Sulfur-crosslinkable rubber composition comprising an organic filler and an organosilane

Abstract

The present invention relates to a vulcanization system VS containing at least sulfur and / or at least one sulfur donor, a rubber component K containing at least one rubber crosslinkable by sulfur, and a sulfur-containing rubber component K containing at least one rubber having a carbon content in the range of 0.2 to 0.45 Bq / g. 14 C content and >20~150m 2 and at least one organosilane having at least one hydrolyzable group and at least one sulfur atom; a kit-of-parts comprising as part (A) a rubber composition comprising said components F and K and as part (B) a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, said organosilane being included in part (A); vulcanized rubber compositions obtainable therefrom, respectively; the use of said products for application in the manufacture of tires, tire components and rubber articles; and the corresponding tires, tire components and rubber articles as such.

Description

[Technical field]

[0001] The present invention relates to a vulcanization system VS containing at least sulfur and / or at least one sulfur donor that releases sulfur under vulcanization conditions, a rubber component K containing at least one rubber that can be crosslinked by sulfur, and a carbon content in the range of 0.20 to 0.45 Bq / g. 14 C content and >20~150m 2 and at least one organosilane having at least one hydrolyzable group and at least one sulfur atom; a kit-of-parts comprising as part (A) a rubber composition comprising said components F and K, and as part (B) a vulcanization system VS comprising at least sulfur, said organosilane being included in part (A); vulcanized rubber compositions obtainable therefrom, respectively; the use of said products for application in the manufacture of tires, tire components and rubber articles; and the corresponding tires, tire components and rubber articles as such. [Background technology]

[0002] The use of reinforcing fillers in rubber compositions is known in the prior art. The use of reinforcing fillers ensures the service characteristics of the vulcanized rubber articles produced therefrom. For example, the use of reinforcing fillers increases the viscosity of the rubber and improves the fracture behavior of the vulcanizate. Here, technical carbon black represents the largest part of the reinforcing fillers. Technical carbon black is produced by incomplete combustion of organic compounds or pyrolysis of hydrocarbons. Most technical carbon black is produced by furnace processes. Due to the high amount of CO2 during the production process, it is desirable to avoid or minimize the use of fossil energy sources for filler production. Furthermore, technical carbon black is often not suitable for use in certain applications due to its color. Known alternatives to the use of technical carbon black as a reinforcing filler consist of precipitated silica and difunctional silanes.

[0003] In the production of treads for automobile tires, 120 to 200 m 2 It has been known to utilize silicas having a BET surface of 0.1 g / g in conjunction with difunctional coupling agents such as sulfur-functional silanes because their use could extend the "magic triangle" of tire performance consisting of wear, rolling resistance, and wet traction compared to the use of industrial carbon black.

[0004] In contrast to the tread, in the dynamic structural parts (carcass, belt, layer, band / strip), wear by abrasion or wet or dry traction play a less important role than in the tire tread. The main objective with dynamic structural parts is to reduce the conversion of mechanical energy into heat. The heat generation is expressed by the loss factor tan delta (tan δ). The loss factor tan δ characterizes the viscoelastic behavior and comes from the ratio of the viscous and elastic components (loss modulus and storage modulus). The storage modulus represents the part of the mechanical energy stored by the system, while the loss modulus represents the mechanical energy converted into thermal energy. Therefore, a low loss factor, as an important indicator of heat generation, is preferred, especially in the case of said dynamic structural parts.

[0005] The heat generation must also be taken into account, since the polymers used already contribute to heat generation due to their dynamic properties. Therefore, the low glass transition temperature T g This reduces the loss factor.

[0006] In rubber compounds for dynamic structural parts, mainly technical carbon blacks with low specific surface area are used with the aim of minimizing heat generation. The heat generation or loss factor can be reduced by decreasing the loading of the reinforcing fillers, increasing the size of the particles of the reinforcing fillers per volume unit under consideration, and / or increasing the distance of the reinforcing particles per volume unit. The volume loading ratio can be reduced by high structuring of the technical carbon blacks (expressed by the so-called Compressed Oil Absorption (COAN)) without affecting the hardness of the structural parts.

[0007] However, this independence does not apply to all parameters. In contrast, a reduction in the loss factor in order to achieve the lowest possible heat generation usually also affects other properties of the vulcanized rubber composition. An increase in crosslink density also reduces the loss factor, regardless of the reinforcing fillers. However, a higher crosslink density has a negative effect on the vulcanized rubber composition, for example with regard to its tear properties (reduced elongation at break) and aging properties.

[0008] An important issue with reinforcing fillers is that the reduction in loss factor is achieved at the expense of dynamic stiffness. At lower values ​​of loss factor tan δ, typically only low dynamic stiffness can be observed. However, such low dynamic stiffness leads to higher deformation of the rubber composition at the same load, which is therefore disadvantageous for the use of the rubber composition, especially for the production of tires or their dynamic structural parts.

[0009] It is therefore desirable to provide a rubber composition which, after vulcanization, has both the lowest possible loss factor and the highest possible dynamic stiffness, so that the conversion of mechanical energy into heat is minimized and the vulcanized rubber composition has only the lowest possible deformation under load. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] DE 10 2008 052 116 [Patent Document 2] International Publication No. 2017 / 085278 [Patent Document 3] International Publication No. 2017 / 194346 [Patent Document 4] European Patent Application Publication No. 3 470 457 Summary of the Invention [Problem to be solved by the invention]

[0011] It is therefore an object of the present invention to provide a vulcanizable rubber composition which, after its vulcanization, has the highest possible dynamic stiffness and at the same time the lowest possible heat generation, and in particular these two parameters can be decoupled so that the rubber composition can be more flexibly and better adjusted with regard to its performance to be achieved. [Means for solving the problem]

[0012] This object is achieved by the subject matter claimed in the claims and by preferred embodiments of these subject matter described in the following specification.

[0013] A first subject of the invention is a vulcanizable rubber composition comprising a rubber component K, a filler component F and a vulcanization system VS, the vulcanization system VS comprises at least sulfur and / or at least one sulfur donor, The rubber component K contains at least one rubber crosslinkable by sulfur, Filler component F is in the range of 0.20 to 0.45 Bq / g carbon. 14 C content and 20~150m 2 / g, preferably >20-150m 2 at least one organic filler having a BET surface area in the range of 0.1 μm / g; The vulcanizable rubber composition further comprises at least one organosilane as a part of a filler component F, the at least one organosilane having at least one hydrolyzable group and at least one sulfur atom, and preferably contained in an amount in the range of 0.25 to 5 phr.

[0014] Another subject of the invention is a method for producing ... mixture of a plurality of compounds, in a spatially separated manner, a rubber composition comprising as part (A) at least the above-mentioned rubber component K used according to the invention and at least a filler component F used according to the invention, where part (A) of the kit of parts does not, however, contain sulfur and / or at least one sulfur donor of the vulcanization system VS used according to the invention; As part (B), a vulcanization system VS used according to the invention, which comprises at least sulfur and / or at least one sulfur donor; The organosilane used according to the present invention is preferably contained in the filler component F in part (A) in an amount ranging from 0.25 to 5 phr.

[0015] Another subject of the invention is a vulcanized rubber composition obtainable by vulcanization of a vulcanizable rubber composition according to the invention or obtainable by combining and mixing the two parts (A) and (B) of the kit-of-parts according to the invention.

[0016] Another subject of the invention is the production of tires, preferably pneumatic and solid tires, and the production of tire components, preferably rubbers with low glass transition temperatures T gand / or for use in the production of tire components such as rubber compositions comprising a rubber having a rubber composition having a tan δ value as low as possible, in particular in the production of tire components selected from the group of components under base components, i.e. tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, or in the production of rubber articles such as technical rubber articles, preferably in the production of drive belts, straps / belts, molded parts such as buffers / cushions, bearings / mounts such as hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

[0017] Another subject of the present invention is a rubber article such as a tyre, preferably a pneumatic or solid tyre, or a rubber component, or a technical rubber article, produced respectively using the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention or the vulcanised rubber composition according to the invention, preferably in the case of the rubber components these are chosen from the components under the base component, i.e. the tread, the shoulder strip (wing), the cap ply, the belt, the bead and / or the bead reinforcements, and in the case of the rubber article such as a technical rubber article these are preferably chosen from drive belts, straps / belts, moulded parts such as buffers / cushions, bearings / mounts such as hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

[0018] Surprisingly, it has been found that the rubber composition according to the invention has a high dynamic stiffness and at the same time a low tan δ value, the better the decoupling of these two properties, the more flexible and better the targeted performance of the rubber composition can be adjusted, especially compared to rubber compositions containing technical carbon black.

[0019] In particular, the combination of the filler utilized according to the invention and the organosilane utilized according to the invention improves the performance of the rubber composition. By (partial) replacing technical carbon black with the filler utilized according to the invention, the tan δ value can be reduced, while the dynamic stiffness remains at least unchanged. Surprisingly, by additionally using the organosilane utilized according to the invention, in addition to a further reduction in the tan δ value, a higher dynamic stiffness can also be achieved. Furthermore, it has been surprisingly found that the combination of the filler utilized according to the invention and the organosilane utilized according to the invention often achieves an equal to higher elongation at break (compared to vulcanized rubber compositions containing carbon black as filler). Furthermore, the hardness of the rubber composition is not adversely affected. The combination of the filler utilized according to the invention and the organosilane utilized according to the invention is particularly advantageous for rubber compositions crosslinked by sulfur.

[0020] The use of the filler according to the invention is also highly advantageous from an environmental point of view. During the production of technical carbon black, large amounts of CO2 are released in the production process. The filler according to the invention therefore represents an environmentally friendly filler alternative and, in contrast to technical carbon black, does not affect the color of the rubber composition. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 shows the reduction in loss factor by partial replacement of technical carbon black with organic filler L1 and addition of sulfur-functional organosilanes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] For example, the term "comprise" as used herein with respect to the vulcanizable rubber composition according to the invention and the process steps or stages of the process described herein preferably has the meaning "consisting of". For example, in this context with respect to the vulcanizable rubber composition according to the invention, one or more of the other optionally included components described herein below may be included therein in addition to the components that are compulsorily present therein. All the components may be present in each of their preferred embodiments described below. With respect to the processes according to the invention described herein, these may have other optional process steps and stages in addition to the compulsory steps and / or stages.

[0023] The amounts of all the components described herein, such as the components contained in the vulcanizable rubber composition according to the invention (including in each case all the mandatory components and also all the optional components), in each case add up to 100% by weight.

[0024] Vulcanizable rubber composition The vulcanizable rubber composition according to the present invention comprises a rubber component K, a filler component F and a vulcanization system VS, the vulcanization system VS comprises at least sulfur and / or at least one sulfur donor, The rubber component K contains at least one rubber crosslinkable by sulfur, Filler component F is in the range of 0.20 to 0.45 Bq / g carbon. 14 C content and 20~150m 2 / g, preferably >20-150m 2 at least one organic filler having a BET surface area in the range of 0.1 μm / g; The vulcanizable rubber composition further comprises at least one organosilane as a part of filler component F, the at least one organosilane having at least one hydrolyzable group and at least one sulfur atom, and the at least one organosilane is preferably contained in an amount ranging from 0.25 to 5 phr.

[0025] Rubber component K The rubber component K of the vulcanizable rubber composition according to the invention comprises at least one rubber which is crosslinkable by a vulcanization system VS which contains at least sulfur.

[0026] Any type of rubber is suitable for producing the rubber composition according to the invention as long as it can be crosslinked by sulfur. Suitable rubbers are diene rubbers, in particular natural rubber (NR), synthetic natural rubber, in particular isoprene rubber (IR), styrene butadiene rubber (SBR), solution polymerized styrene butadiene rubber (SSBR), emulsion polymerized styrene butadiene rubber (ESBR), functionalized SBR, in particular functionalized SSBR, butadiene rubber (BR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR; nitrile rubber), isobutylene isoprene rubber (IIR), brominated isobutylene isoprene rubber (BIIR), chlorinated isobutylene isoprene rubber (CIIR), and mixtures thereof.

[0027] Preferably, the functionalized diene rubber, such as SSBR, has one or more functional groups in one or more side chains and / or end groups, at least one of the functional groups being preferably selected from polar groups, in particular from the group consisting of carboxyl, hydroxy, amino, carboxylic acid ester, carboxylic acid amide or sulfonic acid groups, and mixtures thereof. Functionalized SSBR is known, inter alia, from DE 10 2008 052 116 A1.

[0028] Preferably, the at least one rubber of the rubber component K is natural rubber, solution polymerized styrene butadiene rubber (SSBR), emulsion polymerized styrene butadiene rubber (ESBR) or butadiene rubber, or a mixture of at least two of the above rubbers. Particularly preferred as the rubber of the rubber component K is natural rubber.

[0029] Vulcanized VS The vulcanization system VS of the vulcanizable rubber composition according to the invention comprises at least sulfur and / or at least one sulfur donor which releases sulfur under the vulcanization conditions, the sulfur acting as crosslinker for the polymer both when it is directly contained in the vulcanization system VS and after it has been released from the sulfur donor used.

[0030] Due to the presence of the vulcanization system VS and the sulfur and / or at least one sulfur donor contained therein, the vulcanizable rubber composition according to the invention can be vulcanized.

[0031] Typically, elemental sulfur in the form of S8 rings is used for crosslinking with sulfur. The S8 rings are opened thermally or by alkaline substances. The sulfur can be present in the rubber composition as soluble or insoluble sulfur. The term accelerator refers to an alkaline organic compound that activates the ring opening. As an alternative to or in addition to elemental sulfur, at least one sulfur donor can be utilized. In this case, sulfur is released from such sulfur donor only during vulcanization. Examples of sulfur donors are sulfur-containing compounds such as 4,4'-dithiomorpholine (DTDM) and tetramethylthiuram disulfide (TMTD), utilized in dosages ranging from 0.5 to 2.0 phr, e.g., 1.5 phr (DTDM) or 1.0 phr (TMTD).

[0032] The content of sulfur in the rubber composition according to the present invention is preferably in the range of 0.25 to 10 phr, particularly preferably 0.25 to 7 phr, further particularly preferably 0.5 to 5 phr, and most preferably 1 to 3 or 2 phr.

[0033] Preferably, the vulcanization system VS comprises at least one accelerator for crosslinking by sulfur. If the vulcanization system VS comprises sulfur as crosslinking agent, the above cited sulfur donors are also suitable as such accelerators. Preferably, the at least one accelerator is a dithiocarbamate, a xanthogenate, a thiuram, such as thiuram monosulfide and / or thiuram disulfide and / or tetrabenzylthiuram disulfide (TbzTD) and / or tetramethylthiuram disulfide (TMTD), a thiazole, such as 2-mercaptobenzothiazole and / or dibenzothiazyl disulfide, a sulfenamide, such as N-cyclohexyl-2-benzothiazyl-sulfenamide (CBS) and / or 2-morpholinothiobenzothiazole and and / or N-tert-butyl-2-benzothiazylsulfenamide, guanidines such as N,N'-diphenylguanidine, thiourea, dithiophosphates, dipentamethylene thiuram tetrasulfide, 4,4'-dithiodimorpholine (DTDM), caprolactam disulfide, and mixtures thereof, more particularly preferably N-tert-butyl-2-benzothiazylsulfenamide, tetrabenzylthiuram disulfide and N,N'-diphenylguanidine, and mixtures thereof.

[0034] The proportion of at least one accelerator in the rubber composition according to the present invention is preferably 0.1 to 10 phr, particularly preferably 0.2 to 8 phr, further particularly preferably 0.2 to 6 phr, and most preferably 0.2 to 3 phr.

[0035] The vulcanization system VS of the vulcanizable rubber composition according to the invention may contain other vulcanizing agents other than sulfur and / or sulfur donors, and / or additives that accelerate vulcanization, such as zinc oxide and / or fatty acids, e.g. stearic acid.

[0036] The vulcanization system VS of the vulcanizable rubber composition according to the present invention may contain one or more additives which accelerate vulcanization but cannot initiate vulcanization by themselves, such as vulcanization accelerators, such as saturated fatty acids, preferably having 12 to 24 carbon atoms, particularly preferably having 14 to 20 carbon atoms, most preferably having 16 to 18 carbon atoms, such as stearic acid, and zinc salts of the above fatty acids.

[0037] When additives accelerating vulcanization, in particular the above-mentioned fatty acids and / or their zinc salts, preferably stearic acid and / or zinc stearate, are utilized in the rubber composition according to the present invention, their proportion is preferably 0 to 10 phr, particularly preferably 1 to 8 phr, most preferably 1.5 to 5 phr.

[0038] The vulcanization system VS of the vulcanizable rubber composition according to the invention may further comprise one or more other vulcanizing agents different from the sulfur and / or sulfur donor, preferably zinc oxide, etc. It is particularly preferred to utilize such vulcanizing agents in the vulcanization system VS in addition to the sulfur and / or sulfur donor.

[0039] When other vulcanizing agents such as zinc oxide are utilized in the rubber composition according to the invention, their proportion is preferably 0-10 phr, particularly preferably 1-8 phr, most preferably 2-5 phr.

[0040] In addition to the at least sulfur and / or at least one sulfur donor used, peroxides can also be added to the vulcanization system VS as further crosslinking agents, however this is not preferred.

[0041] The vulcanization of the rubber composition of the present invention is preferably carried out using sulfur and / or at least one sulfur donor, particularly preferably using sulfur in combination with zinc oxide and / or at least one fatty acid, particularly preferably using sulfur and / or at least one sulfur donor, and most particularly preferably using sulfur in combination with zinc oxide and at least one fatty acid.

[0042] Filler component F The filler component F of the vulcanizable rubber composition according to the present invention comprises at least one organic filler. Since the fillers utilized according to the present invention are organic fillers, inorganic fillers such as precipitated silicas do not fall into this category.

[0043] In particular, the terms filler and organic filler are known to those skilled in the art. Preferably, the organic fillers utilized according to the present invention are reinforcing fillers, i.e. active fillers. Reinforcing or active fillers are characterized by a higher specific surface area than inert fillers and, in contrast to inert (non-reinforcing) fillers, can modify the viscoelastic properties of rubber by interacting with the rubber in the rubber composition. For example, they can affect the viscosity of rubber and improve the elongation under tension and the fracture behavior of the vulcanizate, for example in terms of tear strength, tear and wear. On the other hand, inert fillers dilute the rubber matrix, for example reducing the crushing energy.

[0044] The organic filler utilized in accordance with the present invention has a carbon content in the range of 0.20 to 0.45 Bq / g carbon, preferably 0.23 to 0.42 Bg / g carbon. 14 C content. The above quoted required 14 The C content is achieved by the organic fillers obtained from biomass by further processing or reaction, preferably by fractionation, which can be carried out thermally, chemically and / or biologically, preferably thermally and chemically. Thus, in particular fillers obtained from fossil materials such as fossil fuels, can be obtained by the corresponding 14 Since it does not have a C content, it does not fall within the inventive definition of the fillers to be used according to the invention.

[0045] Biomass is in principle defined herein as any biomass, the term "biomass" as used herein includes so-called phytomass, i.e. biomass of plant origin, zoomass, i.e. biomass of animal origin, and microbial biomass, i.e. biomass of microbial origin, including fungi, where the biomass is dry or fresh and originates from dead or living organisms. A biomass particularly preferred herein for the production of fillers is phytomass, preferably dead phytomass. Dead phytomass includes, inter alia, dead plants, discarded plants or separated plants, and parts thereof. These include, for example, cut and torn leaves, cereal stalks, side shoots, twigs and branches, fallen leaves, felled or pruned trees, but also seeds and fruits and parts derived therefrom, but also sawdust, wood chips / chips and other products derived from wood processing.

[0046] The organic filler utilized in accordance with the present invention is 20 to 150 m 2 / g range, preferably >20-150m 2 / g, particularly preferably 25 to 120 m 2 / g, particularly preferably 30 to 110 m 2 / g, most preferably 40 to 100m 2 / g. One method for determining the BET surface area is cited in the Methods section herein below.

[0047] Preferably, the organic filler has an oxygen content in the range of >8% to <30% by weight, particularly preferably >10% to <30% by weight, further particularly preferably >15% to <30% by weight, most preferably >20% to <30% by weight, based on the ash-free and water-free fillers, respectively. The oxygen content can be determined by high-temperature pyrolysis, for example using a EuroEA3000 CHNS-O Analyzer from EuroVector SpA.

[0048] Preferably, the organic filler has a carbon content in the range of >60% to <90% by weight, particularly preferably >60% to <85% by weight, even more particularly preferably >60% to <82% by weight, most preferably >60% to <80% by weight, based on the ash-free and water-free fillers, respectively. One method for determining the carbon content is cited in the Methods section hereinafter. In this respect, the organic filler differs from carbon blacks, such as technical carbon blacks made from fossil raw materials, and also from carbon blacks made from recycled raw materials, since the corresponding carbon content of carbon blacks is at least 95% by weight.

[0049] Preferably, the organic filler is >18 to <150 m 2 / g, particularly preferably 20 to 130 m 2 / g range, more specifically 25-120m 2 / g, and even more preferably 30 to 110 m 2 / g range, especially 40-100m 2 / g range, most preferably 40 to <100m 2 / g. Methods for determining STSA surface area (statistical thickness specific surface area) are cited in the Methods section herein below.

[0050] Preferably, the organic filler has at least one functional group selected from phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof.

[0051] Preferably, the organic fillers utilized according to the present invention are lignin-based organic fillers produced from biomass and / or biomass components. For example, lignin for the production of lignin-based organic fillers can be isolated, extracted and / or dissolved from biomass. A suitable method for obtaining lignin for the production of lignin-based organic fillers from biomass is a pulping process, such as a hydrolysis process or a Kraft pulping process. The term "lignin-based" as used in the present invention preferably means that one or more lignin moieties and / or one or more lignin scaffolds are present in the organic fillers utilized according to the present invention. Lignins are solid biopolymers that are incorporated into plant cell walls and thus ligninize plant cells. They therefore represent an environmentally friendly filler alternative present in biomass, especially biological regenerative raw materials, and therefore especially in hydrothermally treated form.

[0052] Preferably, the lignin, preferably the organic filler used according to the invention itself, if it is a lignin-based filler, is present in at least partially hydrothermally treated form, particularly preferably obtainable by hydrothermal treatment. Particularly preferably, the organic filler used according to the invention is based on lignin, which can be obtained by hydrothermal treatment. Processes suitable for the hydrothermal treatment of lignin and lignin-containing organic fillers in particular are described, for example, in WO 2017 / 085278 and WO 2017 / 194346, as well as in EP 3 470 457. Preferably, the hydrothermal treatment is carried out in the presence of liquid water at temperatures of >100°C to <300°C, particularly preferably >150°C to <250°C. Preferably, the organic filler is a lignin-based filler, preferably at least the lignin, even more preferably the organic filler itself, is at least partially present in a form obtainable by hydrothermal treatment, particularly preferably obtainable by hydrothermal treatment, the hydrothermal treatment preferably being carried out at a temperature in the range of >100°C to <300°C, particularly preferably >150°C to <250°C.

[0053] Preferably, the organic filler has a pH value in the range from 7 to 9, particularly preferably in the range from >7 to <9, very particularly preferably in the range from >7.5 to <8.5.

[0054] The organic fillers used according to the present invention preferably have a d99 value of <25 μm, even more preferably <20 μm, particularly preferably <18 μm, even more particularly preferably <15 μm, even more preferably <12 μm, even more preferably <10 μm, even more preferably <9 μm, even more preferably <8 μm. The method for determining the d99 value is described in the method section below and is carried out by laser diffraction according to ISO 13320:2009. The d90 and d25 values ​​quoted below are also determined in the same way. The skilled person is aware that the organic fillers used according to the present invention are present in the form of particles, and that the average particle size (average grain size) of these particles is described by the above d99 value and also by the d90 and d25 values ​​described above.

[0055] Particularly preferably, the organic fillers utilized according to the present invention have a d99 value of <9 μm, even more preferably <8 μm, preferably determined by laser diffraction, respectively, according to ISO 13320:2009.

[0056] Preferably, the organic filler has a d90 value of <7.0 μm, particularly preferably <6.0 μm, and / or a d25 of preferably <3.0 μm, particularly preferably <2.0 μm, preferably determined by laser diffraction, each according to ISO 13320:2009.

[0057] Preferably, the rubber composition according to the present invention comprises at least one organic filler in an amount ranging from 1 to 150 phr, particularly preferably from 5 to 100 phr, even more preferably from 10 to 80 phr, even more preferably from 15 to 70 phr, most preferably from 15 to 60 phr.

[0058] The phr (parts per hundred parts rubber) designation used herein is a quantity designation commonly used in the rubber industry for compounding. The parts by weight dosage of an individual component is always based on 100 parts by weight of the total weight of all rubbers present in the compound.

[0059] In addition to the at least one organic filler utilized in accordance with the present invention, filler component F may contain one or more other fillers different from the organic filler utilized in accordance with the present invention.

[0060] If the organic filler utilized according to the present invention serves only as a partial replacement for the commonly found industrial carbon blacks, the rubber composition according to the present invention may also contain industrial carbon blacks, in particular furnace carbon blacks, classified as general purpose carbon blacks, for example under ASTM code N660 or ASTM code N550.

[0061] Additionally or alternatively, the rubber composition according to the invention may contain, in particular, inorganic fillers, such as those with various particle sizes, particle surfaces and chemical properties, which have different possibilities to affect certain properties, in particular the processing behavior (rheology). If further fillers are included, these should preferably have properties as similar as possible to the organic fillers used in the rubber composition according to the invention, in particular with regard to their pH value.

[0062] If other fillers are utilized, they are preferably phyllosilicates such as clay minerals, e.g., talc; carbonates such as calcium carbonate; silicates such as calcium, magnesium, and aluminum silicates; and oxides such as magnesium oxide and silica or silicic acid.

[0063] In particular, while the organic fillers utilized in accordance with the present invention serve only as partial replacements for the more common silicic acid or silica, the rubber composition according to the present invention may also contain such inorganic fillers, for example silica or silicic acid.

[0064] However, in the context of the present invention, zinc oxide does not count as an inorganic filler, since it has the task of additive to accelerate vulcanization. Additional fillers must, however, be selected with care, since silica tends to bind organic molecules to its surface and thus inhibit their action.

[0065] Organosilanes At least one organosilane of the vulcanizable rubber composition according to the invention has at least one hydrolyzable group and at least one sulfur atom, preferably at least one sulfur atom being part of a non-hydrolyzable organic group of the organosilane or covalently bonded to such a group in the form of a functional group such as a thiol group, in particular at least one sulfur atom being part of an aliphatic organic group of the organosilane or covalently bonded to such a group in the form of a functional group such as a thiol group.

[0066] Preferably, the at least one organosilane of the vulcanizable rubber composition according to the invention is a compound of general formula (I) and / or (II). Si(X) 4-y (R) y (I), (X) 3-z (T) z Si-(RA)-Si(X) 3-z (T) z (II) [Wherein, in the case of general formula (I), X's each independently represent a hydrolyzable group which reacts with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group and / or a mixture of these groups, and the hydrolyzable group each independently represents an alkoxy group, particularly preferably OC 1~4 alkyl, The parameter y represents an integer ranging from 1 to 3, but is at least 1, and preferably exactly 1; R is a non-hydrolyzable organic group, preferably an aliphatic C3-C 20group, the sulfur atom being preferably part of at least one functional group selected from the group consisting of thiol groups, block thiol groups, di- and / or polysulfide groups such as tetrasulfide groups, and mixtures thereof, more particularly preferably thiol groups, In the formula (II), X's each independently represent a hydrolyzable group which reacts with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group and / or a mixture of these groups, the hydrolyzable group being, independently of one another, an alkoxy group, particularly preferably OC 1~4 alkyl, R is a non-hydrolyzable organic group having two bonds, preferably an aliphatic C6-C6 alkyl group having two bonds containing at least one sulfur atom. 20 group, preferably at least one disulfide and / or polysulfide group, particularly preferably a di- or tetrasulfide group, Each parameter z represents an integer ranging from 0 to 2, preferably 0 or 2; Unlike the RA group, T represents a non-hydrolyzable organic group having no functional group, and is preferably an aliphatic C1-C 20 group, and particularly preferably does not contain a sulfur atom.

[0067] In the case of monosilanes of general formula (I), it is preferred that at least one R group is a mercaptoalkyl group, R being preferably an aliphatic C3-C8 group, particularly preferably an aliphatic C3-C6 group, and that the monosilane has at least one X group, preferably 2 or 3 X groups.

[0068] Preferably, the monosilanes of general formula (I) are selected from the group consisting of 4-mercaptobutyltrialkoxysilanes and / or 6-mercaptohexyltrialkoxysilanes and / or 3-mercaptopropyltrialkoxysilanes, the alkoxy groups preferably denote, independently of one another, methoxy or ethoxy groups.

[0069] Preferably, the at least one organosilane is a compound of general formula (II).

[0070] In the case of the bis(silane) of the general formula (II), the non-hydrolyzable organic group R is an aliphatic C6-C 20 Groups, particularly preferably aliphatic C6-C 10 Preferably, R is a group, R has at least one sulfur atom. Particularly preferably, R has a di- or polysulfide group, more particularly preferably a di- or tetrasulfide group. Preferably, at least one sulfur atom is present in the R group, and particularly preferably, at least one sulfur atom is not adjacent to a silicon atom.

[0071] Preferably, the bis(silane) of general formula (II) has at least one X group, particularly preferably two or three X groups.

[0072] Preferably, the bis(silane) of general formula (II) is selected from the group consisting of bis(dimethylethoxysilylpropyl)tetrasulfide (DMESPT), bis(dimethylethoxysilylpropyl)disulfide (DMESPD), bis(triethoxysilylpropyl)tetrasulfide (TESPT), bis(triethoxysilylpropyl)disulfide (TESPD) and mixtures thereof, particularly preferably, the bis(silane) of general formula (II) is TESPT and / or TESPD, most preferably TESPD.

[0073] Preferably, the at least one organosilane is contained in the vulcanizable rubber composition according to the invention in an amount ranging from 0.25 to 7 phr, particularly preferably from 0.25 to 5 phr, and most particularly preferably from 0.5 to 3 phr.

[0074] Preferably, the at least one organosilane is contained in the vulcanizable rubber composition according to the invention in an amount ranging from 1 to 10% by weight, particularly preferably from 2 to 8% by weight, even more particularly preferably from 2.5 to 6% by weight, and most preferably from 3 to 6 or 5% by weight, based on the organic filler contained therein.

[0075] Other Components of the Vulcanizable Rubber Composition The rubber composition according to the invention may contain further optional components such as plasticizers / softeners and / or antidegradants and / or waxes and / or resins for light stabilization, especially resins which increase adhesion.

[0076] The use of softeners can affect the properties of the unvulcanized rubber composition, such as in particular its processability, and can also affect the properties of the vulcanized rubber composition, such as its flexibility, in particular at low temperatures. Particularly suitable softeners in the context of the present invention are mineral oils from the group of paraffinic oils (substantially saturated linear hydrocarbons) and naphthenic oils (substantially saturated cyclic hydrocarbons). Aromatic hydrocarbon oils can also be used and are even preferred. However, with regard to the adhesion of the rubber composition to other rubber-containing components in a tire, such as the carcass, mixtures of paraffinic and / or naphthenic oils can also be advantageous as softeners. Other possible softeners are, for example, esters of aliphatic dicarboxylic acids, such as adipic or sebacic acid, paraffin waxes and polyethylene waxes. Of the softeners, paraffinic and naphthenic oils are particularly suitable in the context of the present invention. Most preferred, however, are aromatic oils, in particular aromatic mineral oils.

[0077] Preferably, the softeners, of which paraffinic and / or naphthenic, especially aromatic process oils, are utilized in an amount of 0 to 10 phr, particularly preferably 1 to 8 phr, even more particularly preferably 1 to 7 phr, and most preferably 1 to 3 phr.

[0078] Preferably, quinolines such as TMQ (2,2,4-trimethyl-1,2-dihydroquinoline) and diamines such as 6-PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) or IPPD (N-isopropyl-N'-phenyl-p-phenylenediamine), particularly preferably IPPD, are used as deterioration inhibitors. The proportion thereof is preferably 1 to 10 phr, particularly preferably 1 to 7 phr, further particularly preferably 1 to 5 phr, and most preferably 1 to 2 phr.

[0079] Examples of light stabilizing waxes are Negozone 3457 from the H&R Group or Antilux light stabilizing waxes from Rhein Chemie, such as Antilux 111 or Antilux 654. Preferably, their proportion is between 0.25 and 10 phr, particularly preferably between 0.5 and 7 phr, very particularly preferably between 0.5 and 5 phr and most preferably between 0.5 and 2 phr.

[0080] So-called adhesion-promoting resins can be used to improve the adhesion of the vulcanized rubber compound of the invention to other adjacent tire components. Particularly suitable resins are those based on phenol, preferably from the group consisting of phenolic resins, phenol-formaldehyde resins and phenol-acetylene resins. In addition to phenol-based resins, aliphatic hydrocarbon resins, such as Escorez™ 1102 RM from ExxonMobil, and aromatic hydrocarbon resins can also be used. Aliphatic hydrocarbon resins in particular improve the adhesion to other rubber components of the tire. They generally have lower adhesion than phenol-based resins and can be used alone or in a mixture with phenol-based resins.

[0081] If adhesion-promoting resins are used, they are preferably selected from the group consisting of phenol-based resins, aromatic hydrocarbon resins and aliphatic hydrocarbon resins, preferably in a proportion of 0 to 15 phr, particularly preferably 1 to 15 phr, more particularly preferably 2 to 10 phr and most preferably 3 to 8 phr.

[0082] Kit of parts Another subject of the invention is a method for producing ... mixture of a plurality of compounds, in a spatially separated manner, a rubber composition comprising as part (A) at least the above-mentioned rubber component K used according to the invention and at least a filler component F used according to the invention, the part (A) however not comprising the sulfur and / or at least one sulfur donor of the vulcanization system VS used according to the invention; As part (B), a vulcanization system VS used according to the invention, which comprises at least sulfur and / or at least one sulfur donor; and wherein the organosilane used according to the invention is contained in the filler component F in part (A) in an amount preferably in the range of 0.25 to 5 phr.

[0083] Part (A) therefore represents a rubber composition which is not yet vulcanizable by sulfur per se and therefore not vulcanizable by sulfur at this point: vulcanization by sulfur is only possible after mixing of parts (A) and (B), even if sulfur itself is present and / or is released only from at least one sulfur donor.

[0084] Preferably, the components K and F of the rubber composition according to the invention on the one hand and the vulcanization system VS on the other hand are spatially separated from each other in a kit of parts and can therefore be stored. The kit of parts serves to prepare a vulcanizable rubber composition. Thus, for example, a rubber composition constituting one part of the kit of parts, comprising components K and F and optionally other components including a vulcanizing agent different from sulfur, such as zinc oxide and / or at least one fatty acid, can be used as part (A) in stage 1 of the process for preparing a vulcanizable rubber composition, which is further described herein below, and the second part of the kit of parts, i.e. the vulcanization system VS, comprising at least sulfur and / or at least one sulfur donor, as part (B) can be used in stage 2 of said process, the organosilane used according to the invention being included in the filler component F in part (A).

[0085] In contrast to the vulcanizable rubber composition according to the invention, which comprises both components K, F of the rubber composition, the organosilane having at least one hydrolyzable group and at least one sulfur atom, and the associated vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, preferably as a homogeneous mixture so that the vulcanizable rubber composition can be directly vulcanized, the rubber composition comprising components K, F, the organosilane having preferably at least one hydrolyzable group and at least one sulfur atom, and the vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, are spatially separated from one another in the kit-of-parts according to the invention.

[0086] All preferred embodiments described hereinabove with respect to the vulcanizable rubber composition according to the invention are also preferred embodiments with respect to the kit-of-parts according to the invention.

[0087] Preferably, the kit-of-parts according to the invention comprises: A rubber composition comprising, as part (A), at least components K, F, and one organosilane having at least one hydrolyzable group and at least one sulfur atom; As part (B), a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor and also zinc oxide, which may alternatively be present in part (A); Includes.

[0088] Particularly preferably, the kit-of-parts according to the invention comprises: A rubber composition comprising, as part (A), at least components K, F, and one organosilane having at least one hydrolyzable group and at least one sulfur atom; As part (B), a vulcanization system comprising at least sulfur and / or at least one sulfur donor, zinc oxide and at least one saturated fatty acid, such as stearic acid and / or optionally zinc stearate, where at least zinc oxide and / or the fatty acid may alternatively be present in part (A). Includes.

[0089] Process for preparing a vulcanizable rubber composition Another subject of the invention is a process for preparing the vulcanizable rubber composition according to the invention.

[0090] All preferred embodiments described hereinbefore with respect to the vulcanizable rubber composition according to the invention and the kit-of-parts according to the invention are also preferred embodiments with respect to the process according to the invention.

[0091] The preparation of the vulcanizable rubber composition according to the present invention is preferably carried out in two stages, namely stages 1 and 2.

[0092] In a first step (step 1), the rubber composition is first prepared as a base mixture (masterbatch) by mixing all the components utilized in the preparation of the vulcanizable rubber composition according to the invention with one another, but not with the sulfur and / or at least one sulfur donor. In a second step (step 2), the sulfur and / or at least one sulfur donor of the vulcanization system VS, and optionally additional components, are incorporated into the rubber composition obtained after step 1.

[0093] Phase 1 Preferably, at least one rubber, which is contained in the rubber component K of the rubber composition according to the invention, and a resin which may be used optionally different therefrom are provided. However, the latter may alternatively be added subsequently together with other additives. Preferably, the rubber has a temperature of at least room temperature (23° C.) or is preheated, particularly preferably to a temperature of at most 50° C., more particularly preferably to a temperature of at most 45° C., particularly preferably to a temperature of at most 40° C. Particularly preferably, the rubber is pre-masticated for a short time before the other constituents are added. If an inhibitor such as magnesium oxide is used for subsequent vulcanization control, it is preferably added at this point.

[0094] Then, the at least one organic filler utilized according to the present invention, and optionally other fillers, except preferably zinc oxide, are added, since zinc oxide is used as a component of the vulcanization system in the rubber composition according to the present invention as described herein above and is therefore not considered a filler herein. The addition of the at least one organic filler and optionally other fillers is preferably carried out gradually.

[0095] Advantageously, but not compulsorily, the softener, the organosilane utilized according to the present invention, and other components such as vulcanizing agents other than sulfur, e.g., stearic acid and / or zinc stearate and / or zinc oxide, are added only after the addition of at least one organic filler or other fillers, if used. This facilitates the incorporation of at least one organic filler, and other organic fillers, if present. However, it may be advantageous to incorporate the organic filler, or a portion thereof, if present, together with the softener and any other components optionally used.

[0096] The maximum temperature obtained during the preparation of the rubber composition in the first stage ("dump temperature") should not exceed 170°C, since above these temperatures partial decomposition of the reactive rubber and / or organic fillers is possible. However, depending in particular on the rubber used, temperatures of >170°C, for example up to 200°C, may also be possible. Preferably, the maximum temperature in the preparation of the rubber composition in the first stage is between 80°C and <200°C, particularly preferably between 90°C and 190°C, most preferably between 95°C and 170°C.

[0097] The mixing of the components of the rubber composition is usually carried out by means of internal mixers equipped with tangential or intermeshing (i.e. intermeshing) rotors. The latter usually allow better temperature control. Mixers with tangential rotors are also called tangential mixers. However, mixing can also be carried out using, for example, twin-roll mixers. Depending on the rubber used, the mixing process can be carried out conventionally, starting with the addition of the polymer, or vice versa, i.e. adding all the other components of the mixture and then adding the polymer last.

[0098] After the preparation of the rubber composition is complete, it is preferably cooled before carrying out the second stage. This type of process is also called relaxation. The typical relaxation period is 6 to 24 hours, preferably 12 to 24 hours.

[0099] Phase 2 In a second step, at least sulfur and / or at least one sulfur donor of the vulcanization system VS, preferably additional components, are incorporated into the rubber composition of the first step, thereby obtaining a vulcanizable rubber composition according to the invention. Preferably, accelerators for crosslinking with sulfur, if utilized / present, are also incorporated in step 2.

[0100] If zinc oxide and, optionally, at least one saturated fatty acid, such as stearic acid, are utilized as a vulcanization system in addition to the sulfur and / or at least one sulfur donor, the addition of all these components takes place in stage 2. However, these components, except for the sulfur and / or at least one sulfur donor, can also be integrated into the rubber composition already in stage 1.

[0101] The maximum temperature attained during the preparation of the compound of the vulcanization system into the rubber composition in the second stage ("dump temperature") should preferably not exceed 130° C., particularly preferably not exceed 125° C. The preferred temperature range is between 70° C. and 125° C., particularly preferably between 80° C. and 120° C. At temperatures exceeding the maximum temperature of the crosslinking system of 105° C. and 120° C., premature vulcanization may occur.

[0102] After incorporating the vulcanization system in Stage 2, the composition is preferably cooled.

[0103] In the two-stage process described herein above, a rubber composition is first obtained in a first stage and then expanded to a vulcanizable rubber composition in a second stage.

[0104] Process for further processing of the vulcanizable rubber composition according to the present invention Prior to vulcanization, the vulcanizable rubber composition thus prepared undergoes a deformation process, preferably to be customized or adapted to the final article. The rubber composition is formed, preferably by extrusion or calendaring, into the suitable shape required for the vulcanization process. Vulcanization may be carried out by pressure and temperature in a vulcanization mold, or vulcanization is carried out without pressure in a temperature-controlled channel where air or liquid material realizes the heat transfer.

[0105] Vulcanized rubber composition Another subject of the invention is a vulcanized rubber composition obtainable by vulcanization of a vulcanizable rubber composition according to the invention or obtainable by combining and mixing the two parts (A) and (B) of the kit-of-parts according to the invention.

[0106] All preferred embodiments described hereinbefore with respect to the vulcanizable rubber composition according to the invention and the kit-of-parts according to the invention and the process according to the invention are also preferred embodiments with respect to the vulcanized rubber composition according to the invention.

[0107] Typically, vulcanization is carried out under pressure and / or under the influence of heat. Suitable vulcanization temperatures are preferably 100°C to 200°C, particularly preferably 120°C to 180°C, most preferably 140°C to 170°C. Optionally, vulcanization is carried out at a pressure in the range of 50 bar to 300 bar. However, vulcanization can also be carried out at a pressure in the range of 0.1 bar to 1 bar, for example in the case of profiles. The closing pressure of the press typically ranges from 150 bar to 500 bar, depending on the mixture and the product geometry.

[0108] use Another subject of the invention is the production of tires, preferably pneumatic and solid tires, and tire components, preferably rubbers having a low glass transition temperature T gand / or for use in the production of tire components such as rubber compositions comprising a rubber having a rubber composition having a tan δ value as low as possible, in particular in the production of tire components selected from the group of components under base components, i.e. tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, or in the production of rubber articles such as technical rubber articles, preferably in the production of drive belts, straps / belts, molded parts such as buffers / cushions, bearings / mounts such as hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

[0109] The term "technical rubber article" (also mechanical rubber goods, MRG) is known to those skilled in the art. Examples of technical rubber articles are drive belts, straps / belts, molded parts such as shock absorbers / cushions, bearings / mounts, especially hydromounts, conveyor belts, profiles, seals, dampers and / or hoses.

[0110] All preferred embodiments described herein above with respect to the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention, the process according to the invention and the vulcanized rubber composition according to the invention are also preferred embodiments with respect to the above uses according to the invention.

[0111] Tyres and tyre components Another subject of the present invention is a tire, preferably a pneumatic or solid tire, or tire components, produced respectively using the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention or the vulcanized rubber composition according to the invention, preferably in the case of tire components, these are chosen from the components under the base component, i.e. tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement.

[0112] All preferred embodiments described hereinbefore with respect to the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention, the process according to the invention and the vulcanized rubber composition according to the invention as well as the use according to the invention are also preferred embodiments with respect to the above-mentioned tyre according to the invention.

[0113] Rubber articles, in particular technical rubber articles Another subject of the present invention is a rubber article, in particular a technical rubber article, produced by utilizing the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention or the vulcanized rubber composition according to the invention, preferably chosen from drive belts, straps / belts, molded parts, such as dampers / cushions, bearings / mounts, in particular hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

[0114] All preferred embodiments described herein above with respect to the vulcanizable rubber composition according to the invention, the kit-of-parts according to the invention, the process according to the invention and the vulcanized rubber composition according to the invention as well as the use according to the invention are also preferred embodiments with respect to the preferred technical rubber articles according to the invention.

[0115] How to decide 1. 14 Determination of C content 14 The determination of the C content (biologically based carbon content) is carried out by the radiocarbon method according to DIN EN 16640:2017-08.

[0116] 2. Determination of particle size distribution The particle size distribution can be determined by laser diffraction of the material dispersed in water (1% by weight in water) according to ISO 13320:2009, with ultrasonic treatment of 12000 Ws carried out before the measurement. The volume fraction is designated for example as d99 (unit μm) (diameter of the grains of 99% of the volume of the sample is below this value). The d90 and d25 values ​​(unit μm) are determined similarly.

[0117] 3. Determination of Carbon Content The carbon content is determined by elemental analysis in accordance with DIN 51732: 2014-7.

[0118] 4. Determination of oxygen content The oxygen content is determined by high temperature pyrolysis using a EuroEA3000 CHNS-O analyzer from EuroVector SpA. In the process, the CHNS content is determined by the above analyzer and the oxygen is subsequently calculated as the difference (100-CHNS).

[0119] 5. Determination of the dry matter content of utilized organic fillers The dry matter content of the samples was determined in accordance with DIN 51718:2002-06 as follows. For this, an MA100 moisture balance from the company Sartorius was heated to a drying temperature of 105° C. The dried samples, if not already in powder form, were ground or crushed in a mortar to a powder. On the moisture balance, approximately 2 g of the sample to be measured was weighed into a suitable aluminum pan and then the measurement was started. As long as the mass of the sample did not change by more than 1 mg in 30 seconds, this mass was considered constant and the measurement was terminated. The dry matter content then corresponds to the declared content of the sample (in % by mass). At least one duplicate determination was carried out for each sample. The weighted average value was reported.

[0120] 6. Determination of pH value of utilized organic filler The pH was determined according to the ASTM D 1512 standard as follows: If the dry samples were not already in powder form, they were ground or crushed in a mortar to a powder. In each case, 5 g of sample and 50 g of fully deionized water were weighed into a glass beaker. Using a magnetic stirring device equipped with heating function and a stirring flea, the suspension was heated to a temperature of 60° C., with constant stirring, and the temperature was maintained at 60° C. for 30 minutes. The heating function of the stirring device was then stopped so that the mixture could cool while stirring. After cooling, the evaporated water was replenished by adding again fully deionized water and stirred again for 5 minutes. The pH value of the suspension was determined using a calibrated measuring instrument. The temperature of the suspension should be 23° C. (±0.5° C.). Duplicate determinations were made for each sample and the average value was reported.

[0121] 7. Determination of ash content of organic fillers The water-free ash content of the samples was determined by thermogravimetric analysis according to the DIN 51719 standard as follows: Before weighing, the samples were crushed or ground in a mortar. Prior to the ash determination, the dry matter content of the weighed material is determined. The sample material was weighed to the nearest 0.1 mg in a crucible. The furnace containing the sample was heated to a target temperature of 815° C. with a heating rate of 9 K / min and then held at this temperature for 2 hours. The furnace was then cooled to 300° C. before the sample was removed. The sample was cooled to room temperature in a desiccator and weighed again. The remaining ash was correlated with the initial mass and thus the mass percentage of ash was determined. Triplicate determinations were made for each sample and the average values ​​were reported.

[0122] 8. Determination of BET and STSA surface areas of organic fillers The specific surface area of ​​the investigated fillers was determined by nitrogen adsorption according to the ASTM D 6556 (2019-01-01) standard for industrial carbon black, according to which the BET surface area (specific total surface area according to Brunauer, Emmett and Teller) and the external surface area (STSA surface area; statistical thickness specific surface area) were also determined as follows:

[0123] The samples to be analyzed were dried at 105°C prior to the measurement to a dry matter content of ≥ 97.5% by weight. Furthermore, the measuring cell was dried in a drying oven at 105°C for several hours before the sample was weighed. The sample was then filled into the measuring cell using a funnel. If the upper measuring cell shaft was contaminated during filling, it was cleaned using a suitable brush or pipe cleaner. In the case of strongly scattering (electrostatic) materials, glass wool was additionally weighed onto the sample. Glass wool was used to hold back any material that may fly off during the bake-out process and contaminate the unit.

[0124] The samples to be analyzed were baked out at 150° C. for 2 h, and the Al2O3 standard was baked out at 350° C. for 1 h. Depending on the pressure range, the following N2 dosages were used for the determination: p / p0=0~0.01: N2 dosage: 5ml / g p / p0=0.01-0.5: N2 dosage: 4ml / g.

[0125] To determine the BET surface, extrapolation was performed over at least six measurement points in the range of p / p0 = 0.05-0.3. To determine the STSA, extrapolation was performed over at least seven measurement points in the range of adsorbed N2 layer thickness t = 0.4-0.63 nm (corresponding to p / p0 = 0.2-0.5).

[0126] 9. Determination of hardness The determination of the Shore A hardness of the vulcanized rubber compositions was carried out at 23 °C according to ISO 48-4:2018-08 using a digital Shore hardness tester from Sauter GmbH. In order to reach a specimen thickness of at least 6 mm required by the standard, the specimens consisted of no more than three layers. For this, three S2 bars, punched out with a punch to carry out the tensile test according to ISO 37:2011, were stacked on top of each other. For each specimen stack, five measurements were carried out at different points of the stack. The obtained results represent the average value of these five measurements. Between vulcanization and testing, the samples were stored at room temperature in the laboratory for at least 16 h.

[0127] 10. Determination of crosslink density / reaction kinetics The crosslink density and reaction kinetics of the rubber compositions were determined according to DIN 53529-3:1983-06 at 160°C but at a deflection of 0.5 or 3° (depending on the values ​​given in the experimental part). The measurement time was 30 min. The process included the minimum and maximum torques (M L , M H ) was determined. From these, the difference Δ(Δ(M H -M L ) (maximum torque - minimum torque) was calculated. Furthermore, the minimum torque M L Starting from the time, the torque reaches the maximum torque M H The time to reach 10%, 50%, and 90% of the T 10 , T 50 and T 90 and specified.

[0128] 11. Determination of elongation under tension For vulcanized rubber compositions, elongation under tension was determined, including tensile strength and elongation at break, according to ISO 37:2011.

[0129] 12. Dynamic Mechanical Thermal Analysis (DMTA) or Dynamic Mechanical Analysis (DMA) DMTA / DMA serves to characterize the viscoelastic behavior. The tests were carried out according to the standard DIN EN ISO 6721 1-12, in this case 6721-7 was used. The viscoelastic behavior was analyzed by a test device MCR 501 from Anton Paar. In the process, the vulcanized rubber composition was subjected to a sinusoidal oscillatory stress in the range of linear elastic deformation. The tests were carried out with the following parameters: deformation: 1%; frequency: 10 Hz; type of stress: torsion; heating rate: 2 K / min; heating sequence: -70°C to +100°C. The amplitude and phase shift of the deformation were recorded, and the viscoelastic behavior could be described using the complex and loss modulus as well as the mechanical loss factor tan δ.

[0130] In general, the complex or dynamic modulus (G*) is defined as follows: G*=G'+i x G" where G' is the storage modulus (real component; represents the elastic component) G": Loss modulus (imaginary component; represents the viscous component) i: imaginary number

[0131] The loss factor tan δ (tan δ) is defined as follows: tan δ=G" / G'

[0132] 13.Material density of the filler used The material density of the filler was determined by helium pycnometer according to ISO 21687.

[0133] Examples and Comparative Examples The following examples and comparative examples serve to illustrate the invention but should not be construed as limiting it.

[0134] 1. Production of the organic filler used according to the invention 1.1 As a first organic filler according to the invention, lignin L1, obtainable by hydrothermal treatment, was used.

[0135] The hydrothermally obtainable lignin L1 was produced according to the process for producing hydrothermally obtainable lignin described in WO 2017 / 085278.

[0136] For this purpose, a lignin-containing liquid is prepared. First, water and lignin are mixed, thus preparing a lignin-containing liquid with a content of 15% of the organic dry mass. Subsequently, the lignin is largely dissolved in the lignin-containing liquid. For this purpose, the pH value is adjusted by adding NaOH. The preparation of the solution is accelerated by vigorous mixing at 80° C. for 3 hours. The lignin-containing liquid is subjected to a hydrothermal treatment, thus obtaining a solid matter. In the process, the prepared solution is heated at 2 K / min to a reaction temperature of 220° C. and then held for a reaction period of 8 hours. Cooling is then carried out. As a result, an aqueous suspension of solid matter is obtained. By filtration and washing, the solid matter is largely dehydrated and washed. Subsequent drying and heat treatment are carried out under nitrogen in a fluidized bed, drying at a temperature of 50° C. at 1.5 K / min and held for 2.5 hours, followed by heat treatment at a temperature of 190° C. at 1.5 K / min and held for 15 minutes, then cooling again. The dried solids are deagglomerated using nitrogen in a counter jet mill to a d99 value <10 μm (determined according to the determination method described herein above).

[0137] 1.2 As a second organic filler according to the invention, lignin L2, obtainable by hydrothermal treatment, is utilized, which is prepared similarly to the process described in section 1.1 and can be used as an organic filler. However, deviating from the process described in 1.1, the hydrothermal treatment was carried out such that the produced lignin-containing solution was prepared with an organic dry mass content of 10% by mass. After adding NaOH, the lignin-containing liquid was subjected to hydrothermal treatment, heated at 1.5 K / min to a reaction temperature of 230 ° C and maintained for a reaction time of 1 hour. Furthermore, the lignin-containing liquid was modified using formaldehyde before the hydrothermal treatment was carried out. Finally, a final grinding was carried out in a steam jet mill.

[0138] 1.3 However, deviating from the process described in 1.1, a hydrothermal treatment was carried out such that the produced lignin-containing solution was prepared with an organic dry mass content of 9.7% by mass. After adding NaOH, the lignin-containing liquid was subjected to a hydrothermal treatment, heated at 1.5 K / min to a reaction temperature of 240 °C and maintained for a reaction time of 2 hours. Furthermore, the lignin-containing liquid was modified using formaldehyde before the hydrothermal treatment was carried out. Finally, a final grinding was carried out in a counter jet mill.

[0139] 1.4 The lignins L1, L2 and L3 obtainable by hydrothermal treatment were characterized as specified in Table 1.1 below by the method described herein above.

[0140] [Table 1]

[0141] 2. Production of vulcanizable rubber compositions The vulcanizable rubber compositions were prepared by a two-stage process.

[0142] In a first step, the components of the rubber composition according to the invention, including the rubber composition K, the filler component F and the organosilane, were compounded to prepare a rubber composition (master batch) as a base mixture. In a second step, the components of the crosslinking system (vulcanization system VS) were mixed.

[0143] Vulcanizable rubber compositions having an organic filler L1 utilized according to the present invention and a corresponding comparative rubber composition having industrial carbon black as the sole filler were prepared as follows.

[0144] Phase 1 Natural rubber (NR) SMR 5 CV 60 from the trading company Astlett Rubber was used as the rubber. When technical carbon black is used as the sole filler (comparative rubber composition VK1V1), it is added as 33.3% of one batch (together with the additives used, such as zinc oxide, stearic acid and other additives; see table 2.1 below) after 1:30 minutes and as 33.3% of another batch (together with 50% of the process oil used) after 3:30 minutes. After 5 minutes, 33.3% of the last batch of technical carbon black is added together with the remaining 50% of the process oil used. In the case of partial replacement of the technical carbon black with the filler utilized according to the invention (comparative rubber composition VK1V2 and rubber composition VK1B1 according to the invention), 100% of the technical carbon black used is added together with the additives used after 1:30 minutes. 3: After 30 minutes, 50% of the filler utilized according to the invention is added (together with 50% of the process oil used), and after 5 minutes another 50% is added (together with another 50% of the process oil used and, in the case of example VK1B1 according to the invention, also with 100% of the sulfur-functional organosilane).

[0145] For all compositions, the components of the mixture were mixed dispersively and distributively until the mixing process was stopped after 10 minutes (13 minutes for V1B1 only) and the rubber composition was removed from the laboratory mixer. Under these mixing conditions, the rubber composition achieved a final temperature of 130°C to 155°C. After the preparation of the rubber composition was completed, it was cooled before carrying out the second stage (relaxation / storage).

[0146] By means of step 1 described herein above, a rubber composition was obtained which is used according to the invention, comprising natural rubber (K1B1) as rubber component K and lignin L1 obtainable by hydrothermal treatment as organic filler of the filler component. Furthermore, the rubber composition K1B1 according to the invention contained bis(triethoxysilylpropyl) disulfide (TESPD) as sulfur-functional organosilane.

[0147] Further, comparative compositions K1V1 and K1V2 were obtained which also contained natural rubber as the rubber component K. Comparative composition K1V1 contained commercial carbon black as the only organic filler in the filler component, but did not contain lignin L1 and did not contain any sulfur-functional organosilane, and comparative composition K1V2 contained lignin L1 but did not contain any sulfur-functional organosilane.

[0148] The exact composition of the vulcanizable rubber composition can be seen in Table 2.1 below, the amounts being given in phr (parts by weight per 100 parts by weight of rubber).

[0149] Phase 2 In the second stage, sulfur as a crosslinking agent and one (K1V1, K1V2) or several (K1B1) accelerators were incorporated into the rubber composition of the first stage, thus obtaining a vulcanizable rubber composition. The sulfur crosslinking agent and one or several sulfur accelerator systems as co-agents were added to a laboratory mixer and mixed together with the rubber composition from the first stage at a speed of 50 rpm for 5 minutes. In this case, the final temperature was 90°C to 100°C. After incorporating the crosslinking system, the obtained composition was cooled.

[0150] By means of step 2 described herein above, after addition of the vulcanization system VS consisting of crosslinker and accelerator, a vulcanizable rubber composition according to the invention (VK1B1) was obtained, which can be vulcanized after the implementation of step 2 has been completed. Furthermore, two vulcanizable comparative rubber compositions (VK1V1 and VK1V2) were obtained in this way, which can also be vulcanized after the implementation of step 2 has been completed. The exact composition of the vulcanizable rubber compositions can be seen from table 2.1 below.

[0151] [Table 2]

[0152] As technical carbon black, the commercial product Carbon Black N550 from Pentacarbon (distributor of carbon black) was used. The organic filler L1 has already been described herein above. Bis(triethoxysilylpropyl) disulfide (TESPD, Si 266) from Evonik was used as the sulfur-functional organosilane. As process oil, naphthenic softener from Hansen & Rosenthal was used. As antiaging agent, N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) from Lehmann & Voss & Co. under the trade name Luvomax IPPD was used, and as light stabilizing wax, Negozone 3457 F from Hansen & Rosenthal was used. As crosslinker (sulfur), Struktol SU95 from Schill+Seilacher was used. As accelerators the products TBBS-80 (B1), TBzTD-70 (B2) and DPG-80 (B3) from Rhein Chemie were used. As zinc oxide the product WeiBsiegel from Bruggemann was used. As stearic acid the product Palmera B 1805 from Avokal-Heller was used.

[0153] Vulcanizable rubber compositions having fillers L2 and L3 utilized in accordance with the present invention, as well as corresponding comparative rubber compositions having industrial carbon black as the sole filler, were prepared as follows.

[0154] Phase 1 Natural rubber (NR) SMR 5 CV 60 from the commercial company Astlett Rubber was used as the rubber. When technical carbon black is used as the sole filler (comparative rubber compositions VK2V1 and VK2V2), it is added as 33.3% of one batch (together with the additives used, e.g. zinc oxide, stearic acid and other additives; see Table 2.2 below) after 2:00 minutes and as 33.3% of another batch (together with 50% of the process oil used) after 3:00 minutes. After 5 minutes, 33.3% of the last batch of technical carbon black is added together with the remaining 50% of the process oil used. In the case of partial replacement of the technical carbon black with one of the fillers used according to the invention (rubber compositions VK2B1 and VK2B2 according to the invention), 50% of the technical carbon black used is added after 2:00 minutes together with the additives used, and after 3:00 minutes the remaining 50% of the technical carbon black is added together with 50% of the process oil used. After 5:00 minutes, 100% of the filler used according to the invention is added together with 50% of the process oil used and 100% of the sulfur-functional organosilane. When the filler used according to the invention is used as the sole filler (rubber compositions VK2B3, VK2B4 and VK2B5 according to the invention), it is added as 33.3% of one batch (together with the additives used) after 2:00 minutes and as 33.3% of another batch (together with 50% of the process oil used) after 3:00 minutes. After 5 minutes, 33.3% of the final batch of filler utilized in accordance with the present invention is added along with another 50% of the process oil used and 100% of the organosilane utilized in accordance with the present invention.

[0155] For all compositions, the components of the mixture were dispersively and distributively mixed until the mixing process was stopped after 16 minutes and the rubber composition was removed from the laboratory mixer. Under these mixing conditions, the rubber composition achieved a final temperature of 145°C to 155°C. After the preparation of the rubber composition was complete, it was cooled before performing the second stage (relaxation / storage).

[0156] According to step 1 described herein above, five rubber compositions according to the present invention were obtained, which comprised natural rubber as rubber component K and lignin L2 (K2B1 and K2B3) or lignin L3 (K2B2, K2B4 or K2B5) obtainable by hydrothermal treatment as organic filler of the filler component. Furthermore, rubber compositions K2B1, K2B2, K2B3, K2B4 and K2B5 according to the present invention comprised bis(triethoxysilylpropyl) disulfide (TESPD) as sulfur-functional organosilane.

[0157] Furthermore, comparative compositions K2V1 and K2V2 were obtained, which also contained natural rubber as the rubber component K, but did not contain lignin L2 or L3, and contained exclusively commercial carbon black as the organic filler of the filler component, and did not contain any sulfur-functional organosilane.

[0158] The exact composition of the vulcanizable rubber composition can be seen in Table 2.2 below, the amounts being given in phr (parts by weight per 100 parts by weight of rubber).

[0159] Phase 2 In the second stage, one (K2V1) or two (K2V2, K2B1, K2B2, K2B3, K2B4 and K2B5) accelerators were incorporated as crosslinking agents into the rubber composition of the first stage, thus respectively obtaining a vulcanizable rubber composition. The sulfur crosslinking agent and one or two sulfur accelerator systems as co-agents were added to a laboratory mixer and mixed together with the rubber composition from the first stage at a speed of 50 rpm for 5 minutes. In this case, the final temperature was 90°C to 100°C. After incorporating the crosslinking system, the resulting composition was cooled.

[0160] By means of step 2 described herein above, after the addition of the vulcanization system VS consisting of crosslinker and accelerator, five vulcanizable rubber compositions according to the invention (VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5) were obtained, which can be vulcanized after the implementation of step 2 has been completed. Furthermore, in this way, two comparative vulcanizable rubber compositions (VK2V1 and VK2V2) were obtained, which can also be vulcanized after the implementation of step 2 has been completed. The exact composition of the vulcanizable rubber compositions can be seen from table 2.2 below.

[0161] [Table 3]

[0162] The components natural rubber, technical carbon black, process oil, organosilane, zinc oxide, stearic acid, crosslinking agent, light stabilizing wax, antiaging agent, and accelerators B1 and B2 listed in Table 2.2 were used as the products already described in connection with Table 2.1. The organic fillers L2 and L3 have been already described herein above.

[0163] 3. Inspection and testing of vulcanizable rubber compositions and vulcanized compositions obtainable therefrom 3.1 Crosslink density and reaction kinetics The rubber compositions obtained after stage 2 were examined with regard to their raw mix properties, in which the reaction kinetics and crosslink density were measured according to the methods described herein above.

[0164] Table 3.1 shows the minimum and maximum torque (M L , M H ), difference Δ(M H -M L ) and time T 10 , T 50 and T 90 A summary of the results obtained for . Values ​​were determined at a deflection of 3°C.

[0165] [Table 4]

[0166] The rubber composition VK1B1 according to the invention has similar reaction kinetics (T 10 , T 50 , T 90 ) The slight deviation is the difference between the maximum and minimum torques, Δ(M H -M L ) (units dNm)

[0167] Table 3.2 shows the minimum and maximum torque (M L , M H ), difference Δ(M H -M L ) and time T 10 , T 50 and T 90 A summary of the results obtained for . Values ​​were determined at a deflection of 0.5°C.

[0168] [Table 5]

[0169] The rubber compositions VK2B1 and VK2B2 according to the invention, characterized by partial replacement of carbon black with lignin-based fillers L2 or L3, exhibit similar or improved reaction kinetics (T 10 , T 50 , T 90 The rubber compositions VK2B3, VK2B4 and VK2B5 according to the invention, characterized by the complete replacement of carbon black with the lignin-based fillers L2 and L3, show increased incubation times (better scorch times) and longer T 90 Brings value.

[0170] 3.2 Tensile strength, elongation at break, Shore A hardness The resulting rubber compositions K1V1, K1V2 and K1B1 were all vulcanized at 160° C., the vulcanization time being adapted to the reaction kinetics of the respective mixture. The vulcanization time was 6 minutes for mixture VK1V1, 7 minutes for mixture VK1V2 and 5 minutes for mixture VK1B1. The tensile strength, elongation at break and Shore A hardness were subsequently determined according to the methods described herein above.

[0171] Table 3.3 gives an overview of the results obtained for the comparative examples VK1V1 and VK1V2 and for the rubber composition VK1B1 vulcanized according to the invention.

[0172] [Table 6]

[0173] The rubber composition VK1B1 according to the invention has a similar tensile strength as the comparative rubber compositions VK1V1 and VK1V2. By partial replacement of the technical carbon black with the organic filler L1 and the addition of a sulfur-functional organosilane, equal hardness (Shore A) and equal elongation at break are achieved.

[0174] The resulting rubber compositions K2V1, K2V2, as well as K2B1, K2B2, K2B3, K2B4 and K2B5 were all vulcanized at 160° C., the vulcanization times being adapted to the data on the reaction kinetics of the respective mixtures. The vulcanization times were 7 minutes for mixture VK2V1, 6 minutes for mixture VK2V2, 7 minutes for mixture VK2B1, 7 minutes for mixture VK2B2, 9 minutes for mixture VK2B3, 11 minutes for mixture VK2B4 and 10 minutes for mixture VK2B5. The tensile strength, elongation at break and Shore A hardness were subsequently determined according to the methods described herein above.

[0175] Table 3.4 gives an overview of the results obtained for the comparative examples VK2V1 and VK2V2 and for the rubber compositions VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5, which were vulcanized according to the invention.

[0176] [Table 7]

[0177] Compared to the comparative rubber compositions VK1V1 and VK1V2, the rubber compositions VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 according to the invention have similar or decreased tensile strengths, whereas the hardness (Shore A) remains unchanged or increases, when the carbon black is partially or completely replaced by the lignin-based fillers L2 or L3.

[0178] 3.3 Dynamic Mechanical Thermal Analysis (DMTA) The vulcanized rubber compositions were analyzed by dynamic mechanical thermal analysis (DMTA) according to the method described hereinabove to characterize their viscoelastic behavior. Table 3.5 summarizes the results obtained for the comparative examples VK1V1 and VK1V2, and for the rubber composition vulcanized according to the invention VK1B1.

[0179] [Table 8]

[0180] In vulcanized rubber compositions, it is fundamentally desirable to achieve the highest possible dynamic stiffness and the lowest possible tan δ value. One important indicator of dynamic stiffness is the complex modulus G*. The vulcanized rubber composition VK1B1 according to the invention shows increased stiffness compared to the comparative examples VK1V1 and VK1V2. Usually, a high dynamic stiffness G* (60°C) increases the loss factor tan δ. However, a low heat generation and therefore a low tan δ value is preferred. Surprisingly, the opposite effect was observed by combining the partial replacement of technical carbon black with organic filler L1 with the addition of sulfur-functional organosilanes, since at the same time a reduction in the loss factor occurred with an increased stiffness G* (60°C) (see VK1B1 vs. VK1V1 and VK1V2).

[0181] Thus, the use of organic filler L1 in combination with organosilanes can reduce heat generation and at the same time increase dynamic stiffness. Furthermore, equal hardness can be achieved.

[0182] The results shown in Table 3.5 for the loss factor tan δ are shown graphically in Figure 1, which shows the reduction in loss factor by partial replacement of technical carbon black with organic filler L1 and the addition of a sulfur-functional organosilane.

[0183] Table 3.6 gives an overview of the results obtained for the comparative examples VK2V1 and VK2V2 and for the rubber compositions VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5, which were vulcanized according to the invention.

[0184] [Table 9]

[0185] The dynamic stiffness, expressed by the complex modulus, of the vulcanized rubber compositions VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 according to the invention is surprisingly higher than that of the comparative examples VK2V1 and VK2V2 with technical carbon black as the sole filler. At the same time, the rubber compositions VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 vulcanized according to the invention surprisingly show a significantly lower loss factor tan δ than that of the comparative examples VK2V1 and VK2V2 with technical carbon black as the sole filler. Compared to the rubber composition VK2B3 with lignin L2 as the sole filler, the rubber compositions VK2B4 and VK2B5 with lignin L3 as the sole filler show a particularly significant improvement in these parameters compared to the rubber compositions VK2V1 and VK2V2 with carbon black as the sole filler. The combination of high dynamic stiffness and low loss factor as an indicator of hysteresis, the conversion of mechanical energy to heat, is unique to these lignin-based fillers. This reduction in heat generation reduces the rolling resistance of the tire, with a positive effect on the fuel consumption and CO2 emissions of the vehicle. By better decoupling these two important technical values ​​of rubber compared to rubber compositions containing industrial carbon black, the lignin-based compositions disclosed herein are highly favorable for use in rubber articles used under dynamic deformation, for example for use in compounds for tire carcasses to improve the rolling resistance of tires, or for use in technical rubber articles.

Claims

1. A vulcanizable rubber composition comprising a rubber component K, a filler component F, and a vulcanization system VS, the vulcanization system VS comprises at least sulfur and / or at least one sulfur donor, The rubber component K includes at least one rubber that can be crosslinked by sulfur, The filler component F is in the range of 0.20 to 0.45 Bq / g carbon. 14 C content and >20~150m 2 at least one organic filler having a BET surface area in the range of 1 / g; The rubber composition further comprises at least one organosilane as a part of the filler component F, the at least one organosilane having at least one hydrolyzable group and at least one sulfur atom, and being contained in an amount ranging from 0.25 to 5 phr.

2. 2. The rubber composition according to claim 1, wherein the at least one rubber of the rubber component K crosslinkable by sulfur is a diene rubber selected from the group consisting of natural rubber (NR), synthetic natural rubber, in particular isoprene rubber (IR), styrene-butadiene rubber (SBR), solution-polymerized styrene-butadiene rubber (SSBR), emulsion-polymerized styrene-butadiene rubber (ESBR), in particular functionalized SSBR, butadiene rubber (BR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR; nitrile rubber), isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), and mixtures thereof, preferably natural rubber, styrene-butadiene rubber, or solution-polymerized styrene-butadiene rubber, and mixtures thereof.

3. The organic filler is >18 to <150 m 2 / g, preferably 20 to 130m 2 / g, particularly preferably 25 to 120m 2 / g, more particularly preferably 30 to 110 m 2 / g, especially 40-100m 2 / g, most preferably 40 to <100m 2 / g range of STSA surface area and / or 25-120 m 2 / g, particularly preferably 30 to 110 m 2 / g, most preferably in the range of 40 to 100m 2 2. The rubber composition according to claim 1, characterized in that it has a BET surface area in the range of 0.1 / g and / or a d99 of < 25 μm, preferably < 20 μm, particularly preferably < 18 μm, even particularly preferably < 15 μm, even more preferably < 12 μm, even more preferably < 10 μm, even more preferably < 9 μm, even more preferably < 8 μm, wherein d99 is preferably determined by laser diffraction in accordance with ISO 13320:2009, in each case.

4. 2. Rubber composition according to claim 1, characterized in that the organic filler has an oxygen content in the range of >8% to <30% by weight, preferably >10% to <30% by weight, particularly preferably >15% to <30% by weight and most preferably >20% to <30% by weight, or a carbon content in the range of >60% to <90% by weight, preferably >60% to <85% by weight, particularly preferably >60% to <82% by weight and most preferably >60% to <80% by weight, based on the ash-free and water-free filler, respectively.

5. 2. The rubber composition according to claim 1, characterized in that it contains the at least one organic filler in an amount ranging from 1 to 150 phr, preferably from 5 to 100 phr, particularly preferably from 10 to 80 phr, even more particularly preferably from 15 to 70 phr, and most preferably from 15 to 60 phr.

6. 2. The rubber composition according to claim 1, characterized in that the organic filler is a lignin-based filler, preferably at least the lignin, even more preferably the organic filler itself, is at least partially present in a form obtainable by hydrothermal treatment, particularly preferably obtainable by hydrothermal treatment, the hydrothermal treatment being preferably carried out at a temperature in the range of >100°C to <300°C, particularly preferably >150°C to <250°C.

7. 2. The rubber composition according to claim 1, wherein the at least one organosilane is a compound of general formula (I) and / or (II). Si(X) 4-y (R) y (I)、 (X) 3-z (T) z Si-(RA)-Si(X) 3-z (T) z (II) [Wherein, in the case of general formula (I), X's each independently represent a hydrolyzable group reactive with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group and / or a mixture of these groups, and the hydrolyzable groups each independently represent an alkoxy group, particularly preferably OC 1～4 alkyl, the parameter y represents an integer ranging from 1 to 3, but is at least 1 and preferably exactly 1; R is a non-hydrolyzable organic group, preferably an aliphatic C 3 ~C 20 group, wherein the sulfur atom is preferably part of at least one functional group selected from the group consisting of thiol groups, block thiol groups, di- and / or polysulfide groups, and mixtures thereof, particularly preferably thiol groups, In the formula (II), X's each independently represent a hydrolyzable group reactive with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group and / or a mixture of these groups, and the hydrolyzable groups each independently represent an alkoxy group, particularly preferably OC 1～4 alkyl, RA is a non-hydrolyzable organic group having two bonds, preferably an aliphatic C group having two bonds containing at least one sulfur atom. 6 ~C 20 group, preferably at least one disulfide and / or polysulfide group, particularly preferably a di- or tetrasulfide group, each parameter z represents an integer ranging from 0 to 2, preferably 0 or 2; Unlike the RA group, T represents a non-hydrolyzable organic group having no functional group, and is preferably an aliphatic C 1 ~C 20 [Based on]

8. the at least one organosilane at least one mercaptoalkyl group R, where R is preferably an aliphatic C 3 ~C 8 groups, particularly preferably aliphatic C 3 ~C 6 and monosilanes of general formula (I) containing at least one X group, preferably containing two or three X groups, particularly preferably selected from the group consisting of 4-mercaptobutyltrialkoxysilanes and / or 6-mercaptohexyltrialkoxysilanes and / or 3-mercaptopropyltrialkoxysilanes, the alkoxy groups preferably being, independently of one another, methoxy or ethoxy groups, and / or Bis(silane) of general formula (II) wherein the non-hydrolyzable organic group R A is preferably an aliphatic C 6 ~C 20 groups, particularly preferably aliphatic C 6 ~C 10 group, which contains at least one sulfur atom, preferably a di- or polysulfide group, particularly preferably a di- or tetrasulfide group, and which contains at least one X group, preferably two or three X groups.

2. The rubber composition according to claim 1, characterized in that the bis(silane) of general formula (II) is preferably a bis(silane) of general formula (II), particularly preferably a bis(silane) of general formula (II) selected from the group consisting of bis(dimethylethoxysilylpropyl)tetrasulfide (DMESPT), bis(dimethylethoxysilylpropyl)disulfide (DMESPD), bis(triethoxysilylpropyl)tetrasulfide (TESPT), bis(triethoxysilylpropyl)disulfide (TESPD) and mixtures thereof, further particularly preferably TESPT and / or TESPD, and most preferably TESPD.

9. 2. The rubber composition according to claim 1, wherein the organosilane is contained in an amount ranging from 0.25 to 3 phr, preferably from 0.5 to 3 phr, and / or in an amount ranging from 1 to 10% by weight, preferably from 2 to 8% by weight, particularly preferably from 2.5 to 6% by weight, most preferably from 3 to 6% by weight, based on the organic filler.

10. 2. The rubber composition according to claim 1, wherein the sulfur crosslinking agent is contained in an amount ranging from 0.25 to 10 phr, preferably from 0.25 to 7 phr, particularly preferably from 0.5 to 5 phr, and most preferably from 1 to 3 phr.

11. The rubber composition may comprise at least one accelerator for crosslinking with sulfur, the accelerator preferably being part of the vulcanization system VS of the rubber composition, preferably a dithiocarbamate, a xanthogenate, a thiuram, such as thiuram monosulfide and / or thiuram disulfide and / or tetrabenzylthiuram disulfide (TbzTD), a thiazole, such as 2-mercaptobenzothiazole and / or dibenzothiazyl disulfide, a sulfenamide, such as N-cyclohexyl-2-benzothiazyl-sulfenamide and / or 2-morpholinothiobenzothiazole and / or N-t 2. The rubber composition according to claim 1, characterized in that the additive is selected from the group consisting of N-tert-butyl-2-benzothiazyl-sulfenamide, guanidine, such as N,N'-diphenylguanidine, thiourea, dithiophosphate, dipentamethylenethiuram tetrasulfide, 4,4'-dithiodimorpholine, caprolactam disulfide, and mixtures thereof, particularly preferably N-tert-butyl-2-benzothiazyl-sulfenamide, tetrabenzylthiuram disulfide, and N,N'-diphenylguanidine, and mixtures thereof.

12. In a spatially separated manner, a rubber composition comprising, as part (A), at least the rubber component K and at least a filler component F, respectively, as defined in claim 1, wherein part (A) does not, however, comprise sulfur and / or at least one sulfur donor of the vulcanization system VS as defined in claim 1; 10. The vulcanization system VS according to claim 1, which comprises as part (B) at least sulfur and / or at least one sulfur donor; A kit of parts comprising: the organosilane of claim 1 in a filler component F in part (A) in an amount ranging from 0.25 to 5 phr.

13. 13. A vulcanized rubber composition obtainable by vulcanization of the vulcanizable rubber composition according to claim 1 or by vulcanization of a vulcanizable rubber composition obtainable by combining and mixing both parts (A) and (B) of the kit-of-parts according to claim 12.

14. 14. Use of the vulcanizable rubber composition according to claim 1, the kit-of-part according to claim 12 or the vulcanized rubber composition according to claim 13 for use in the production of tires, preferably pneumatic and solid tires, in the production of tire components preferably selected from base components, i.e. components under tread, shoulder strips (wings), cap ply, belt, bead and / or bead reinforcements, and / or in the production of preferred technical rubber articles, preferably selected from drive belts, straps / belts, molded parts, such as buffers / cushions, bearings / mounts, in particular hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

15. 14. A tire, preferably a pneumatic tire or a solid tire, tire component or preferred technical rubber article produced by utilizing the vulcanizable rubber composition according to claim 1, the kit-of-parts according to claim 12 or the vulcanized rubber composition according to claim 13, respectively, preferably in the case of tire components these are selected from the components under base components, i.e. tread, shoulder strips (wings), cap plies, belts, beads and / or bead reinforcements, preferably rubber articles, such as in the case of preferred technical rubber articles these are preferably selected from drive belts, straps / belts, molded parts, such as buffers / cushions, bearings / mounts, in particular hydromounts, conveyor belts, profiles, seals, rings and / or hoses.

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