Vulcanisable rubber mixture, and vulcanised material having improved rolling properties

Abstract

The invention relates to a vulcanisable rubber mixture comprising: a) one or more diene rubbers; b) one or more fillers selected from the group consisting of fillers having free OH groups on the filler surface; c) one or more organosilicon-modified resins; and d) one or more plasticiser oils, in a combined mass fraction in the range from 1 to 60 phr.

Description

Description Vulcanizable rubber compound and vulcanizate with improved rolling properties The invention relates to a vulcanizable rubber mixture, a vulcanizate producible therefrom, and a rubber product containing this vulcanizate. Also disclosed is the use of a corresponding vulcanizable rubber mixture or a corresponding vulcanizate in the production of rubber products to improve their rolling properties. The automotive industry is one of the sectors that has faced fundamental challenges since the beginning of the 21st century and has simultaneously been shaped by numerous technological innovations. Growing customer awareness of environmental aspects such as emissions profiles and resource efficiency requires new mobility concepts. At the same time, demand for improved vehicle performance and requirements regarding driving safety are increasing. Meeting these challenges is not solely the responsibility of the actual vehicle manufacturers. In practice, many of these aspects are strongly influenced by tire properties, making the optimization of tire properties an important area of ​​innovation. Several relevant properties of pneumatic automotive tires, such as wet grip and abrasion resistance, are closely linked to the rubber composition of the tread. Therefore, many research efforts focus on optimizing the properties of the rubber composition and its additives. Significant progress has been made in this field in recent decades. A key innovation has been the at least partial replacement of carbon black fillers with silicon-containing compounds, in particular silicon dioxide compounds, such as fumed silica, or silicates. It has been shown that particularly favorable properties can be obtained if the silicon-containing compounds are modified on their surface by organosilanization, which is also referred to as organosilylation. For this purpose, the silicon-containing compounds are reacted with organosilicon compounds, in particular organyloxysilylorganic compounds, i.e. with compounds which have at least one CO-Si bond and at least one organic radical attached via a Si-C bond. In the course of the chemical reaction, which is usually a condensation reaction, a modification with the organic radical of the organosilicon compounds occurs at the interface between the silicon-containing compounds.This organic residue can be used to specifically influence the compatibility of the fillers in the rubber compound and their interactions with the rubber. In many cases, it is preferable for the organic residues to carry functional groups that can crosslink with the rubber compound during vulcanization, thus increasing the degree of crosslinking in the vulcanizate. This is why organosilicon compounds are sometimes also referred to as silane coupling agents. This principle is disclosed, for example, in DE 2536674 C3 or DE 2255577 A1. The concept developed for the modification of silicon-containing compounds was subsequently adapted to resins. For example, WO2018 / 191187 A1 proposed resins provided with a corresponding filler-reactive group to also enable bonding to the filler. A beneficial effect on the physicochemical properties of the vulcanizable rubber compounds produced with them or the vulcanizates produced from them by vulcanization was also observed. Such resins are sometimes referred to by the inventors as organosilicon-modified resins. Despite the fundamental advantages of using corresponding organosilicon-modified resins with filler-reactive groups, their use in vulcanizable rubber compounds is sometimes viewed as disadvantageous. In particular, it is often perceived as a disadvantage that, although an improvement in the trade-off between rolling resistance and wet grip can be achieved in many cases, this improvement is often still insufficient. Therefore, there is a need to achieve an improved solution to the trade-off between wet grip and rolling resistance using vulcanizable rubber compounds in which organosilicon-modified resins are used. The primary object of the present invention was to eliminate or at least reduce the above-described disadvantages of the prior art. In particular, the object of the present invention was to provide a vulcanizable rubber compound and corresponding vulcanizates producible therefrom that possess excellent mechanical properties and, in particular, optimally resolve the conflicting objectives of good wet grip on the one hand and favorable rolling resistance on the other. In this respect, it was desirable that the abrasion resistance of the vulcanizates should not be reduced or only slightly reduced, ideally even achieving an improvement in abrasion resistance. It was a supplementary object of the present invention that the vulcanizable rubber mixtures and vulcanizates to be specified should be producible, if possible, using production processes that are already used today in the field of rubber processing. It was a further object of the present invention to provide a corresponding rubber product which comprises the vulcanizate to be specified. It was a secondary object of the present invention to provide a use of a corresponding vulcanizable rubber mixture or a corresponding vulcanizate in the production of rubber products to improve the rolling properties. The inventors of the present invention have now recognized that the objects described above can surprisingly be achieved if specific amounts of a plasticizer oil, as defined in the claims, are used in vulcanizable rubber mixtures which comprise organosilicon-modified resins and fillers having free OH groups on the filler surface, in particular silicon-containing fillers. The above-mentioned objects are accordingly achieved by the subject matter of the invention as defined in the claims. Preferred embodiments of the invention emerge from the subclaims and the following statements. Such embodiments, which are designated as preferred below, are combined in particularly preferred embodiments with features of other embodiments designated as preferred. Combinations of two or more of the embodiments designated as particularly preferred below are thus very particularly preferred. Likewise preferred are embodiments in which a feature of one embodiment designated as preferred to any extent is combined with one or more further features of other embodiments designated as preferred to any extent. Features of preferred vulcanizates, rubber products, and uses emerge from the features of preferred vulcanizable rubber mixtures. To the extent that both specific amounts or proportions of a mixture component, for example for the diene rubbers or the organosilicon-modified resins, and preferred embodiments of the mixture component are disclosed below, the specific amounts or proportions of the preferably configured mixture components are also disclosed. Furthermore, it is disclosed that, with the corresponding specific total amounts or total proportions of the mixture components, at least some of the mixture components can be preferably configured, and in particular, that preferably configured mixture components can in turn be present in the specific amounts or proportions within the specific total amounts or total proportions. The invention relates to a vulcanizable rubber mixture comprising: a) one or more diene rubbers, b) one or more fillers selected from the group consisting of fillers having free OH groups on the filler surface, c) one or more organosilicon-modified resins, and d) one or more plasticizer oils, in a combined mass fraction in the range of 1 to 60 phr. Vulcanizable rubber mixtures per se and their typical components as well as typical production processes for obtaining corresponding vulcanizable rubber mixtures are comprehensively known to the person skilled in the art in the field of rubber processing. In accordance with standard practice, the above-defined components of the vulcanizable rubber compound are each used as "one or more." The term "one or more" In line with industry practice, this refers to the chemical nature of the corresponding compounds and not to their quantity. For example, the vulcanizable rubber compound, as a diene rubber, may exclusively comprise SBR, which would mean that the vulcanizable rubber compound comprises a large number of the corresponding molecules. Where mass fractions are specified below, these are in many cases given as combined mass fractions of one or more components, as is customary in the industry, thereby expressing that the mass fraction of the correspondingly formed components taken together meets the corresponding criteria. The phr (parts per hundred parts of rubber by weight) specification used here is the quantity specification commonly used in the rubber industry for mixture recipes, which indicates the mass fractions of the components in the rubber mixture based on the mass of the high-molecular-weight rubbers (weight-average molar mass Mw according to GPC greater than 60,000 g / mol) present in the rubber mixture, whereby the combined mass fraction of the high-molecular-weight rubbers in the rubber mixture corresponds to 100 phr. The vulcanizable rubber mixture according to the invention comprises at least one diene rubber. According to the expert understanding, diene rubbers are rubbers obtained by (co)polymerization of dienes and / or cycloalkenes and thus have C=C double bonds either in the main chain or in the side groups. It can be seen as an advantage of the vulcanizable rubber mixture according to the invention that it is very flexible with regard to the diene rubbers to be used, so that in principle all rubbers customary in the industry can be used. However, in the opinion of the inventors, a Vulcanizable rubber mixture, wherein the one or more diene rubbers are selected from the group consisting of natural polyisoprene, synthetic polyisoprene, epoxidized polyisoprene, butadiene rubber, solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, polynorbornene, ethylene-propylene-diene rubber, nitrile rubber, acrylate rubber, styrene-isoprene-butadiene terpolymer, butyl rubber and halobutyl rubber, wherein the one or more diene rubbers are preferably selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized Styrene-butadiene rubber (ESBR),wherein the one or more diene rubbers are particularly preferably selected from the group consisting of solution-polymerized styrene-butadiene rubber and emulsion-polymerized styrene-butadiene rubber. In this respect, additionally or alternatively, a vulcanizable rubber mixture according to the invention is also preferred, wherein at least one of the diene rubbers, preferably all of the one or more diene rubbers, is an end-group-modified and / or chain-modified diene rubber, preferably an end-group-modified diene rubber. To obtain vulcanizable rubber mixtures that can be converted into particularly high-performance vulcanizates by vulcanization, SBR, BR, and IR or NR have proven particularly suitable as diene rubbers. Thus, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises, as the diene rubber, styrene-butadiene rubber, preferably solution-polymerized styrene-butadiene rubber, preferably in a combined mass fraction of 30 phr or more, particularly preferably 50 phr or more, very particularly preferably 70 phr or more. Additionally or alternatively, a A vulcanizable rubber mixture according to the invention, wherein the vulcanizable rubber mixture comprises butadiene rubber as diene rubber, preferably in a combined mass fraction of 30 phr or more, particularly preferably 50 phr or more, very particularly preferably 70 phr or more. Preference is again given additionally or alternatively to a vulcanizable rubber mixture according to the invention, wherein the vulcanizable rubber mixture comprises natural polyisoprene and / or synthetic polyisoprene, preferably natural polyisoprene, as diene rubber, preferably in a combined mass fraction in the range from 1 to 40 phr, particularly preferably in the range from 2 to 35 phr, very particularly preferably in the range from 5 to 30 phr. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is preferred, wherein the diene rubber(s) have a weight-average molecular mass Mw, measured by GPC, in the range from 200,000 to 5,000,000 g / mol, preferably in the range from 250,000 to 2,500,000. To optimally adapt the physicochemical and mechanical properties of the vulcanizates produced to the respective application requirements, it has proven advantageous to mix two or more rubbers together. Accordingly, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises two or more, preferably three or more, different diene rubbers as the diene rubber. The vulcanizable rubber mixture according to the invention comprises one or more fillers selected from the group consisting of fillers with free OH groups on the filler surface. The person skilled in the art will understand that these are fillers which, due to the OH functionality on their surface, can enter into a condensation reaction with Si-OR functionalities, which in the Within the scope of the present invention, they can be introduced via the organosilicon-modified resin. Alongside other compounds, for example layered silicates such as kaolin, these are in particular amorphous silicon dioxide compounds, fillers with free OH groups on the filler surface. The vulcanizable rubber mixture according to the invention accordingly preferably comprises one or more silicon-containing fillers, which are particularly preferably selected from the group consisting of amorphous, i.e. non-crystalline, silicon dioxides. Among the amorphous silicon dioxides, the compounds which - for historical reasons - are also referred to as "silicic acids" or, based on the English term, "silica" are of outstanding importance in the rubber industry, especially the tire industry, so that the use of these "silicic acids" as silicon-containing fillers is preferred in essentially all cases.Accordingly, a vulcanizable rubber mixture according to the invention is very particularly preferred, wherein the one or more silicon-containing fillers are selected from the group consisting of pyrogenic silicon dioxide and precipitated silicon dioxide, particularly preferably precipitated silicon dioxide. In principle, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more silicon-containing fillers have a nitrogen surface area (BET surface area) according to DIN ISO 9277:2014-01 and DIN 66132:1975-07 in the range from 35 to 350 m 2 / g, preferably in the range of 45 to 260 m 2 / g, particularly preferably in the range of 100 to 220 m 2 / g. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more silicon-containing fillers have a CTAB surface according to ASTM D 3765-03 in the range of 35 to 350 m 2 / g, preferably in the range of 45 to 300 m 2 / g, particularly preferably in the range of 60 to 280 m 2 / g. With regard to the usable amounts of filler, the inventors have found that the vulcanizable rubber mixtures according to the invention advantageously exhibit excellent results even for high filler contents. In the inventors' estimation, however, the solution identified within the scope of the present invention exhibits the greatest advantages particularly at medium filler contents. Accordingly, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises the one or more fillers with free OH groups on the filler surface, preferably the one or more silicon-containing fillers, in a combined mass fraction in the range from 5 to 250 phr, preferably in the range from 20 to 180 phr, particularly preferably in the range from 30 to 160 phr, and most particularly preferably in the range from 40 to 130 phr. In addition to the fillers used according to the invention with free OH groups on the filler surface, preferably the silicon-containing fillers, further fillers that do not have free OH groups on the filler surface may also be present, thereby enabling a specific adaptation of the properties of the vulcanizable rubber mixture. A vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises one or more further fillers selected from the group consisting of fillers that do not have free OH groups on the filler surface, wherein the combined mass fraction of the further fillers is preferably in the range from 0.1 to 100 phr, particularly preferably in the range from 0.5 to 50 phr. In addition to the diene rubbers and fillers as well as the resins and plasticizer oils further characterized below, other typical components can be used in the vulcanizable rubber mixtures according to the invention, which, for example, Influence the physical-chemical properties, e.g. the processing and vulcanization properties, of the vulcanizable rubber compounds or the mechanical properties of the vulcanizates produced from them. An example in this respect is a vulcanizable rubber mixture according to the invention, wherein the vulcanizable rubber mixture comprises one or more further additives, wherein the further additives are preferably selected from the group consisting of coupling agents, methylene donors, ageing inhibitors, for example N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), activators, for example zinc oxide and fatty acids, waxes, mastication aids, for example 2,2'-dibenzamidodiphenyl disulfide (DBD) and processing aids, wherein the vulcanizable rubber mixture preferably comprises the further additives in a combined mass fraction in the range of 0.1 to 20 phr, preferably in the range of 0.5 to 15 phr, particularly preferably in the range of 1 to 10 phr. In addition to the organosilicon-modified resins specified further below, conventional resins can also be used. An example of this is a vulcanizable rubber mixture according to the invention, wherein the vulcanizable rubber mixture comprises one or more further resins that are not organosilicon-modified resins, preferably plasticizer resins and / or reinforcing resins, preferably in a combined mass fraction in the range of 0.5 to 50 phr, more preferably in the range of 1 to 40 phr, most preferably in the range of 5 to 30 phr. The expert in the field of rubber processing is easily able to distinguish resins from diene rubbers and any liquid polymer components, which in practice is particularly via the average molecular weight or the glass transition temperature. An example is a vulcanizable rubber mixture according to the invention, wherein the one or more further resins have a glass transition temperature, measured by DSC, T g of -20 °C or more, preferably of -15 °C or more, particularly preferably of -10 °C or more. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is also exemplary, wherein the one or more further resins have a weight-average molar mass Mw, measured by GPC, in the range from 200 to 50,000 g / mol, preferably in the range from 400 to 40,000 g / mol, particularly preferably in the range from 600 to 30,000 g / mol, very particularly preferably in the range from 800 to 20,000 g / mol. With regard to the vulcanization behavior, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises 0.5 to 8.0 phr, preferably 0.8 to 6 phr, particularly preferably 1 to 4 phr, of sulfur. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is also preferred, wherein the vulcanizable rubber mixture comprises further vulcanization components, wherein the further vulcanization components are selected from the group consisting of crosslinkers, vulcanization retarders, and vulcanization accelerators, for example, thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators, or guanidine accelerators. In addition to sulfur and sulfur donors, peroxide crosslinkers, for example, can also be used. Suitable peroxidic crosslinkers include, for example, organic peroxides such as dicumyl peroxide, di-(2,4-dichlorobenzoyl) peroxide, tert-butyl peroxybenzoate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, butyl-4,4-di-(tert- butylperoxy)valerate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, di-(2-tert-butylperoxyisopropyl)benzene or tert-butylcumyl peroxide, whereby these crosslinkers can also be used in any combination with each other. Further alternatives include, for example, the compounds described in WO 2018 / 191187 A1, paragraph

[0094] , cross-linking agents mentioned above are used. A particularly important component of the vulcanizable rubber mixtures according to the invention are the organosilicon-modified resins, which are sometimes also referred to as so-called organosilicon-modified resins. Examples of corresponding organosilicon-modified resins are disclosed, for example, in WO 2018 / 191187 A1. These organosilicon-modified resins comprise the typical oligomeric or (co)polymeric backbone of conventional resins, but also have at least one filler-reactive group. Since the boundaries between oligomeric and polymeric compounds are ultimately blurred and a distinction provides no advantage for the invention, in the context of the present invention, both cases are referred to as a (co)polymeric backbone or a (co)polymer chain, which accordingly also includes chains that could be referred to as (co)oligomer chains. With regard to the fillers used in rubber mixtures according to the invention with free OH groups on the filler surface, the filler-reactive group must be a group that can react with such surface-free OH groups. According to the invention, these filler-reactive groups could, in principle, be a variety of functional groups that enable the required reactivity with OH groups, for example, isocyanate groups for the formation of carbamates. The filler-reactive group can, for example, be those with Hydroxy groups and / or ethoxy groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or aminosiloxane and / or carboxy 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 a component of such functionalizations. In the opinion of the inventors, however, a silicon-based linkage is particularly suitable for the vulcanizable rubber mixtures according to the invention. The person skilled in the art will understand that the relevant reaction here is again organosilanization, ororganosilylation, and that the specific organosilicon-modified resins of the present invention are organosilicon-modified for this purpose, so that the organosilicon-modified resins are ultimately organyloxysilylorganic compounds and the same functional groups can be used that are known for this purpose from so-called silane coupling agents. According to the inventors' assessment, with regard to the mass fraction of these organosilicon-modified resins, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises the one or more organosilicon-modified resins in a combined mass fraction in the range of 0.5 to 60 phr, preferably in the range of 1 to 50 phr, particularly preferably in the range of 5 to 40 phr. In this respect, the inventors have also found in their own experiments that the combination of plasticizer oils with organosilicon-modified resins is particularly advantageous at lower resin contents, because particularly advantageous rebound resilience can be consistently achieved, whereas a decrease can occur in the combination of the corresponding components at high proportions of modified resin. Against this background, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises the one or more organosilicon-modified resins in a combined mass fraction in the range from 0.1 to 20 phr, preferably in the range from 0.5 to 15 phr, particularly preferably in the range from 1 to 10 phr, and / or wherein the vulcanizable rubber mixture comprises the one or more organosilicon-modified resins in a combined mass fraction of 17 phr or less, preferably of 13 phr or less, particularly preferably of 10 phr or less, very particularly preferably 8 phr or less. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises two or more different organosilicon-modified resins. The inventors have succeeded in identifying particularly suitable organosilicon-modified resins, the use of which can achieve particularly advantageous rolling resistance and favorable wet grip behavior, so that the conflict of objectives in this regard is resolved in an advantageous manner. Firstly, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more organosilicon-modified resins have a glass transition temperature, measured by DSC, T gof -20 °C or more, preferably of -15 °C or more, particularly preferably of -10 °C or more. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is also preferred, wherein the one or more organosilicon-modified resins have a weight-average molar mass Mw, measured by GPC, in the range from 200 to 60,000 g / mol, preferably in the range from 400 to 50,000 g / mol, particularly preferably in the range from 500 to 40,000 g / mol, very particularly preferably in the range from 600 to 35,000 g / mol. The number-average molar mass is determined by gel permeation chromatography according to DIN 55672-1: 2016-03 (GPC with tetrahydrofuran as eluent, polystyrene standard; Size exclusion chromatography (SEC = size exclusion chromatography). Although modification of the organosilicon-modified resins along the backbone is possible, the inventors consider terminal modification particularly advantageous, assuming that the resulting terminal attachment to the filler is sterically advantageous. Accordingly, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more organosilicon-modified resins are terminally organosilicon-modified resins. With regard to the chemical structure of the organosilicon modification, the inventors believe that this can be conveniently defined generically by linking the necessary silicon-containing functional group to the (co)polymer chain of the resin via a linker unit T. In this respect, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more organosilicon-modified resins comprise at least one structural element of formula II): II) (R 1 R 2 R 3 )Si - T -, where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom, where T is a linear or branched, preferably linear, organic compound unit having 1 to 60, preferably 2 to 40, particularly preferably 5 to 20, non-hydrogen atoms, via which the structural element of the formula II) is bonded to the (Co-)polymer chain of the organosilicon-modified resin. The expert understands that the (R 1 R 2 R 3 )Si group has the role of binding to the free OH groups on the filler surface, with possible configurations of the residues being disclosed, for example, in WO 2019 / 105614 A1. This (R 1 R 2 R 3 )Si group can be defined with respect to the radicals R 1 , R 2 and R 3 can be chosen quite flexibly, provided, however, that the organic group is at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom. As a result, the specific organosilicon-modified resins are organyloxysilylorganic compounds, which indicates to the person skilled in the art that the organosilicon-modified resin is suitable for organosilanization. The word component "organyloxysilyl" expresses that the corresponding organosilicon-modified resins have at least one organic radical that is bonded to the central silicon atom of the (R 1 R 2 R 3 )Si group. This organyloxy group, e.g., an alkoxy group such as an ethoxy group, is the leaving group that can be released during a condensation reaction on the surface of the filler with free OH groups on the filler surface, thus creating Si-O-Si bonds, for example, in the case of silicon-containing fillers. Even if organosilicon-modified resins can be used in which two of the three radicals R 1 , R 2 and R 3 are directly bonded to the central silicon via a carbon atom and therefore have only one leaving group, in practice, organosilicon-modified resins are preferred that have three, usually even identical, leaving groups, which in practice are often ethoxy groups, which are released as ethanol during the reaction. The corresponding design is usually with a view to the synthesis of the compounds, This is preferred due to lower manufacturing costs and the handling of the released leaving groups, which can be relatively easily removed from the mixture. Furthermore, corresponding organosilicon-modified resins with two or more leaving groups can, at least potentially, also bond with different filler particles. Despite the great flexibility in the design of the rests R 1 , R 2 and R 3 In the light of the above, any limitation is preferred that leads towards the particularly preferred (R 1 R 2 R 3 )Si group with three, mostly comparatively short-chain, alkoxy groups. Thus, a vulcanizable rubber mixture according to the invention is particularly preferred, wherein the radicals R 1 , R 2 and R 3are independently linear or branched alkoxy groups or alkyl groups having 1 to 10 carbon atoms, wherein at least one of the radicals R 1 , R 2 and R 3 is an alkoxy group. A vulcanizable rubber mixture according to the invention is preferred, wherein the radicals R 1 , R 2 and R 3 are independently linear alkoxy groups or alkyl groups. In this respect, additionally or alternatively, a vulcanizable rubber mixture according to the invention is also preferred, wherein the radicals R 1 , R 2 and R 3 independently of one another are alkoxy groups or alkyl groups having 1 to 5 carbon atoms, preferably having 2 or 3 carbon atoms. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is also preferred, wherein at least two, preferably all, of the radicals R 1 , R 2 and R 3Alkoxy groups. In principle, a vulcanizable rubber mixture according to the invention is particularly preferred, wherein the radicals R 1 , R 2 and R 3 are identical. A vulcanizable rubber mixture according to the invention is particularly preferred, wherein the radicals R 1 , R 2 and R 3 ethoxy groups. The above definitions define organic groups and organic compound units. The term organic is clear to the person skilled in the art and means that these units are part of a organic molecule and in most cases means that the non-hydrogen atoms are selected from the group of non-metals. In accordance with the expert understanding, organic groups (e.g. -CH3) are connected via a and organic linking units (e.g. -CH2-CH2- or -CH2-CHR x - CH2-, where R xfor example, can again be an organic group) is linked to other components of the respective compound via two attachment points. The reference to "non-hydrogen atoms" in organic groups and compound units is useful for the skilled person and is familiar to them based on their specialist knowledge. This can be used to express that organic compound units or groups can not only be pure hydrocarbon units or hydrocarbon groups, but can regularly also contain heteroatoms, as a result of which the organic compound units or groups also contain functional groups such as ester groups or ether groups. The skilled person will therefore readily understand that, in addition to the "non-hydrogen atoms" defined above, hydrogen atoms can of course also be present and will be present in the vast majority of cases. However, due to their monovalent nature, these will not be present in the chain but will rather fill the valences remaining on the "non-hydrogen atoms".The phrase “organic group with three non-hydrogen atoms” means, in accordance with the expert understanding, for example, that the organic group comprises, in addition to hydrogen atoms, three further non-hydrogen atoms. For essentially all embodiments, in accordance with the expert understanding, a vulcanizable rubber mixture according to the invention is preferred, wherein the non-hydrogen atoms are selected from the group consisting of C, N, O, S, P, F, Cl and Br, are preferably selected from the group consisting of C, N, O and S. It is clear to the person skilled in the art that the definition of organic compound units or groups results in an implicit functional restriction in that these are, of course, groups or compound units whose constitution does not contradict any fundamental chemical principles, so that the above units, for example, do not consist exclusively of halides. With a view to the time- and cost-efficient production of the organosilicon-modified resins, the inventors propose that it is expedient to provide at least one heteroatom and preferably also further functional groups in the linker unit T. This not only facilitates the binding of the organosilicon modification to the (co)polymer chain of the organosilicon-modified resin. Rather, the inventors' experiments have also shown that the properties of the organosilicon-modified resins and their effect in the vulcanizable rubber mixture can be influenced by the choice of functional groups and heteroatoms. In this context, a vulcanizable rubber mixture according to the invention is preferred, wherein the one or more organosilicon-modified resins comprise at least one structural element of the formula III): III) (R 1 R 2 R 3)Si - U - A - V -, where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3 is bonded to the Si atom via an oxygen atom, wherein U is a linear or branched, preferably linear, organic compound unit having 1 to 30, preferably 2 to 25, particularly preferably 5 to 20, non-hydrogen atoms, wherein U preferably comprises at least one functional group selected from the group consisting of amide- Groups, ester groups, carboxylic acid groups, ether groups and hydroxyl groups, particularly preferably selected from the group consisting of amide groups, ether groups and hydroxyl groups, where A is a heteroatom, preferably nitrogen or oxygen, particularly preferably oxygen, where V is a linear or branched, preferably linear, organic compound unit having 1 to 20, preferably 2 to 15, particularly preferably 5 to 10, non-hydrogen atoms, via which the structural element of the formula III) is attached to the (co)polymer chain of the organosilicon-modified resin, where V is preferably an aromatic organic chain, where V particularly preferably comprises an aromatic ring having 6 carbon atoms. Based on the inventors' experiments, it is particularly preferred if the bonding to the (co)polymer chain of the organosilicon-modified resin occurs via an aromatic ring system. A vulcanizable rubber mixture according to the invention is preferred, wherein the one or more organosilicon-modified resins comprise at least one structural element of formula IV): IV) (R 1 R 2 R 3 )Si - (CH2)i - W- A - Ar-, where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom, where i is in the range from 1 to 20, preferably in the range from 2 to 15, particularly preferably in the range from 3 to 10, where A is a heteroatom, preferably nitrogen or oxygen, particularly preferably oxygen, where Ar is an aromatic ring, preferably an aromatic ring having 6 carbon atoms, via which the structural element of the formula III) is bonded to the (co)polymer chain of the organosilicon-modified resin, where W is a linear or branched, preferably linear, organic compound unit having 2 to 20, preferably 3 to 15, particularly preferably 4 to 10, non-hydrogen atoms, where W comprises at least one functional group selected from the group consisting of amide groups, ester groups, carboxylic acid groups, ether groups and hydroxy groups, preferably selected from the group consisting of amide groups, ether groups and hydroxy groups. In their own experiments, the inventors succeeded in identifying two structural elements for organosilicon modification, which, in combination with the specific plasticizer oils, achieve particularly good results in resolving the conflict between rolling resistance and wet grip. Particularly preferred is a vulcanizable rubber mixture according to the invention, wherein the one or more organosilicon-modified resins contain at least one structural element of the formula V): VI), where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group is at least one of the radicals R 1 , R 2 and R 3 is bonded to the Si atom via an oxygen atom. As explained above, the organosilicon-modified resins comprise a (co)polymer chain as their backbone. These are copolymers that are or can be produced by polymerization from a specific monomer composition. In accordance with expert understanding and standard practice in the field of technology, it is expedient to define such (co)polymers by the manufacturing process or the starting materials used for production, since it is largely impossible to define the corresponding materials in their entirety conclusively in any other way. In accordance with standard practice in the field of technology, manufacturability is specified in relation to the monomer composition, which, in accordance with expert understanding, includes all monomeric constituents that are converted into monomer units of the (co)polymer chain during polymerization. Accordingly, other constituents that may be present in the reaction mixture during polymerization but are not incorporated into the (co)polymer chain during polymerization, such as solvents, are not included in the monomer composition. The starting point for the further description of the (co)polymer chain is thus initially a vulcanizable rubber mixture according to the invention, wherein the one or more organosilicon-modified resins comprise a (co)polymer chain which can be prepared by polymerizing a monomer composition. Based on this, a vulcanizable rubber mixture according to the invention is preferred, wherein the monomer composition comprises one or more polymerizable monomers selected from the group consisting of unsaturated aliphatic monomers and unsaturated aromatic monomers, preferably selected from the group consisting of unsaturated aromatic monomers, wherein the monomer composition preferably consists of these monomers. Additionally or alternatively, a vulcanizable rubber mixture according to the invention is preferred, wherein the monomer composition comprises one or more polymerizable monomers selected from the group consisting of Acrylates, methacrylates, terpenes, unsaturated fatty acids and vinyl aromatic compounds, wherein the monomer composition preferably consists of these monomers. According to the inventors' assessment, a vulcanizable rubber mixture according to the invention is particularly preferred, wherein the monomer composition comprises one or more polymerizable monomers selected from the group consisting of ethylenically unsaturated aromatic monomers, preferably α-methylstyrene and / or styrene, wherein the monomer composition preferably consists of these monomers. Accordingly, a vulcanizable rubber mixture according to the invention is also particularly preferred, wherein the one or more organosilicon-modified resins comprise a (co)polymer chain of polymerized α-methylstyrene and / or styrene, preferably α-methylstyrene and styrene. The second essential component of the vulcanizable rubber mixtures according to the invention are the plasticizer oils. According to the inventors, in principle all typical plasticizer oils are suitable for use in the vulcanizable rubber mixtures according to the invention. However, according to the inventors, preference is given to a vulcanizable rubber mixture according to the invention in which the one or more plasticizer oils are selected from the group consisting of MES (mild extraction solvate), RAE (residual aromatic extract), TDAE (treated distillate aromatic extract), rubber-to-liquid oils (RTL), and biomass-to-liquid oils (BTL), preferably selected from the group consisting of MES, RAE, and TDAE, particularly preferably TDAE. An example is a vulcanizable rubber mixture according to the invention, wherein the one or more plasticizer oils are selected from the group consisting of mineral oil plasticizers, preferably aromatic, naphthenic and paraffinic mineral oil plasticizers. A vulcanizable rubber mixture according to the invention is preferred, wherein the one or more plasticizer oils are selected from the group consisting of plasticizer oils, preferably bio-based plasticizer oils, with a mass fraction of naphthenic compounds of 2.5% or more, preferably 5% or more, particularly preferably 7.5% or more, based on the mass of the plasticizer oil, and / or wherein the one or more plasticizer oils are selected from the group consisting of plasticizer oils, preferably bio-based plasticizer oils, with a mass fraction of paraffinic compounds of 2.5% or more, preferably 5% or more, particularly preferably 7.5% or more, based on the mass of the plasticizer oil, and / or wherein the one or more plasticizer oils are selected from the group consisting of plasticizer oils, preferably bio-based plasticizer oils, with a mass fraction of aromatic compounds of 0.1% or more, preferably 2.5% or more,particularly preferably 5% or more, based on the mass of the process oil, With regard to the mass fractions, the inventors were able to identify ranges with which reliably good results can be achieved in the conflicting objectives between rolling resistance and wet grip. A vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises the one or more plasticizer oils in a combined mass fraction in the range from 2 to 50 phr, particularly preferably in the range from 5 to 45 phr, most preferably in the range from 10 to 40 phr. In the opinion of the inventors, it is particularly expedient to provide certain minimum contents in order to achieve the most pronounced effect possible. Accordingly, additionally or alternatively, a vulcanizable rubber mixture according to the invention is preferred, wherein the vulcanizable rubber mixture comprises the one or more plasticizer oils in a combined mass fraction in the range from 5 phr or more, preferably 10 phr or more, particularly preferably 15 phr or more. The inventors have recognized that particularly advantageous results can be achieved when the content of plasticizer oil is specifically matched to the content of organosilicon-modified resin. In this respect, the inventors consider a vulcanizable rubber mixture according to the invention to be preferred, wherein the quotient of the combined mass fraction of the plasticizer oils divided by the combined mass fraction of the organosilicon-modified resins is 5 or less, preferably 2.5 or less, particularly preferably 1.5 or less, and / or wherein the quotient of the combined mass fraction of the plasticizer oils divided by the combined mass fraction of the organosilicon-modified resins is in the range from 0.8 to 5, preferably in the range from 1.0 to 4, particularly preferably in the range from 1.2 to 3. Vulcanizates or rubber products can be produced in the usual way from the vulcanizable rubber mixtures according to the invention. The corresponding process for producing a vulcanizate or a rubber product comprises, in addition to producing the vulcanizable rubber mixture according to the invention, for example, the additional step of vulcanizing the vulcanizable rubber mixture according to the invention, preferably as part of a rubber blank, particularly preferably an unvulcanized vehicle tire blank, to obtain a vulcanizate, preferably as part of a rubber product, preferably a pneumatic vehicle tire. The vulcanizable rubber mixture according to the invention is vulcanized, for example, by the process customary in the tire industry, for example by sulfur-based crosslinking. The invention accordingly also relates to a vulcanizate, which can be produced or is produced by vulcanization of a vulcanizable Rubber mixture. A vulcanizate according to the invention is preferred in this respect, wherein the vulcanizate can be produced by vulcanization at a temperature in the range of 120 to 200°C, preferably in the range of 130 to 180°C. Accordingly, the invention also relates to a rubber product comprising a vulcanizate according to the invention. An example of a rubber product according to the invention is one in which the rubber product is selected from the group consisting of shoe soles, belts, hoses, and straps. However, for essentially all cases, a rubber product according to the invention is preferred, wherein the rubber product is a vehicle tire, preferably a pneumatic vehicle tire. Finally, the use of a vulcanizable rubber mixture according to the invention and / or a vulcanizate according to the invention in the production of rubber products for improving the rolling properties is also disclosed. In the following, the invention and preferred embodiments of the invention are further explained and described with reference to experiments. A. Production of vulcanizable rubber compounds: The vulcanizable rubber compounds were produced according to the process commonly used in the rubber industry under standard conditions in three stages in a laboratory mixer (300 mL, Brabender Mixer, CW Brabender GmbH & Co., South Hackensack, NJ, US). In the first mixing stage (basic mixing stage, rotor speed: 70 rpm, starting temperature: approx. 130 °C, final temperature: approx. 149 °C), all components except the vulcanization system (sulfur and vulcanization-influencing substances) were mixed. By adding the vulcanization system in the second stage (final mixing stage; rotor speed: 55 rpm, Temperature: approx. 80 °C,) the vulcanizable rubber mixture was produced. The substances used are listed in Table 1. Table 1 - Substances used Standardized, vulcanized vulcanizates were produced as test specimens from all vulcanizable rubber compounds by vulcanization (vulcanization conditions: t: 20 min, T: 160 °C). B. Determination of the physico-chemical properties of the vulcanizates: The following physicochemical properties were determined on the vulcanizates produced using the determination methods described below: Shore A hardness at room temperature (25 °C) according to DIN EN ISO 868:2003-10; Loss factor tan ö at 0 °C and 70 °C from temperature-dependent dynamic-mechanical measurement using an Eplexor according to DIN 53513: 1990-03 (constant force, 10 % compression, ± 0.2 % strain amplitude, frequency 10 Hz) and temperature at maximum loss factor (T @ tan ö max); and Abrasion at room temperature according to DIN ISO 4649:2021 (method A with non-rotating test specimens). The loss factor tan δ (0 °C) serves as an indicator of a tire's wet grip. The higher the loss factor tan δ (0 °C), the better the wet grip properties. The loss factor tan δ (70 °C) serves as an indicator of a tire's rolling resistance, with a lower loss factor tan δ (70 °C) indicating lower rolling resistance. The greater the difference A tan δ (loss factor tan δ (0 °C) - loss factor tan δ (70 °C)), the more advantageous the respective vulcanizate is with regard to the trade-off between wet grip properties and rolling resistance. C. 1 . Series of experiments: In the first series of tests, ten vulcanizable rubber compounds were produced, the composition of which is given in Table 2. Table 2 - Vulcanizable rubber compounds according to the first test series (all data in phr) The material properties determined for the corresponding vulcanizates are summarized in Table 3. Table 3 - Material properties for the 1st test series D. 2nd series of experiments: In the second series of tests, four vulcanizable Rubber compounds were produced, the composition of which is given in Table 4. Table 4 - Vulcanizable rubber compounds according to 2. Test series (all data in phr) The material properties determined for the corresponding vulcanizates are summarized in Table 5. Table 5 - Material properties for the 2nd test series E. 3rd series of experiments: In the third series of tests, eight vulcanizable Rubber compounds were produced, the composition of which is given in Table 6. Table 6 - Vulcanizable rubber compounds according to the 3rd test series (all data in phr) The material properties determined for the corresponding vulcanizates are summarized in Table 7. Table 7 - Material properties for the 3rd test series F Rating: The results of the 1st, 2nd and 3rd series of tests show that vulcanizates can be obtained from vulcanizable rubber mixtures according to the invention which advantageously resolve the conflict of objectives between rolling resistance and wet grip. By using the plasticizer oils in combination with the organosilicon-modified resins, vulcanizates are obtained for all vulcanizable rubber mixtures according to the invention whose A tan δ as an indicator for the trade-off between rolling resistance and wet grip is consistently improved compared to those of the respective comparison system without plasticizer oil. The third series of tests clearly demonstrates that the use of plasticizer oils according to the invention is advantageous compared to other plasticizers such as liquid polybutadiene in resolving the conflict of objectives between wet grip and rolling resistance.

Claims

Claims 1. Vulcanizable rubber mixture comprising: a) one or more diene rubbers, b) one or more fillers selected from the group consisting of fillers having free OH groups on the filler surface, c) one or more organosilicon-modified resins, and d) one or more processing oils, in a combined mass fraction in the range of 1 to 60 phr.

2. Vulcanizable rubber composition according to claim 1, wherein the vulcanizable rubber composition comprises the one or more fillers in a combined mass fraction in the range of 5 to 250 phr.

3. Vulcanizable rubber mixture according to one of claims 1 or 2, wherein the one or more fillers are selected from the group consisting of amorphous silicon dioxides.

4. A vulcanizable rubber composition according to any one of claims 1 to 3, wherein the vulcanizable rubber composition comprises the one or more organosilicon-modified resins in a combined mass fraction in the range of 0.5 to 60 phr.

5. Vulcanizable rubber mixture according to one of claims 1 to 4, wherein the one or more organosilicon-modified resins comprises at least one structural element of formula II): II) (R 1 R 2 R 3 )Si - T - where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom, wherein T is a linear or branched organic compound unit having 1 to 60 non-hydrogen atoms, via which the structural element of formula II) is bonded to the (co)polymer chain of the organosilicon-modified resin.

6. Vulcanizable rubber mixture according to one of claims 1 to 5, wherein the one or more organosilicon-modified resins comprise at least one structural element of formula III): III) (R 1 R 2 R 3 )Si - U - A - V -, where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom, wherein U is a linear or branched organic compound unit having 1 to 30 non-hydrogen atoms, wherein A is a heteroatom, wherein V is a linear or branched organic compound unit having 1 to 20 non-hydrogen atoms, via which the structural element of formula III) is bonded to the (co)polymer chain of the organosilicon-modified resin.

7. Vulcanizable rubber mixture according to one of claims 1 to 6, wherein the one or more organosilicon-modified resins comprise at least one structural element of formula IV): IV) (R 1 R 2 R 3 )Si - (CH2)i - W - A - Ar- where the radicals R 1 , R 2 and R 3 are independently linear or branched organic groups having 1 to 20 non-hydrogen atoms, wherein the organic group comprises at least one of the radicals R 1 , R 2 and R 3is bonded to the Si atom via an oxygen atom, where i is in the range from 1 to 20, where A is a heteroatom, where Ar is an aromatic ring, via which the structural element of formula III) is bonded to the (co)polymer chain of the organosilicon-modified resin, where W is a linear or branched organic compound unit having 2 to 20 non-hydrogen atoms, where W comprises at least one functional group selected from the group consisting of amide groups, ester groups, carboxylic acid groups, ether groups and hydroxy groups.

8. Vulcanizable rubber mixture according to one of claims 1 to 7, wherein the one or more processing oils are selected from the group consisting of processing oils having a mass fraction of naphthenic compounds of 2.5% or more, based on the mass of the processing oil.

9. A vulcanizable rubber mixture according to any one of claims 1 to 8, wherein the vulcanizable rubber mixture comprises the one or more processing oils in a combined mass fraction in the range of 2 to 50 phr.

10. Vulcanizable rubber mixture according to one of claims 1 to 9, wherein the quotient of the combined mass fraction of the plasticizer oils divided by the combined mass fraction of the organosilicon-modified resins is in the range of 0.8 to 5.

11. Vulcanizate, producible or produced by vulcanization of a vulcanizable rubber mixture according to one of claims 1 to 10.

12. A rubber product comprising a vulcanizate according to claim 11.

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