mixture according to the invention is of the low-cis type, i.e. the cis content in the butadiene rubber is less than 90 wt.%. Sulphur-curable rubber mixture according to one of the Claims 1 until 3 , wherein the two organosilicon compounds contain at least 1 to 30 phf, preferably 5 to 15 phf of a silane A, which is selected from the silanes having the general molecular formulas AI) and A-XI): AI) (R ¹ ) _o Si-R ²⁰ -(SR ³⁰ ) _m -S _x -(R ³⁰ -S) _m -R ²⁰ -Si(R ¹ ) _o ; A-XI) (R ¹ ) _o Si-R ² -(SR ³ ) _q -SX; and 0.5 to 30 phf, preferably 3 to 10 phf of a silane B, which is selected from the silanes with the general molecular formulas BI), B-01) and B-02): BI) (R ¹ ) _o Si-R ⁴ -(SR ⁵ ) _u -SR ⁴ -Si(R ¹ ) _o ; B-01) (R ¹ ) _o Si-R ¹⁰ -Si(R ¹ ) _o ; B-02) (R ¹ ) _o Si-R ⁹ ; wherein the indices o are independently equal to 1, 2 or 3; and wherein the radicals R ¹ are identical or different from one another and are selected from C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₂₀ phenoxy groups, C ₂ -C ₁₀ cyclic dialkoxy groups, C ₂ -C ₂₀ dialkoxy groups, C ₄ -C ₂₀ cycloalkoxy groups, C ₆ -C ₂₀ aryl groups, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups, C ₇ -C ₂₀ aralkyl groups, halides or alkylpolyether groups -O-(R ⁶ -O) _r -R ⁷ , wherein the radicals R ⁶ are identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C ₁ -C ₃₀ -hydrocarbon groups, r is an integer from 1 to 30 and the radicals R ⁷ are unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl groups, or two R ¹ correspond to a dialkoxy group having 2 to 10 carbon atoms, in which case 0 is < 3, or two or more silanes according to the formulas AI), A-XI), BI), B-01) and/or B-02) can be bridged via radicals R ¹ or by condensation, in which case 0 per molecule is <3; and in which the condition applies that in the formulas AI), A-XI), BI), B-01) and B-02) in each (R ¹ ) _o Si group at least one R ¹ is selected from those possibilities mentioned above, in which this R ¹ is bonded to the silicon atom via an oxygen atom or is a halide; and wherein the radical R ⁹ is selected from C ₆ -C ₂₀ aryl groups, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups, C ₇ -C ₂₀ aralkyl groups; and wherein the radicals R ² , R ³ , R ⁴ , R ⁵ , R ^10, R ²⁰ , R ³⁰ are the same or different in each molecule and within a molecule and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C ₁ -C ₃₀ hydrocarbon groups; and wherein x is an integer from 2 to 10; and wherein m is 0 or 1 or 2 or 3; and q is 1 or 2 or 3; and u is 1 or 2 or 3; and X is a hydrogen atom or a -C(=O)-R ⁸ group, where R ⁸ is selected from hydrogen, C ₁ -C ₂₀ alkyl groups, C ₆ -C ₂₀ aryl groups, C ₂ -C ₂₀ alkenyl groups and C ₇ -C ₂₀ aralkyl groups. Sulphur-curable rubber compound according to Claim 4 , where 5 phf to 15 phf of the silane according to formula A-XII) are contained as silane A: A-XII) (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -SC(=O)-CH ₃ . Sulphur-curable rubber compound according to Claim 4 or 5 , where 3 phf to 10 phf of the silane according to formula B-II) are contained as silane B: B-II) (EtO) ₃ Si-(CH ₂ ) ₃ -S-(CH ₂ ) ₆ -S-(CH ₂ ) ₃ -Si(OEt) ₃ . Sulphur-curable rubber mixture according to one of the Claims 4 until 6 , wherein the molar ratio of silane A to silane B is 20:80 to 90:10, preferably 45:55 to 80:20. Sulphur-curable rubber mixture according to one of the Claims 1 until 7 , where the min at least one high-surface-area silicon dioxide has a CTAB surface area according to ASTM D 3765 of more than 200 m2/g, preferably 245 to 300 m2/g. Sulphur-curable rubber mixture according to one of the Claims 1 until 8 , wherein the rubber mixture according to the invention does not contain any liquid rubbers. Vulcanizate obtained by sulfur vulcanization of at least one rubber mixture according to one of the Claims 1 until 9 is preserved. Vehicle tyre, characterized in that it contains in at least one component at least one vulcanizate according to Claim 10 has. Vehicle tires according to Claim 11 , characterized in that it contains at least one vulcanizate according to Claim 10 at least in the tread and/or the sidewall, particularly preferably at least in the tread. Use of the rubber mixture according to one of the Claims 1 until 9 for the production of technical rubber articles such as bellows, conveyor belts, air springs, belts, straps or hoses, as well as shoe soles.