A rubber composition containing an organic filler that can be crosslinked with sulfur.

Abstract

The present invention relates to a vulcanizable rubber composition comprising a vulcanizing system VS containing at least sulfur and / or at least one sulfur donor, at least one rubber that can be crosslinked by sulfur and / or the sulfur donor, and at least one lignin-based organic filler, wherein the lignin-based organic filler, unlike carbon black, has a carbon content in the range of 0.20 to 0.45 Bq / g 14 It has a C content of >24.0~150m 2 The present invention relates to rubber compositions having a BET surface area in the range of / g, wherein the amount of any carbon black optionally present in the rubber composition as at least one second filler F2 in an amount in the range of 1 to <140 phr is <40 phr, and the amount of any organosilane optionally present in the rubber composition having at least one hydrolyzable group and at least one sulfur atom is <7 phr, vulcanized rubber compositions which can be obtained therefrom, kits of parts comprising a rubber composition comprising the above rubber and organic filler F1 as part A) and a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor as part B), the use of the above products for use in the manufacture of tires, tire components and rubber articles, and corresponding tires, tire components and rubber articles themselves.

Description

[Technical Field]

[0001] The present invention relates to a vulcanizable rubber composition comprising a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor that releases sulfur under vulcanization conditions, at least one rubber that can be crosslinked by sulfur and / or the sulfur donor, and at least one organic filler; a kit of parts comprising a rubber composition comprising the above rubber and filler as part A) and a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor as part B); vulcanizable rubber compositions that can be obtained from these, respectively; the use of the above products for use in the manufacture of tires, tire components and rubber articles; and the corresponding tires, tire components and rubber articles themselves. [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 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 vulcanized product. Here, industrial carbon black represents the largest portion of reinforcing fillers. Industrial carbon black is produced by the incomplete combustion of organic compounds or the thermal decomposition of hydrocarbons. Most industrial carbon black is produced by furnace processes. Because of the high CO2 content during the production process, it is desirable to avoid or minimize the use of fossil energy sources for filler production. Furthermore, industrial carbon black is often unsuitable for certain applications due to its color. Known alternatives to the use of industrial carbon black as a reinforcing filler are precipitated silica and bifunctional silanes.

[0003] In the production of treads for automobile tires, 120-200m 2It was known to use silica having a BET surface area of / g together with a bifunctional coupling agent such as sulfur-functional silane. This is because when using them, the "magic triangle" of tire performance consisting of wear, rolling resistance, and wet traction can be expanded compared to the use of industrial carbon black.

[0004] In contrast to the tread, in dynamic structural parts (carcass, belt, layer, band / strip), wear by abrasion or wet or dry traction does not play a more important role than in the case of a tire tread. The main purpose of using dynamic structural parts is to reduce the conversion of mechanical energy into heat. Heat generation is expressed by the loss coefficient tan delta (tanδ). The loss coefficient tanδ characterizes viscoelastic behavior and is derived from the ratio of the viscous component and the elastic component (loss modulus and storage modulus). The storage modulus represents a part of the mechanical energy stored by the system, and the loss modulus represents the conversion of mechanical energy into thermal energy. Therefore, a low loss coefficient is particularly preferred as an important indicator of heat generation, especially in the case of the above-mentioned dynamic structural parts.

[0005] In heat generation, the polymer used must also be taken into account because it already contributes to heat generation due to its dynamic properties. Therefore, the loss coefficient is reduced by a low glass transition temperature T g g.

[0006] In rubber compounds for dynamic structural parts, industrial carbon black having a mainly low specific surface area is used for the purpose of minimizing heat generation. Heat generation or the loss coefficient can be reduced by a decrease in the filling degree of the reinforcing filler, an increase in the particles of the reinforcing filler per unit volume under consideration, and / or an increase in the distance between the reinforcing particles per unit volume. The volume filling ratio can be reduced by a high structuring of industrial carbon black (expressed by the so-called compression oil absorption amount (COAN)) without affecting the hardness of the structural part.

[0007] However, this independence does not apply to all parameters. In contrast, the reduction of the loss factor to achieve the lowest possible heat generation usually affects other properties of the vulcanized rubber composition. Regardless of the reinforcing filler, the loss factor also decreases with an increase in the crosslink density. However, a higher crosslink density has an adverse effect on the vulcanized rubber composition, for example, with respect to its tear properties (decrease in elongation at break) and aging properties.

[0008] An important issue regarding the reinforcing filler is that the reduction of the loss factor is achieved at the expense of the dynamic stiffness. At lower values of the loss factor tanδ, typically only low dynamic stiffness can be observed. However, such low dynamic stiffness causes higher deformation of the rubber composition under the same load and is thus disadvantageous especially for using the rubber composition to produce tires or their dynamic structural parts.

[0009] Therefore, there is a need to provide a rubber composition that has both the lowest possible loss factor and the highest possible dynamic stiffness after vulcanization, 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

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

[0011] [Non-Patent Document 1] A. Sluiter et al. (2008), “Determination of Structural Carbohydrates and Lignin in Biomass”, NREL Technical Report NREL / TP-510-42618 [Overview of the project] [Problems that the invention aims to solve]

[0012] Therefore, an object of the present invention is to provide a vulcanizable rubber composition that, after vulcanization, has the highest possible dynamic rigidity and the lowest possible heat generation, and in particular, a rubber composition in which these two parameters can be separated so that they can be adjusted more flexibly and better with respect to the performance that the rubber composition is to achieve. [Means for solving the problem]

[0013] This objective is achieved by the subject matter claimed in the claims and preferred embodiments of these subjects described in the following specification.

[0014] The first subject of the present invention is a vulcanizable rubber composition, A vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, A rubber that can be crosslinked with sulfur and / or a sulfur donor, provided that if at least one halobutyl rubber is present, it is present in the rubber composition in an amount of <70 phr, The first filler F1 is an organic filler of which at least one type of organic filler can be obtained from lignin-containing biomass having a Claesson lignin content of at least 60% by mass relative to its dry matter content, and It contains organic filler F1, Unlike carbon black, Range of 0.20 to 0.45 Bq / g carbon 14 It contains C, >24.0~150m 2 Having a BET surface area in the range of / g, It is present in the rubber composition in an amount ranging from 1 to <140 phr. The amount of any carbon black optionally present in the rubber composition as at least one type of second filler F2 is <40 phr. Any amount of any organosilane optionally present in the rubber composition, having at least one hydrolyzable group and at least one sulfur atom, is <7 phr. The vulcanizable rubber compositions VK1V2, VK1B1, VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 disclosed in the experimental section of international application PCT / EP2022 / 076858 are excluded. This rubber composition excludes VKV3, the vulcanizable rubber composition disclosed in the experimental section of international application PCT / EP2022 / 073490 (published as international publication 2023 / 025808).

[0015] Another subject of the present invention is, in a spatially separated form, As part A), a rubber composition used in accordance with the present invention, comprising at least the above rubber and at least the above filler F1, wherein part A of the parts kit is a rubber composition that does not contain sulfur and / or at least one sulfur donor of vulcanizing system VS used in accordance with the present invention, Part B) is a vulcanization system VS used in accordance with the present invention, comprising at least sulfur and / or at least one sulfur donor. This is a kit of parts that includes [the specified part].

[0016] Another subject of the present invention is a vulcanizable rubber composition that can be obtained by vulcanizing a vulcanizable rubber composition according to the present invention, or by vulcanizing a vulcanizable rubber composition that can be obtained by combining and mixing two parts A) and B) of a parts kit according to the present invention.

[0017] Another subject of the present invention is the production of tires, preferably pneumatic tires and solid tires, and the production of tire components, preferably natural rubber and / or low glass transition temperature T used in their production. g The use of the vulcanizable rubber composition according to the present invention, a kit of parts according to the present invention, or the vulcanizable rubber composition according to the present invention is for use in the production of tire components, particularly for use in the production of tire components selected from the group of base components, i.e., components under the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, or for use in the production of rubber articles such as technical rubber articles, preferably for use in the production of drive belts, straps / belts, molded parts, e.g., buffers / cushions, bearings / mounts, e.g., liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses, such as the vulcanizable rubber composition according to the present invention, a kit of parts according to the present invention, or the vulcanizable rubber composition according to the present invention, such that the lowest possible tanδ value of the vulcanizable rubber composition, such as a rubber composition containing rubber having, is targeted.

[0018] Another subject of the present invention is a tire, preferably a pneumatic tire or a solid tire, or a rubber component, or a technical rubber article, etc., which is produced using the vulcanizable rubber composition, a kit of parts according to the present invention, or a vulcanizable rubber composition according to the present invention, respectively, wherein, preferably, in the case of a rubber component, these are selected from base components, i.e., components under the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, and in the case of a technical rubber article, etc., these are preferably selected from drive belts, straps / belts, molded parts, e.g., buffers / cushions, bearings / mounts, e.g., liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses, which are a tire, rubber component, or a rubber article.

[0019] Another subject of the present invention is the use of organic filler F1 to increase the dynamic stiffness, decrease the tanδ value, or both, of a vulcanizable rubber composition that can be obtained from a vulcanizable rubber composition containing organic filler F1, preferably one obtained from the vulcanizable rubber composition according to the present invention, compared to a vulcanizable rubber composition that does not contain organic filler F1 but contains carbon black as a filler.

[0020] Surprisingly, the rubber composition according to the present invention was found to have both high dynamic rigidity and a low tanδ value. The target performance of the rubber composition can be flexibly and effectively adjusted, especially compared to rubber compositions containing industrial carbon black in an amount of ≥40 phr, as these two properties can be well separated.

[0021] Specifically, the use of organic filler F1 and optionally carbon black such as industrial carbon black, as used in this invention, improves the performance of the rubber composition, although the latter is used in amounts less than 40 phr at most. By (partially) replacing industrial carbon black with the filler used in this invention, the tanδ value can be reduced while the dynamic stiffness remains at least unchanged. Surprisingly, compared to rubber compositions containing ≥40 phr of carbon black, using organic filler F1 can achieve higher dynamic stiffness in addition to a further reduction in the tanδ value. Furthermore, surprisingly, it has been found that often equal to or higher elongation at break is achieved (compared to vulcanized rubber compositions containing carbon black as an additional filler of ≥40 phr). Moreover, the hardness of the rubber composition was not adversely affected. The use of organic filler F1 as used in this invention is particularly advantageous for sulfur-crosslinked rubber compositions.

[0022] The use of filler organic F1 according to the present invention is highly advantageous from an environmental standpoint. During the production of industrial carbon black, large amounts of CO2 are released in the production process. Therefore, filler F1 according to the present invention represents an environmentally friendly filler alternative and, in contrast to industrial carbon black, does not affect the color of the rubber composition. [Modes for carrying out the invention]

[0023] For example, the term “including” as used in the present invention with respect to the vulcanizable rubber composition according to the present invention and the process steps or stages of the process described herein preferably means “consisting of.” For example, in this context with respect to the vulcanizable rubber composition according to the present invention, one or more of the optional components described below herein may be included in addition to the components that are compulsorily present therein. All components may be present in each of their preferred embodiments described below. With respect to the process according to the present invention as described herein, these may have other optional process steps and stages in addition to compulsory steps and / or stages.

[0024] The components, etc., contained in the vulcanizable rubber composition according to the present invention (in any case, including all mandatory components and all optional components) and the total amount of all compositions described herein is in any case 100% by mass.

[0025] vulcanizable rubber composition The vulcanizable rubber composition according to the present invention comprises a vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, at least one rubber that is crosslinkable by sulfur and / or sulfur donor, provided that at least one halobutyl rubber is present in the rubber composition in an amount of <70 phr, and at least one organic filler as a first filler F1, wherein the amount of any carbon black optionally present in the rubber composition as at least one second filler F2 is <40 phr, and the amount of any organosilane optionally present in the rubber composition having at least one hydrolyzable group and at least one sulfur atom is <7 phr. Several vulcanizable rubber compositions are excluded, namely the vulcanizable rubber compositions VK1V2, VK1B1, VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 disclosed in the experimental section of international application PCT / EP2022 / 076858, and the vulcanizable rubber composition VKV3 disclosed in the experimental section of international application PCT / EP2022 / 073490 (published as international publication 2023 / 025808).

[0026] Preferably, the vulcanizable rubber compositions R-FPM2, R-OF2, and R-OF3 disclosed in the experimental section of European Patent Application No. 22 208 442.8 are also excluded.

[0027] Preferably, the vulcanizable rubber compositions KV1VS, KI1VS, KI2VS, and KI3VS disclosed in the experimental section of international application PCT / EP2022 / 073490 (published as international publication 2022 / 243486) are also excluded.

[0028] The phr (parts by mass per 100 parts by mass of rubber) designation used herein is a quantity designation commonly used in the rubber industry for compound formulation. The dosage of parts by mass of individual components is always the dosage relative to 100 parts by mass of the total mass of all rubber present in the compound.

[0029] Preferably, covalent bonding occurs via at least a portion of the oxygen atoms of at least one functional group selected from phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups, and mixtures thereof, and / or via at least a portion of the carbon atoms of organic filler F1 that are ortho relative to the phenolic OH group and / or phenolate group, and does not occur in the other organic modifier, and in particular does not occur in any organic modifier containing at least one organic residue that, before bonding to organic filler F1, contained at least one functional group RFG resulting in bonding to the organic filler, and is reactive with at least one functional group of organic filler F1 and / or the carbon atoms that are ortho relative to the phenolic OH group and / or phenolate group, wherein the at least one reactive functional group RFG does not contain any silicon atoms and is selected from the group consisting of acid groups and their salts, anhydrides, halides and esters, acid groups, epoxide groups, thiirane groups, alcohol groups, thiol groups, thioester groups, aldehyde groups, isocyanate groups, and mixtures thereof.

[0030] As previously stated, the rubber composition of the present invention may optionally contain one or more types of carbon black, such as industrial carbon black, as a second filler F2. However, in the case where any type of carbon black is additionally present in addition to the organic filler F1, its amount in the rubber composition is less than 40 phr. Preferably, the amount of any carbon black optionally present in the rubber composition as at least one type of second filler F2 is in the range of 0 to < 39 phr, more preferably 0 to 35 phr, even more preferably 0 to 30 or 0 to < 30 phr, even more preferably 0 to ≤ 29 phr, even more preferably 0 to 25 phr, even more preferably 0 to 20 or ~15 phr, and even more preferably 0 to 10 or ~5 phr. Alternatively, the amount of any carbon black optionally present in the rubber composition as at least one type of second filler F2 is preferably in the range of 0.01 or 0.1 or 1 to <39 phr, more preferably 0.01 or 0.1 or 1 to 35 phr, even more preferably 0.01 or 0.1 or 1 to 30 or 0.01 or 0.1 or 1 to <30 phr, even more preferably 0.01 or 0.1 or 1 to ≤29 phr, more preferably 0.01 or 0.1 or 1 to 25 phr, even more preferably 0.01 or 0.1 or 1 to 20 or ~15 phr, and even more preferably 0.01 or 0.1 or 1 to 10 or ~5 phr. Most preferably, the rubber composition does not contain or is essentially free of any carbon black as the second filler F2. In this context, the term "essentially not" means that carbon black is not added to the rubber composition, at least not intentionally, but nevertheless, it does not mean that any carbon black residue / contaminant may be present in small amounts, for example, <1% by mass, <0.5% by mass, <0.1% by mass, <0.01% by mass, or <0.001% by mass, relative to the total mass of the rubber composition.

[0031] Preferably, the relative mass ratio of organic filler F1 to carbon black in the presence of filler F2 is in the range of 50:1 or 49:1 to 1:2, more preferably 40:1 to 1:1.75, even more preferably 30:1 to 1:1.50, even more preferably 25:1 to 1:1.25, even more preferably 20:1 to 1:1, and even more preferably 15:1 to >1:1, or the rubber composition does not contain or essentially contains any carbon black as filler F2. In this context, the term "essentially does not contain" means that the amount of carbon black present as filler F2 in the rubber composition is less than 2.0% by mass, preferably less than 1.5% by mass, more preferably less than 1.0% by mass, and even more preferably less than 0.5% by mass, relative to the total mass of both organic filler F1 and carbon black filler F2 present in the rubber composition.

[0032] As previously stated, the rubber composition of the present invention may optionally contain at least one organosilane having at least one hydrolyzable group and at least one sulfur atom. However, wherever such organosilane is present, its amount in the rubber composition is less than 7 phr. Preferably, the amount of any organosilane having at least one hydrolyzable group and at least one sulfur atom optionally present in the rubber composition is <5 phr, more preferably the rubber composition does not contain or is essentially free of any organosilane having at least one hydrolyzable group and at least one sulfur atom, and even more preferably the rubber composition does not contain or is essentially free of any type of organosilane. In this context, the term "essentially not" means that no organosilane having at least one hydrolyzable group and at least one sulfur atom, or any organosilane of any kind, is intentionally added to the rubber composition, but nevertheless, it cannot be prevented that such organosilane residues / contaminants may be present in small amounts, for example, <0.5% by mass, <0.25% by mass, <0.1% by mass, <0.01% by mass, or <0.001% by mass, relative to the total mass of the rubber composition.

[0033] Vulcanized VS The vulcanization system VS of the vulcanizable rubber composition according to the present invention comprises at least sulfur and / or at least one sulfur donor. The sulfur donor releases sulfur under vulcanization conditions. The sulfur acts as a crosslinking agent for the polymer whether it is directly contained in the vulcanization system VS or released from the sulfur donor used.

[0034] The presence of a vulcanizing VS system and sulfur and / or at least one sulfur donor contained therein allows the vulcanizable rubber composition according to the present invention to be vulcanized.

[0035] Typically, sulfur elements in the form of an S8 ring are used for sulfur-based crosslinking. The S8 ring is opened thermally or by an alkaline substance. Sulfur can be present in rubber compositions as soluble or insoluble sulfur. The term accelerator refers to an alkaline organic compound that activates ring opening. As a substitute for or in addition to the sulfur element, at least one sulfur donor may be used. In this case, sulfur is released from such sulfur donors only during vulcanization. Examples of sulfur donors are sulfur-containing compounds such as 4,4'-dithiodimorpholine (DTDM) and tetramethylthiuram disulfide (TMTD), which are used in dosages ranging from 0.5 to 2.0 phr, for example, 1.5 phr (DTDM) or 1.0 phr (TMTD).

[0036] The proportion of sulfur and / or sulfur donor 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, even more preferably 0.5 to 5 phr, and most preferably 1 to 3 or 2 phr.

[0037] Preferably, the vulcanization system VS comprises at least one accelerator for crosslinking with sulfur. If the vulcanization system VS contains sulfur as a crosslinking agent, the sulfur donors cited above are also suitable as such accelerators. Preferably, at least one accelerator is selected from the group consisting of dithiocarbamates, xanthogenetes, thirams, such as thirams monosulfide and / or thirams disulfide and / or tetrabenzylthirams disulfide (TBzTD), thiazoles, such as 2-mercaptobenzothiazole and / or dibenzothiadyl disulfide, sulfenamides, such as N-cyclohexyl-2-benzothiadyl sulfenamide (CBS) and / or 2-morpholinothiobenzothiazole and / or N-tert-butyl-2-benzothiadylsulfenamide, guanidines, such as N,N'-diphenylguanidine, thiourea, dithiophosphates, dipentamethylenethuram tetrasulfide, caprolactam disulfide, and mixtures thereof, and more preferably, is selected from the group consisting of N-tert-butyl-2-benzothiadyl sulfenamide and N,N'-diphenylguanidine, and mixtures thereof.

[0038] 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, even more preferably 0.2 to 6 phr, and most preferably 0.2 to 3 phr.

[0039] The vulcanization system VS of the vulcanizable rubber composition according to the present invention may include sulfur and / or other vulcanizing agents other than sulfur donors, and / or additives that promote vulcanization, such as zinc oxide and / or fatty acids such as stearic acid.

[0040] The vulcanization system VS of the vulcanizable rubber composition according to the present invention may include one or more additives that promote vulcanization but cannot initiate vulcanization on their own. Examples of such additives include saturated fatty acids having preferably 12 to 24 carbon atoms, particularly preferably 14 to 20, and most preferably 16 to 18 carbon atoms, such as stearic acid, and vulcanization accelerators such as zinc salts of the above fatty acids.

[0041] When additives that promote vulcanization, particularly the above-mentioned fatty acids and / or their zinc salts, preferably stearic acid and / or zinc stearate, are used in the rubber composition according to the present invention, their proportions are preferably 0 to 10 phr, particularly preferably 1 to 8 phr, and most preferably 1.5 to 5 phr.

[0042] The vulcanizing system VS of the vulcanizable rubber composition according to the present invention may further contain one or more other vulcanizing agents, preferably zinc oxide, that are different from sulfur and / or sulfur donors. It is particularly preferable to use such vulcanizing agents in the vulcanizing system VS in addition to sulfur and / or sulfur donors.

[0043] When other vulcanizing agents, such as zinc oxide, are used in the rubber composition according to the present invention, their proportions are preferably 0 to 10 phr, particularly preferably 1 to 8 phr, and most preferably 2 to 5 phr.

[0044] In addition to the sulfur and / or at least one sulfur donor used, a peroxide may also be added to the vulcanization system VS as another crosslinking agent. However, this is not preferred.

[0045] 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 even more preferably using sulfur in combination with zinc oxide and at least one fatty acid.

[0046] rubber The vulcanizable rubber composition according to the present invention comprises at least one rubber that can be crosslinked by sulfur and / or a sulfur donor via a vulcanization system VS. However, if at least one halobutyl rubber, such as brominated isobutylene isoprene rubber (BIIR) and / or chlorinated isobutylene isoprene rubber (CIIR), is present in the rubber composition in an amount of <70 phr, preferably <65 phr, more preferably <60 phr, even more preferably <55 phr or <50 phr or <45 phr or <40 phr, and even more preferably <35 phr or <30 phr or <25 phr or <20 phr or <15 phr or <10 phr or <5 phr. Most preferably, no halobutyl rubber is present in the rubber composition. That is, in this case, at least one rubber is selected from suitable rubbers excluding halobutyl rubber.

[0047] Any type of rubber is suitable for the production of rubber compositions according to the present invention, insofar as it can be crosslinked with sulfur and / or at least one sulfur donor. Suitable rubbers are diene rubbers selected from the group consisting of diene rubbers, especially natural rubber (NR), synthetic natural rubbers, especially isoprene rubber (IR), ethylene propylene diene monomer rubber (EPDM), styrene butadiene rubber (SBR), solution polymerized styrene butadiene rubber (SSBR), emulsion polymerized styrene butadiene rubber (ESBR), functionalized SBR, especially 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.

[0048] Preferably, functionalized diene rubbers such as SSBRs have one or more functional groups on one or more side chains and / or terminal groups, and at least one functional group is preferably selected from polar groups, particularly from the group consisting of carboxyl, hydroxyl, amino, carboxylic acid ester, carboxylic acid amide, or sulfonic acid groups, and mixtures thereof. Functionalized SSBRs are known, in particular from German Patent Application Publication No. 10 2008 052 116.

[0049] Preferably, at least one type of rubber is natural rubber (NR), ethylene propylene diene monomer rubber (EPDM), 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. Natural rubber (NR) is particularly preferred as the rubber.

[0050] Organic Filler F1 Organic filler F1 can be obtained from lignin-containing biomass having at least 60% by mass of Claesson lignin relative to its dry matter content, and unlike carbon black, it has a carbon content in the range of 0.20 to 0.45 Bq / g. 14 It has a C content of >24.0~150m 2 It has a BET surface area in the range of / g and is present in the rubber composition in an amount ranging from 1 to <140 phr.

[0051] Since the filler F1 used in accordance with the present invention is an organic filler, inorganic fillers such as precipitated silica do not fall into this category. Furthermore, since the organic filler F1 is different from any type of carbon black material, carbon black also does not fall into this category.

[0052] In particular, the terms filler and organic filler are known to those skilled in the art. Preferably, the organic filler F1 used according to the present invention is a reinforcing filler, i.e., an active filler. A reinforcing filler or an active filler is characterized by a higher specific surface area than an inert filler and, in contrast to an inert (non-reinforcing) filler, can change the viscoelastic properties of the rubber by interacting with the rubber within the rubber composition. For example, they can affect the viscosity of the rubber and improve the elongation under tension and the fracture behavior of the vulcanizate, e.g., with respect to tear strength, tear and abrasion. On the other hand, an inert filler dilutes the rubber matrix and, for example, reduces the crushing energy.

[0053] The organic filler F1 used according to the present invention has a C content in the range of 0.20 to 0.45 Bq / g carbon, preferably 0.23 to 0.42 Bg / g carbon. 14 has. The required 14 C content is achieved by an organic filler obtained from biomass by further treatment or reaction, preferably carried out thermally, chemically and / or biologically, preferably by a fractionation carried out thermally and chemically. Thus, in particular, fillers obtained from fossil materials such as fossil fuels do not have the corresponding 14 C content and do not fall within the definition according to the present invention of the filler to be used according to the present invention.

[0054] Biomass is defined herein, in principle, as any biomass, and the term “biomass” 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 microorganism origin, including fungi. Biomass can be dry biomass or fresh biomass, and originates from dead or living organisms. The biomass particularly preferred herein for filler production is phytomass, preferably dead phytomass. Dead phytomass includes, among other things, dead plants, waste plants or isolated plants, and parts thereof. These include, for example, excised and torn leaves, grain stalks, lateral shoots, twigs and branches, fallen leaves, felled or pruned wood, as well as seeds and fruits and parts derived therefrom, as well as sawdust, wood chips / chips and other products derived from wood processing.

[0055] The organic filler F1 used in accordance with the present invention has a volume of >24.0~150m 2 / g, or >24.0~149m 2 A range of / g, preferably 25-150m 2 Range of / g, particularly preferably 25-140, or ~130, or ~120m 2 The range is / g, particularly preferably 30 or 35 to 110m 2 The range is / g, most preferably 40-100m 2 It has a BET surface area (specific total surface area according to Brunauer, Emmett, and Teller) in the range of / g. The method for determining the BET surface area is referenced below in the "Method" section of this specification.

[0056] Preferably, the organic filler F1 has an STSA surface area that is different from its BET surface area by at most 20%, more preferably at most 15%, even more preferably at most 10%, even more preferably at most 7.5%, and even more preferably at most 6.5 or 5.0%.

[0057] Those skilled in the art recognize that the surface of particulate materials such as organic filler F1 consists of an outer and an inner surface. The relevant measurement quantity is the specific surface area. The specific surface area can be measured as the outer surface area by statistical thickness specific surface area (STSA surface area), or as the total surface area including the outer and inner surface areas by nitrogen surface area (BET surface area) according to Brunauer-Emmett Teller. The difference between the inner and outer surface areas is substantially due to the porosity of the material. Compared to the surface surrounding the particle, the inner surface area also relates to the surface present in the pores. A coarsely refined material with a relatively small outer (i.e., STSA) surface area can nevertheless have a large total (i.e., BET) surface area (including the outer and inner surface areas) if it is highly porous. Therefore, the difference between the BET surface area and the STSA surface area is porosity. The smaller the difference, the less porous the material.

[0058] Preferably, the organic filler F1 is >20 or >22 or >23 or 24 to <150 m 2 / g, preferably 20 or >22 or >23 or 24-130m 2 / g, particularly preferably 25-120m 2 / g, more preferably 30-110m 2 / g, especially 40-100m 2 / g, most preferably 40 to <100m 2 It has an STSA surface area in the range of / g. The method for determining the STSA surface area (statistical thickness-specific surface area) is referenced below in the "Method" section of this specification.

[0059] Preferably, the organic filler F1 is <0.1 cm 3 / g, more preferably <0.01cm 3 / g, particularly preferably <0.005cm 3 It has a pore volume of / g.

[0060] The organic filler F1 used in accordance with the present invention has a d99 value of preferably <25 μm, more preferably <20 μm, particularly preferably <18 μm, even more preferably <15 μm, even more preferably <12 μm, even more preferably <10 μm, even more preferably <9 μm, and even more preferably <8 μm. A method for determining the d99 value is described below in the "Method" section of this specification and is carried out by laser diffraction in accordance with ISO 13320:2009. The d90 and d25 values ​​cited below are determined similarly. Those skilled in the art will recognize that the organic filler F1 used in accordance with the present invention exists in the form of particles, such as particulate carbon material, and that the average particle size (average crystal grain size) of these particles is described by the d99 value above, and also by the d90 and d25 values ​​described above.

[0061] Preferably, the organic filler F1 has a d90 value of <7.0 μm, particularly preferably <6.0 μm, and / or a d25 value of <3.0 μm, particularly preferably <2.0 μm, determined by laser diffraction according to ISO 13320:2009.

[0062] Preferably, the organic filler F1 has an oxygen content in the range of >8% to <30% by mass, particularly preferably >10% to <30% by mass, even more preferably >15% to <30% by mass, and most preferably >20% to <30% by mass, relative to the ash-free and water-free fillers, respectively. The oxygen content can be determined by high-temperature pyrolysis using, for example, a EuroEA3000 CHNS-O Analyzer from EuroVector SpA.

[0063] Preferably, the organic filler F1 has a carbon content in the range of >60% to <90% by mass, particularly preferably >60% to <85% by mass, even more preferably >60% to <82% by mass, and most preferably >60% to <80% by mass, relative to the ash-free and water-free fillers, respectively. A method for determining the carbon content is referenced below in the "Method" section of this specification. In this regard, since the organic filler F1 has a carbon content of at least 95% by mass, it differs from both industrial carbon black produced from fossil raw materials and carbon black produced from recycled raw materials.

[0064] Preferably, the organic filler F1 has at least one functional group selected from a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group, and mixtures thereof.

[0065] Preferably, the organic filler F1 has a pH value in the range of 7 to 9, particularly preferably in the range of >7 to <9, and even more preferably in the range of >7.5 to <8.5.

[0066] Preferably, the organic filler F1 used in accordance with the present invention is a lignin-based filler, and preferably the organic filler F1 exists in a form that can be obtained by hydrothermal treatment of lignin-containing biomass, the hydrothermal treatment being carried out at a temperature preferably in the range of >100°C to <300°C, and particularly preferably >150°C to <250°C.

[0067] Therefore, the organic filler F1 used according to the present invention is a lignin-based organic filler produced from biomass and / or biomass components. For example, lignin for the production of lignin-based organic filler F1 can be isolated, extracted, and / or dissolved from biomass. A preferred method for obtaining lignin for the production of lignin-based organic filler 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 filler F1 used according to the present invention. Lignin is a solid biopolymer that is incorporated into plant cell walls and thus causes ligninization of plant cells. Therefore, they represent environmentally friendly filler substitutes that are present in biomass, particularly in biologically recycled raw materials, and therefore especially in hydrothermally treated forms.

[0068] Preferably, lignin, and preferably the organic filler F1 used according to the present invention, exist in a form that is at least partially hydrothermally treated, and particularly preferably can be obtained by hydrothermal treatment. Particularly preferably, the organic filler used according to the present invention is based on lignin that can be obtained by hydrothermal treatment. Processes particularly suitable for the hydrothermal treatment of lignin and lignin-containing organic fillers are described, for example, in International Publications 2017 / 085278 and 2017 / 194346, and European Patent Application Publication 3 470 457. Preferably, the hydrothermal treatment is carried out in the presence of liquid water at a temperature 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 lignin, and more preferably the organic filler itself, is present at least partially in a form that can be obtained by hydrothermal treatment, and particularly preferably can be obtained by hydrothermal treatment, which is carried out at a temperature preferably in the range of >100°C to <300°C, and particularly preferably >150°C to <250°C.

[0069] Optionally, starting materials used for hydrothermal treatment, such as lignin-containing raw materials, particularly lignin, may be reacted with at least one crosslinking agent before the hydrothermal treatment is carried out. The crosslinking agent preferably has at least one functional group that can react with the crosslinkable groups of lignin. Preferably, the crosslinking agent has at least one functional group selected from aldehydes, carboxylic acid anhydrides, epoxides, hydroxyl groups, and isocyanate groups or combinations thereof. Preferably, the crosslinking agent is selected from aldehydes, epoxides, acid anhydrides, polyisocyanates and / or polyols, particularly from aldehydes such as formaldehyde, furfural and / or sugar aldehydes. The crosslinking agent can react with the free ortho and para positions of the phenol ring with the aromatic and aliphatic OH groups and / or carboxyl groups of lignin.

[0070] Preferably, the organic filler F1 is a lignin-containing biomass, particularly a lignin-containing phytomass, more preferably a particulate carbon material from a lignin-containing phytomass, or a particulate carbon material that can be obtained therefrom, as a lignin-containing raw material. The organic filler F1 can be obtained from a lignin-containing biomass having a Claesson lignin content of at least 60% by mass relative to its dry matter content. Preferably, the lignin-containing biomass, such as a lignin-containing phytomass, has a Claesson lignin content of at least 65% by mass, preferably at least 70% by mass, more preferably at least 75% by mass, particularly preferably at least 80% by mass, and particularly at least 85% by mass, relative to its dry matter content. According to Tappi T 222 om-02 (https: / / www.tappi.org / content / SARG / T222.pdf), Claesson lignin is a product quantified in this analytical method, with analytical measurement after treatment in 72% H2SO4. The method is further described in the "Methods" section.

[0071] Preferably, the organic filler F1, especially if it is a particulate material such as particulate carbon material, can be obtained by hydrothermal treatment. During the hydrothermal treatment, preferably a salt, particularly a metal halide such as zinc chloride and / or potassium chloride and / or sodium chloride, is intentionally added to the raw material, such as a lignin-containing raw material, used as a starting material for the hydrothermal treatment. Preferably, the salt of the metal halide, such as zinc chloride and / or potassium chloride and / or sodium chloride, is present during the hydrothermal treatment only in amounts naturally present in the water, such as tap water, used for the hydrothermal treatment.

[0072] The organic filler F1 is present in the rubber composition in an amount ranging from 1 to <140 phr. Preferably, the organic filler F1 is present in the rubber composition in an amount ranging from 1 to 139 or 1 to 138 phr, preferably 5 to 130 or ~115 phr, particularly preferably 10 to 100 or ~80 phr, even more particularly preferably 15 to 70 phr, and most preferably 15 to 60 phr or 20 to 55 phr.

[0073] As previously stated, in addition to the at least one organic filler F1 used in accordance with the present invention, the rubber composition may include one or more other fillers different from the organic filler F1 used in accordance with the present invention.

[0074] If the organic fillers used in accordance with the present invention serve only as partial substitutes for commonly found industrial carbon blacks, the rubber composition according to the present invention may also contain industrial carbon black, particularly furnace carbon black, which is classified as general-purpose carbon black under ASTM Code N660 or ASTM Code N550, for example, as a second filler F2. However, if such carbon blacks are present, their maximum amount in the rubber composition is <40 phr.

[0075] Furthermore, or as an alternative, the rubber composition according to the present invention may include an inorganic filler, for example, as a third filler F2, having various particle sizes, particle surface characteristics and chemical properties, which may have different properties, particularly affecting the processing behavior (rheology). If another filler F3 is included, it should preferably have properties as similar as possible to the organic filler F1 used in the rubber composition according to the present invention, particularly with respect to their pH values.

[0076] If other fillers F3 are used, they are preferably phyllosilicates such as clay minerals, e.g., talc; carbonates such as calcium carbonate; silicates such as calcium silicate, magnesium and aluminum; and oxides such as magnesium oxide and silica or silicic acid.

[0077] In particular, if the organic filler F1 used in accordance with the present invention serves only as a commonly found partial substitution of silica or silica, the rubber composition according to the present invention may also include such inorganic filler F3, for example, silica or silica.

[0078] In the context of this invention, zinc oxide does not fall under the category of inorganic filler F3 because it is responsible for acting as an additive that promotes vulcanization. However, additional fillers must be selected carefully, as silica tends to bind organic molecules to its surface and thus inhibit their action.

[0079] Other components of vulcanizable rubber compositions As previously stated, the rubber composition of the present invention may optionally contain at least one organosilane having at least one hydrolyzable group and at least one sulfur atom. However, in the case of any such organosilane present, its amount in the rubber composition is less than 7 phr.

[0080] If such organosilanes exist, at least one sulfur atom is preferably 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, and in particular at least one sulfur atom is 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.

[0081] At least one organosilane is preferably 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) [In the formula, in the case of general formula (I), Each X independently represents a hydrolyzable group that reacts with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group, and / or a mixture thereof, and each hydrolyzable group independently represents an alkoxy group, particularly preferably OC. 1~4 Selected from alkyl groups, The parameter y represents an integer in the range of 1 to 3, but is at least 1, and preferably exactly 1. R is a non-hydrolyzable organic group, preferably an aliphatic C3-C group having at least one sulfur atom. 20 The group is represented, and the sulfur atom is preferably part of at least one functional group selected from the group consisting of di and / or polysulfide groups such as thiol groups, block thiol groups, and tetrasulfide groups, and mixtures thereof, and more preferably thiol groups. In the formula, in the case of general formula (II), Each X independently represents a hydrolyzable group that reacts with a phenolic OH group, a phenolate group, an aliphatic OH group, a carboxylic acid group, a carboxylate group, and / or a mixture thereof, and each hydrolyzable group independently represents an alkoxy group, particularly preferably OC. 1~4Selected from alkyl groups, RA is a non-hydrolyzable organic group having two bonds, preferably an aliphatic C6-C group having two bonds containing at least one sulfur atom. 20 The group represents, preferably at least one disulfide and / or polysulfide group, particularly preferably a di or tetrasulfide group. Each parameter z represents an integer in the range of 0 to 2, preferably meaning 0 or 2. Unlike the RA group, T represents a non-hydrolyzable organic group that does not have a functional group, preferably an aliphatic C1-C1 group. 20 It is a group, and is particularly preferably free of sulfur atoms.

[0082] In the case of a monosilane of general formula (I), at least one R group is a mercaptoalkyl group, and R is preferably an aliphatic C3-C8 group, particularly preferably an aliphatic C3-C6 group, and the monosilane preferably has at least one X group, preferably two or three X groups.

[0083] Preferably, the monosilane of general formula (I) is selected from the group consisting of 4-mercaptobutyltrialkoxysilane and / or 6-mercaptohexyltrialkoxysilane and / or 3-mercaptopropyltrialkoxysilane, and the alkoxy groups preferably independently represent methoxy or ethoxy groups.

[0084] Preferably, at least one organosilane is a compound of general formula (II). In the case of bis(silane) of general formula (II), the non-hydrolyzable organic group RA is an aliphatic C6-C6 group. 20 Base, particularly preferably aliphatic C6-C 10Preferably, the RA group has at least one sulfur atom. Particularly preferably, the RA has a di or polysulfide group, and even more preferably a di or tetrasulfide group. Preferably, at least one sulfur atom is present within the RA group, and particularly preferably, at least one sulfur atom is not adjacent to a silicon atom. Preferably, the bis(silane) of general formula (II) has at least one X group, particularly preferably two or three X groups. 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, and most preferably TESPD.

[0085] If such organosilanes are present, they are preferably included in the vulcanizable rubber composition according to the present invention in an amount in the range of 0.25 to <7 phr, particularly preferably 0.25 to 5 phr, and even more preferably 0.5 to 3 phr. If such organosilanes are present, they are preferably included in the vulcanizable rubber composition according to the present invention in an amount in the range of 1 to 10% by mass, particularly preferably 2 to 8% by mass, even more preferably 2.5 to 6% by mass, and most preferably 3 to 6 or ~5% by mass, relative to the organic filler F1 contained therein.

[0086] The rubber composition according to the present invention may include other optional components such as plasticizers / softeners and / or degradation inhibitors and / or light-stabilizing waxes and / or resins, particularly resins that increase adhesive strength.

[0087] By using a softening agent, the properties of the non-vulcanized rubber composition, particularly its processability, can be affected, and the properties of the vulcanized rubber composition, particularly its flexibility at low temperatures, can also be affected. Particularly preferred softening agents in the context of the present invention are mineral oils from the group of paraffinic oils (substantially saturated cyclic hydrocarbons) and naphthenic oils (substantially saturated cyclic hydrocarbons). Aromatic hydrocarbon oils can also be used and are even more preferred. However, with respect to the adhesion of the rubber composition to other rubber-containing components in the tire, such as the carcass, a mixture of paraffinic and / or naphthenic oils may also be advantageous as a softening agent. Other possible softening agents include, for example, aliphatic dicarboxylic acids, such as esters of adipic acid or sebacic acid, paraffinic wax, and polyethylene wax. Of the softening agents, paraffinic oils and naphthenic oils are particularly preferred in the context of the present invention. However, the most preferred are aromatic oils, particularly aromatic mineral oils.

[0088] Preferably, a softening agent, of which paraffinic and / or naphthenic, particularly aromatic process oils, is used in an amount of 0 to 10 phr, particularly preferably 1 to 8 phr, even more preferably 1 to 7 phr, and most preferably 1 to 3 phr.

[0089] 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 degradation inhibitors. Preferably, their proportions are 1 to 10 phr, particularly preferably 1 to 7 phr, even more preferably 1 to 5 phr, and most preferably 1 to 2 phr.

[0090] Examples of light-stabilizing waxes include Negozone 3457 from H&R Group or Antilux light-stabilizing waxes from Rhein Chemie, such as Antilux 111 or Antilux 654. Preferably, their proportions are 0.25 to 10 phr, particularly preferably 0.5 to 7 phr, even more preferably 0.5 to 5 phr, and most preferably 0.5 to 2 phr.

[0091] So-called adhesion-enhancing resins can be used to improve the adhesion of the vulcanized rubber compound of the present invention to other adjacent tire components. Particularly preferred resins are phenol-based resins 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 particularly improve adhesion to other rubber components of the tire. They generally have lower adhesion than phenol-based resins and can be used alone or in mixtures with phenol-based resins. However, preferably, no such resins exist, and especially no phenol-based resins.

[0092] Even if an adhesion-enhancing resin is used, it is preferably selected from the group consisting of phenol-based resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins. Preferably, their proportions are 0 to 15 phr, particularly preferably 1 to 15 phr, even more preferably 2 to 10 phr, and most preferably 3 to 8 phr.

[0093] Parts kit Another subject of the present invention is, in a spatially separated form, As part A), a rubber composition used in accordance with the present invention, comprising at least the above rubber and at least the above filler F1, wherein part A of the parts kit is a rubber composition that does not contain sulfur and / or at least one sulfur donor of vulcanizing system VS used in accordance with the present invention, Part B) is a vulcanization system VS used in accordance with the present invention, comprising at least sulfur and / or at least one sulfur donor. A kit of parts including, or preferably consisting of, these.

[0094] Therefore, part A) represents a rubber composition that is not yet vulcanizable by sulfur itself, and therefore not vulcanizable by sulfur at this point. Vulcanization with sulfur is only possible after parts A) and B) are mixed, regardless of whether sulfur itself is present and / or released from only one sulfur donor.

[0095] Preferably, the rubber and fillers of the rubber composition according to the present invention and the vulcanizing system VS on the other are spatially separated from each other in a kit of parts and can therefore be stored. The kit of parts is useful for preparing a vulcanizable rubber composition. For example, a rubber composition constituting one part of the kit of parts, which optionally includes other components, such as zinc oxide and / or at least one fatty acid, including rubber and fillers and a vulcanizing agent other than sulfur, can be used as part A) in step 1 of the process of preparing a vulcanizable rubber composition as further described below herein, and a second part of the kit of parts, i.e., a vulcanizing system VS as part B), which includes at least sulfur and / or at least one sulfur donor, can be used in step 2 of the process.

[0096] All preferred embodiments described herein with respect to the vulcanizable rubber composition according to the present invention are also preferred embodiments relating to a kit of parts according to the present invention.

[0097] Preferably, the kit of parts according to the present invention is Part A) comprises a rubber composition containing at least one type of rubber, at least one type of organic filler F1, optionally another filler such as filler F2 and / or F3, and optionally at least one type of organosilane. Part B) is a vulcanizing system VS comprising at least sulfur and / or at least one sulfur donor, and further zinc oxide, wherein the zinc oxide may be present in part A) as an alternative, and Includes.

[0098] Particularly preferred is a kit of parts according to the present invention. Part A) comprises a rubber composition containing at least one type of rubber, at least one type of organic filler F1, and optionally another filler such as filler F2, Part B) is 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, wherein at least zinc oxide and / or fatty acids may be present in Part A) by alternative means. Includes.

[0099] Process for preparing a vulcanizable rubber composition Another subject of the present invention is a process for preparing a vulcanizable rubber composition according to the present invention.

[0100] All preferred embodiments described herein with respect to the vulcanizable rubber composition and the kit of parts according to the present invention are also preferred embodiments with respect to the process according to the present invention.

[0101] The preparation of the vulcanizable rubber composition according to the present invention is preferably carried out in two steps, namely steps 1 and 2.

[0102] In the first step (Step 1), the rubber composition is initially prepared as a base mixture (masterbatch) by mixing all the components used to prepare the vulcanizable rubber composition according to the present invention with each other, but without mixing with sulfur and / or at least one sulfur donor. In the second step (Step 2), the sulfur and / or at least one sulfur donor of the vulcanizing system VS, and optionally additional components, are mixed into the rubber composition obtained after Step 1.

[0103] Stage 1 Preferably, the present invention provides at least one rubber included in the rubber composition, and a different resin which may be used at an optional rate. However, the latter may be added subsequently together with another additive as an alternative. Preferably, the rubber is preheated to a temperature of at least room temperature (23°C), or particularly preferably up to 50°C, even more preferably up to 45°C, and especially preferably up to 40°C. Particularly preferably, the rubber is pre-mixed for a short time before the other components are added. If an inhibitor such as magnesium oxide is used for subsequent vulcanization control, it is preferably added at this point.

[0104] Next, at least one organic filler F1 used in accordance with the present invention, and optionally other fillers such as fillers F2 and / or F3, are added, except preferably zinc oxide. This is because zinc oxide is used as a component of the vulcanization system in the rubber composition according to the present invention, as described above herein, and is therefore not considered a filler. The addition of at least one organic filler and optionally other fillers is preferably carried out gradually.

[0105] While advantageous, it is not mandatory, and other components such as emollients, at least one organosilane used at will, and sulfurizing agents other than sulfur, such as stearic acid and / or zinc stearate and / or zinc oxide, are added only after the addition of at least one organic filler F1 and / or other fillers, if used. This promotes the incorporation of at least one organic filler F1 and, if other fillers are present, their incorporation. However, it may be advantageous to incorporate organic filler F1, or, if other fillers are present, a portion thereof, together with the emollient and any other components used at will.

[0106] The maximum temperature obtained during the preparation of the rubber composition in the first step ("damp temperature") should not exceed 170°C, as exceeding these temperatures may cause partial decomposition of the reactive rubber and / or organic fillers. However, depending particularly on the rubber used, temperatures >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 step is 80°C to <200°C, particularly preferably 90°C to 190°C, and most preferably 95°C to 170°C.

[0107] The mixing of components of a rubber composition is typically carried out using an internal mixer equipped with tangential or intermeshing (i.e., intermeshing) rotors. The latter usually allows for better temperature control. A mixer with tangential rotors is also called a tangential mixer. However, mixing can also be carried out using, for example, a twin-roll mixer. Depending on the rubber used, the mixing process may be carried out conventionally, starting with the addition of the polymer, or conversely, by adding all other components of the mixture first and then adding the polymer last.

[0108] After the preparation of the rubber composition is complete, it is preferably cooled before carrying out the second step. This type of process is also called relaxation. A typical relaxation period is 6 to 24 hours, preferably 12 to 24 hours.

[0109] Stage 2 In the second step, at least sulfur and / or at least one sulfur donor of the vulcanizing system VS, preferably additional components, are incorporated into the rubber composition of the first step, thereby obtaining the vulcanizable rubber composition according to the present invention. Preferably, if sulfur crosslinking accelerators are used / present, they are also incorporated in step 2.

[0110] If zinc oxide, and optionally at least one saturated fatty acid such as stearic acid, are used as a vulcanizing system in addition to sulfur and / or at least one sulfur donor, the addition of all these components is carried out in step 2. However, these components can also be integrated into the rubber composition in step 1, except for the sulfur and / or at least one sulfur donor.

[0111] In the second stage, the maximum temperature obtained during the preparation of the vulcanization system admixture into the rubber composition ("damp temperature") should preferably not exceed 130°C, and particularly preferably not exceed 125°C. The preferred temperature range is 70°C to 125°C, and particularly preferably 80°C to 120°C. At temperatures exceeding the maximum temperature of 105°C to 120°C for the crosslinking system, premature vulcanization may occur.

[0112] After mixing the vulcanization system in step 2, the composition is preferably cooled.

[0113] In the two-step process described herein, the rubber composition is first obtained in the first step and then expanded in the second step to a vulcanizable rubber composition.

[0114] Prior to vulcanization, the vulcanizable rubber composition thus prepared may undergo a deformation process to be customized or adapted to the final article, preferably. The rubber composition may be formed into a suitable shape required for the vulcanization process, preferably by extrusion or calendering. Vulcanization may be carried out by pressure and temperature in a vulcanization mold, or without pressure in a temperature-controlled channel where air or liquid material enables heat transfer.

[0115] vulcanized rubber composition Another subject of the present invention is a vulcanizable rubber composition that can be obtained by vulcanizing a vulcanizable rubber composition according to the present invention, or by vulcanizing a vulcanizable rubber composition that can be obtained by combining and mixing two parts A) and B) of a parts kit according to the present invention.

[0116] All preferred embodiments described herein with respect to the vulcanizable rubber composition and kit of parts according to the present invention, as well as the process according to the present invention, are also preferred embodiments with respect to the vulcanizable rubber composition according to the present invention.

[0117] Typically, vulcanization is carried out under pressure and / or under the influence of heat. Preferred vulcanization temperatures are preferably 100°C to 200°C, particularly preferably 120°C to 180°C, and most preferably 140°C to 170°C. Optionally, vulcanization is carried out at pressures in the range of 50 bar to 300 bar. However, vulcanization can also be carried out at pressures in the range of 0.1 bar to 1 bar, for example, in the case of profiles. The closing pressure of the press is typically in the range of 150 bar to 500 bar, depending on the mixture and product geometry.

[0118] Use of vulcanizable rubber compositions Another subject of the present invention is the production of tires, preferably pneumatic tires and solid tires, and the production of tire components, preferably natural rubber and / or low glass transition temperature T used in their production. g The use of the vulcanizable rubber composition according to the present invention, a kit of parts according to the present invention, or the vulcanizable rubber composition according to the present invention is for use in the production of tire components, particularly for use in the production of tire components selected from the group of base components, i.e., components under the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, or for use in the production of rubber articles such as technical rubber articles, preferably for use in the production of drive belts, straps / belts, molded parts, e.g., buffers / cushions, bearings / mounts, e.g., liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses, such as the vulcanizable rubber composition according to the present invention, a kit of parts according to the present invention, or the vulcanizable rubber composition according to the present invention, such that the lowest possible tanδ value of the vulcanizable rubber composition, such as a rubber composition containing rubber having, is targeted.

[0119] The term “technical rubber articles” (also known as mechanical rubber articles, MRGs) is known to those skilled in the art. Examples of technical rubber articles include drive belts, straps / belts, molded parts, such as buffers / cushions, bearings / mounts, especially fluid-filled mounts, conveyor belts, profiles, seals, dampers and / or hoses.

[0120] All preferred embodiments described herein with respect to the vulcanizable rubber composition, the parts kit according to the present invention, the process according to the present invention, and the vulcanizable rubber composition according to the present invention are also preferred embodiments with respect to the above-mentioned uses of the present invention.

[0121] Tires and tire components Another subject of the present invention is tires, preferably pneumatic tires or solid tires, or tire components, produced using the vulcanizable rubber composition according to the present invention, a kit of parts according to the present invention, or the vulcanizable rubber composition according to the present invention, respectively. Preferably, in the case of tire components, these are selected from the base components, i.e., the components below the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement.

[0122] All preferred embodiments described herein with respect to the vulcanizable rubber composition, the parts kit according to the present invention, the process according to the present invention, the vulcanizable rubber composition according to the present invention, and the use according to the present invention are also preferred embodiments with respect to the above-mentioned tire according to the present invention.

[0123] Rubber articles, especially technical rubber articles Another subject of the present invention is rubber articles, particularly technical rubber articles, preferably selected from drive belts, straps / belts, molded parts, such as buffers / cushions, bearings / mounts, especially liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses, produced by utilizing the vulcanizable rubber composition according to the present invention, kits of parts according to the present invention, or vulcanizable rubber composition according to the present invention.

[0124] All preferred embodiments described herein relating to the vulcanizable rubber composition, the parts kit according to the present invention, the process according to the present invention, the vulcanizable rubber composition according to the present invention, and the use according to the present invention are also preferred embodiments relating to preferred technical rubber articles according to the present invention.

[0125] Uses organic filler F1 Another subject of the present invention is the use of organic filler F1, particularly without the presence of any additional organosilane having at least one hydrolyzable group and at least one sulfur atom, to increase the dynamic stiffness of a vulcanizable rubber composition that can be obtained from a vulcanizable rubber composition preferably obtained from the vulcanizable rubber composition according to the present invention, compared to a vulcanizable rubber composition that does not contain organic filler F1 but contains only carbon black as a filler, or carbon black in an amount of ≥40 phr as a filler, preferably increasing the complex modulus G*, decreasing the tanδ value, or preferably doing both simultaneously. A method for determining the dynamic stiffness, including the tanδ value and the complex modulus G*, is described in the Methods section.

[0126] All preferred embodiments described herein relating to the vulcanizable rubber composition according to the present invention, the parts kit according to the present invention, the method according to the present invention, the vulcanizable rubber composition according to the present invention, and the use according to the present invention, and preferably technical rubber articles and tires according to the present invention, are also preferred embodiments relating to the use of filler F1 according to the present invention.

[0127] How to decide 1. 14 Determination of C content 14 The determination of the carbon content (biologically based carbon content) is carried out by the radiocarbon dating method in accordance with DIN EN 16640:2017-08.

[0128] 2. Determination of particle size distribution The particle size distribution can be determined by laser diffraction of the material dispersed in water (1% by mass in water) according to ISO 13320:2009, with sonication at 12000 Ws performed before measurement. The volume fraction is specified, for example, as d99 (in μm) (the diameter of 99% of the crystal grains in the sample volume is less than this value). The d90 and d25 values ​​(in μm) are determined similarly.

[0129] 3. Determination of carbon content The carbon content is determined by elemental analysis in accordance with DIN 51732: 2014-7.

[0130] 4. Determination of oxygen content The oxygen content is determined by high-temperature pyrolysis using the 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).

[0131] 5. Determination of the dry matter content of the organic filler used. The dry matter content of the samples was determined as follows, in accordance with DIN 51718:2002-06. For this purpose, a Sartorius MA100 moisture balance was heated to a drying temperature of 105°C. If the dry sample was not yet in powder form, it was ground or pulverized in a mortar and pestle to produce a powder. Approximately 2 g of the sample to be measured was weighed into a suitable aluminum pan using a moisture balance, and then the measurement was started. The measurement was considered to be constant unless the mass of the sample changed by more than 1 mg for 30 seconds, and the measurement was stopped. The dry matter content then corresponds to the stated content (unit mass %) of the sample. At least one duplicate determination was performed for each sample. The weighted average value was reported.

[0132] 6. Determination of the pH value of the organic filler used. The pH was determined as follows, in accordance with ASTM D 1512 standard. If the dry sample was not yet in powder form, it was ground or pulverized in a mortar and pestle to produce a powder. In either case, 5 g of the sample and 50 g of completely deionized water were weighed into a glass beaker. Using a magnetic stirrer equipped with a heating function and a stirring bar (stirring flea), the suspension was heated to 60°C while constantly stirring, and the temperature was maintained at 60°C for 30 minutes. Subsequently, the heating function of the stirrer was stopped to allow the mixture to cool while stirring. After cooling, evaporated water was replenished by adding completely deionized water again, and the mixture was stirred again for 5 minutes. The pH value of the suspension was determined using calibrated measuring instruments. The temperature of the suspension should be 23°C (±0.5°C). Duplicate determination was performed for each sample, and the average value was reported.

[0133] 7. Determination of the ash content of organic fillers The water-free ash content of the samples was determined by thermogravimetric analysis according to DIN 51719 as follows. Before weighing, the samples were crushed or ground in a mortar. The dry material content of the weighed material was determined before ash content determination. The sample material was weighed into a crucible to the nearest 0.1 mg. The furnace containing the samples was heated to a target temperature of 815°C at 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 samples were removed. The samples were cooled to room temperature in a desiccator and weighed again. The remaining ash content was correlated with the initial mass, and thus the mass percentage of ash content was determined. Triplicate determinations were performed for each sample, and the average value was reported.

[0134] 8. Determination of BET and STSA surface area of ​​organic fillers The specific surface area of ​​the filler under investigation was determined by nitrogen adsorption in accordance with the ASTM D 6556 (2019-01-01) standard for industrial carbon black. According to this standard, the BET surface area (specific total surface area according to Brunauer, Emmett, and Teller) and external surface area (STSA surface area; statistical thickness specific surface area) were also determined as follows.

[0135] The analyte samples were dried at 105°C to a dry matter content of ≥97.5% by mass prior to measurement. Furthermore, the measuring cells were dried in a drying oven at 105°C for several hours before weighing the samples. The samples were then filled into the measuring cells using a funnel. If the upper measuring cell shaft became contaminated during filling, it was cleaned using a suitable brush or pipe cleaner. In the case of highly volatile (electrostatic) materials, glass wool was additionally weighed onto the sample. Glass wool was used to hold any materials that might scatter during the firing process and contaminate the unit.

[0136] The sample to be analyzed was heated at 150°C for 2 hours, and the Al2O3 standard was heated at 350°C for 1 hour. The following N2 dosages were used to determine the appropriate pressure range. p / p0 = 0~0.01: N2 Dosage: 5 ml / g p / p0 = 0.01~0.5: N2 dosage: 4 ml / g.

[0137] To determine the BET surface, extrapolation was performed at at least six measurement points in the range of p / p0 = 0.05 to 0.3. To determine the STSA, extrapolation was performed at at least seven measurement points in the range of t = 0.4 to 0.63 nm (corresponding to p / p0 = 0.2 to 0.5) of the adsorbed N2 layer thickness.

[0138] 9. Determining Hardness The Shore A hardness of vulcanized rubber compositions was determined at 23°C according to ISO 48-4:2018-08 using a digital Shore hardness tester from Sauter GmbH. To achieve the minimum specimen thickness of 6 mm required by the standard, the specimens consisted of no more than three layers. For this purpose, three S2 bars, punched out for tensile testing according to ISO 37:2011, were stacked on top of each other. For each sample stack, five measurements were taken at different points on the stack. The results obtained represent the average of these five measurements. Between vulcanization and testing, the samples were stored in the laboratory at room temperature for at least 16 hours.

[0139] 10. Determination of crosslinking density / reaction kinetics The crosslinking density and reaction kinetics of the rubber composition were determined according to DIN 53529-3:1983-06 at 160°C, with a deflection of 0.5 or 3° (as specified in the experimental section). The measurement time was 30 minutes. In the process, minimum and maximum torque (M) were measured. L M H ) was determined. From these, the difference Δ(Δ(M) H -M L The (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 required to reach 10%, 50%, and 90% of the target was determined. 10 , T 50 and T 90 I specified that.

[0140] 11. Determination of elongation under tension For the vulcanized rubber composition, the elongation under tension was determined, including the tensile strength and elongation at the break point, in accordance with ISO 37:2011.

[0141] 12. Dynamic Mechanical Thermal Analysis (DMTA) or Dynamic Mechanical Analysis (DMA) DMTA / DMA is useful for characterizing viscoelastic behavior. The rubber-based component possesses both elasticity and viscosity. This behavior is typically characterized by the tangent delta, abbreviated as tanδ. The tangent delta is the ratio of the loss modulus to the storage modulus, where the storage modulus represents the stored energy representing the elastic portion, and the loss modulus corresponds to the proportion of energy lost through conversion to heat due to internal friction. The tests were conducted according to ISO standard 4664-3:2021. Viscoelastic behavior was analyzed using the Netzsch EPLEXOR 2000 test apparatus. In the time-sweep process, sinusoidal vibration stress was applied to the vulcanized rubber composition within the range of linear elastic deformation. The tests were performed with the following parameters: Static load (force): 50N Dynamic load (force): 25N Contact force: 0.30N Temperature: 60℃; Immersion time: 300 seconds; Frequency: 10Hz; Undermeasured load: Front and dynamic loads Sample shape: 16.15 mm cylinder.

[0142] These test conditions were used to predict the potential for reducing tire rolling resistance.

[0143] In general, a complex number or dynamic modulus (G*) is defined as follows: G* = G' + ixG" However, G': Storage modulus (real component; represents the elastic component) G: Loss modulus (represents the imaginary component; viscosity component) i: Imaginary number

[0144] The loss coefficient tanδ(tanδ) is defined as follows: tanδ=G" / G'

[0145] 13. Determination of Claesson's lignin content The Claesson lignin content is determined according to Tappi T 222 om-02 (https: / / www.tappi.org / content / SARG / T222.pdf). The Claesson lignin content is determined after treating lignin-containing biomass in 72% H2SO4. The method includes the following steps: extract the lignin-containing biomass using benzene and ethanol, then add 72% concentrated sulfuric acid, and heat the resulting mixture at 30°C for 4 hours. Then dilute with water to a sulfuric acid content of 3%, and heat the resulting mixture at reflux temperature for 2 hours. Remove any insoluble material present in the mixture by filtration and weigh as Claesson lignin as described by A. Sluiter et al. (2008), "Determination of Structural Carbohydrates and Lignin in Biomass," NREL Technical Report NREL / TP-510-42618.

[0146] Examples and Comparative Examples The following examples and comparative examples are helpful in illustrating the present invention, but should not be construed as limiting them.

[0147] 1. Production of organic fillers used in accordance with the present invention 1.1 As the first organic filler according to the present invention, lignin L1, which can be obtained by hydrothermal treatment, was used.

[0148] Lignin L1 obtainable by hydrothermal treatment was produced according to the method for producing hydrothermal lignin described in International Publication No. 2017 / 085278. The reaction with formaldehyde was carried out prior to the hydrothermal treatment described in International Publication No. 2021 / 005230, and the heat treatment was carried out after the hydrothermal treatment described in International Publication No. 2022 / 043470.

[0149] For this purpose, a liquid containing lignin was prepared. First, water and lignin were mixed to prepare a lignin-containing liquid with a dry matter content of 9.7% by mass. Subsequently, the lignin was mostly dissolved in the lignin-containing liquid. For this purpose, the pH value was adjusted by adding NaOH. The preparation of the solution was accelerated by vigorous mixing at 80°C for 3 hours. Next, the lignin-containing liquid was modified using formaldehyde. The lignin-containing liquid was then subjected to hydrothermal treatment to obtain a solid. In this process, the prepared solution was heated to a reaction temperature of 240°C at 1.5 K / min and then held for a reaction period of 2 hours. Subsequently, it was cooled. As a result, an aqueous suspension of the solid was obtained. By filtration and washing, the solid was mostly dehydrated and washed. The subsequent drying and heat treatment were carried out in a fluidized bed under nitrogen. For drying, the temperature was raised to 50°C at 1.5 K / min and held for 2.5 hours. Subsequently, for heat treatment, the temperature was raised to 190°C at 1.5 K / min and held for 15 minutes, and then cooled again. The dried solid was pulverized in a jet mill using nitrogen as the jet gas to a d99 value < 10 μm (determined according to the determination method described above in this specification). The resulting product was slowly granulated using roller compression (cantilever). Granulation was carried out so that the sieve residue had an L1 of 1315 ppm (45 μm).

[0150] 1.2 As a second organic filler according to the present invention, lignin L2 obtainable by hydrothermal treatment was used. The lignin L2 obtainable by hydrothermal treatment was produced according to the method for producing lignin obtainable by hydrothermal treatment described in International Publication No. 2017 / 085278. The reaction with formaldehyde was carried out before the hydrothermal treatment described in International Publication No. 2021 / 005230, and the heat treatment was carried out after the hydrothermal treatment described in International Publication No. 2022 / 043470.

[0151] For this purpose, a liquid containing lignin was prepared. First, water and lignin were mixed to prepare a lignin-containing liquid with a dry matter content of 15.8% by mass. Subsequently, the lignin was mostly dissolved in the lignin-containing liquid. For this purpose, the pH value was adjusted by adding NaOH. The preparation of the solution was accelerated by vigorous mixing at 80°C for 3 hours. Next, the lignin-containing liquid was modified with formaldehyde at 80°C for 1 hour. The lignin-containing liquid was then subjected to hydrothermal treatment. In the hydrothermal treatment, the prepared solution was heated to a reaction temperature of 230°C at 1.5 K / min and then held for a reaction period of 2 hours. Subsequently, it was cooled. As a result, an aqueous suspension of the solid was obtained. The solid was mostly dehydrated and washed by filtration and washing. Subsequent drying and heat treatment were carried out in a furnace under nitrogen. For drying, the temperature was raised to 105°C at 0.5 K / min and held for 12 hours. Subsequently, for heat treatment, the temperature was raised to 190°C at 0.3 K / min and held for 60 minutes, and then cooled again. Nitrogen was flowed through the system during heating, drying, heat treatment, and cooling to maintain an oxygen content of less than 1.5%. The resulting dried solid was pulverized in a jet mill using nitrogen as the jet gas (determined according to the determination method described above in this specification) to a d99 value < 10 μm. The resulting product was slowly granulated using roller compression (cantilever). Granulation was carried out so that the sieve residue had an L2 of 316 ppm (45 μm).

[0152] 1.3 The lignins L1 and L2 that can be obtained by hydrothermal treatment are characterized as specified in Table 1.1 below by the methods described above in this specification.

[0153] [Table 1]

[0154] 2. Production of vulcanizable rubber compositions A vulcanizable rubber composition was prepared by a two-step process.

[0155] In the first step, a rubber composition (masterbatch) as a base mixture was prepared by compounding the components of the rubber composition according to the present invention, which include rubber composition K and filler component F. In the second step, the components of the crosslinking system (vulcanization system VS) were mixed together.

[0156] A vulcanizable rubber composition having an organic filler L1 or L2 used in accordance with the present invention, a vulcanizable rubber composition having an organic filler L1 or L2 and industrial carbon black as a second filler used in accordance with the present invention, and a corresponding comparative rubber composition having industrial carbon black as a single filler were prepared as follows.

[0157] Stage 1 Natural rubber (NR) SVR CV 60 from the trading company Weber & Schaer was used as the rubber.

[0158] When industrial carbon black was used as a filler alone (comparative rubber composition VK1V1), it was added at 2:00 min as 33.3% of one batch (together with the additives used, e.g., zinc oxide, stearic acid, and other additives; see Table 2.2 (Table 3) below), and at 3:00 min as 33.3% of another batch (together with 50% of the process oil used). At 5 min, 33.3% of the last batch of industrial carbon black was added together with the remaining 50% of the process oil used.

[0159] When the filler used in accordance with the present invention is used as a single filler (rubber compositions VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention), it is added as a 33.3% batch (together with the additives used) after 2:00 minutes, and as another 33.3% batch (together with 50% of the process oil used) after 3:00 minutes. After 5 minutes, 33.3% of the last batch of the filler used in accordance with the present invention is added together with another 50% of the process oil used.

[0160] In the case of partial substitution of industrial carbon black with fillers used according to the present invention (rubber composition VK1B1 and rubber composition VK1B2), 100% of the industrial carbon black used is added together with the additive used after 2:30 minutes. After 3:30 minutes, 50% of the fillers used according to the present invention are added (together with 50% of the process oil used), and after 5:30 minutes, another 50% is added (together with another 50% of the process oil used).

[0161] For all compositions, the components of the mixture were mixed dispersively and distributedly until the mixing process was stopped after 10 minutes, and the rubber composition was removed from the laboratory mixer. Under these mixing conditions, the rubber composition achieved a final temperature of 130°C–140°C in all cases. After the preparation of the rubber composition was complete, it was cooled before carrying out the second stage (relaxation / storage).

[0162] Step 1 described above in this specification yielded six types of rubber compositions according to the present invention, each containing natural rubber as rubber component K and lignin L1 (K1B1 and K1B4) or lignin L2 (K1B2, K1B3, K1B5 and K1B6) obtainable by hydrothermal treatment as an organic filler component. In the case of K1B1 and K1B2, the rubber composition according to the present invention also contained carbon black as a second filler component.

[0163] Furthermore, comparative compositions K1V1 were obtained. These also contained natural rubber as the rubber component K, but did not contain lignin L1 or L2, and exclusively contained commercially available carbon black as the organic filler component.

[0164] The precise composition of vulcanizable rubber compositions can be found in Table 2.1 below. The quantities are listed in phr (parts per 100 parts by mass of rubber).

[0165] Stage 2 In the second step, one (K1V1), two (K1B1, K1B2, K1B3, and K1B4, and K1B5), or three (K1B6) accelerators were incorporated into the rubber composition from the first step, thus obtaining a vulcanizable rubber composition. A sulfur crosslinking agent and one or more sulfur accelerator systems were added as co-actors to a laboratory mixer and mixed together with the rubber composition from the first step at a speed of 50 rpm for 5 minutes. In this case, the final temperature was 90°C to 100°C. After mixing in the crosslinking system, the resulting composition was cooled.

[0166] Step 2 described above in this specification yielded six vulcanizable rubber compositions according to the present invention (VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6) after the addition of a vulcanization system VS consisting of a crosslinking agent and an accelerator. These can be vulcanized after the completion of Step 2. Furthermore, a comparative vulcanizable rubber composition (VK1V1) was obtained in this manner. These can also be vulcanized after the completion of Step 2. The exact compositions of the vulcanizable rubber compositions can be found in Tables 2.1 and 2.2 below.

[0167] As industrial carbon black, we used commercially available carbon black N550 from Lehmann & Voss & Co. (the carbon black supplier). As process oil, we used a naphthenic softener (VIVATEC 500) from Hansen & Rosenthal. As an antioxidant, we used N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD) from Lehmann & Voss & Co., traded as LUVOMAXX IPPD, and as a light-stabilizing wax, we used NEGOZONE 3457 F from Hansen & Rosenthal. As a crosslinking agent (sulfur), we used Struktol® SU95 from Schill+Seilacher. As a crosslinking agent (sulfur donor), we used Avorator DTDM 80 GE, a polymer-bound sulfur donor based on 4,4'-dithiodimorpholine from Avokal®. As accelerators, we used Rhenogran® TBBS-80 (B1) from Rhein Chemie, Rhenogran® TBzTD-70 (B2) from Rhein Chemie, and Avorator® TMTD-80 (B3) from Avokal®. As zinc oxide, we used Weisssiegel from Bruggemann. As stearic acid, we used Palmera B 1805 from Avokal®.

[0168] [Table 2]

[0169] [Table 3]

[0170] 3. Inspection and testing of vulcanizable rubber compositions and vulcanizable compositions that can be obtained therefrom. 3.1 Crosslinking density and reaction kinetics The rubber compositions obtained after step 2 were examined for the properties of their raw material mixtures. In the process, the reaction kinetics and crosslink density were measured according to the methods described above in this specification.

[0171] Table 3.1 (Table 4) shows the minimum and maximum torque (M) of comparative example VK1V1. L M H ), difference Δ(M H -M L ) and time T 10 , T 50 and T 90 The following is a summary of the results obtained. The value was determined by a deflection of 0.5°C.

[0172] [Table 4]

[0173] Table 3.2 (Table 5) shows the minimum and maximum torque (M) of the vulcanized rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5 and VK1B6 according to the present invention. L M H ), difference Δ(M H -M L ) and time T 10 , T 50 and T 90 The results obtained regarding this are summarized below. The value was determined by a deflection of 0.5°.

[0174] [Table 5]

[0175] The rubber compositions VK1B1 and VK1B2 according to the present invention, characterized by partial substitution of carbon black with lignin-based fillers L1 or L2, exhibit increased incubation time (better scorch time) and longer T compared to the comparative example VK1V1. 90This yields a significant improvement. Surprisingly, rubber compositions VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention, characterized by the complete substitution of carbon black with lignin-based filler L1 or L2, show a much increased incubation time (better scorch time) compared to comparative example VK1V1, and a significantly longer T 90 It brings about a value.

[0176] 3.2 Tensile strength, elongation at break, Shore A hardness The resulting rubber composition K1V1 was vulcanized at 160°C, with the vulcanization time adjusted according to the reaction kinetics of each mixture. For mixture VK1V1, the vulcanization time was 7 minutes. Subsequently, the tensile strength, elongation at break, and Shore A hardness were determined according to the methods described above.

[0177] Table 3.3 (Table 6) summarizes the results obtained for comparative example VK1V1.

[0178] [Table 6]

[0179] The resulting rubber compositions K1B1, K1B2, K1B3, K1B4, K1B5, and K1B6 were vulcanized at 160°C, with the vulcanization time adapted to the reaction kinetic data for each mixture. The vulcanization times were 7 minutes for mixture VK1B1, 7 minutes for mixture VK1B2, 9 minutes for mixture VK1B3, 11 minutes for mixture VK1B4, 9 minutes for mixture VK1B5, and 10 minutes for mixture VK1B6. Subsequently, the tensile strength, elongation at break, and Shore A hardness were determined according to the methods described above in this specification.

[0180] Table 3.4 (Table 7) summarizes the results obtained for the vulcanized rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention.

[0181] [Table 7]

[0182] Compared to comparative rubber composition VK1V1, the rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention show a decrease in tensile strength when carbon black is partially replaced with lignin-based filler L1 or L2 (VK1B1 and VK1B2), and a significant decrease in tensile strength when carbon black is completely replaced with lignin-based filler L1 or L2 (VK1B3, VK1B4, VK1B5, and VK1B6), while the hardness (Shore A) remains unchanged or increases.

[0183] 3.3 Dynamic Mechanical Thermal Analysis (DMTA) The vulcanized rubber compositions were analyzed by dynamic mechanical thermal analysis (DMTA) according to the methods described above herein to characterize their viscoelastic behavior. It is fundamentally desirable for the vulcanized rubber compositions to achieve the highest possible dynamic stiffness and the lowest possible tanδ value. One important indicator of dynamic stiffness is the complex modulus G*. Typically, high dynamic stiffness G* (60°C) increases the loss coefficient tanδ. However, low heat generation, and therefore low tanδ values, are preferred.

[0184] Table 3.5 (Table 8) summarizes the results obtained for comparative example VK1V1.

[0185] [Table 8]

[0186] Table 3.6 (Table 9) summarizes the results obtained for the vulcanized rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention.

[0187] [Table 9]

[0188] The dynamic stiffness of the vulcanized rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6 according to the present invention, as expressed by a complex modulus, is remarkably higher than that of comparative example VK1V1, which has industrial carbon black as the sole filler. At the same time, the rubber compositions VK1B1, VK1B2, VK1B3, VK1B4, VK1B5, and VK1B6 vulcanized according to the present invention exhibit a loss coefficient tanδ that is remarkably comparable to, or significantly lower than, that of comparative example VK1V1, which has industrial carbon black as the sole filler.

[0189] Rubber compositions VK1B3, VK1B5, and VK1B6, which have lignin L2 as a sole filler, show particularly significant improvements in these parameters compared to rubber composition VK1V1, which has carbon black as a sole filler. The combination of high dynamic stiffness and low loss coefficient, as an indicator of hysteresis, which is the conversion of mechanical energy to heat, is unique to these lignin-based fillers. This reduction in heat generation reduces tire rolling resistance and has a positive effect on vehicle fuel consumption and CO2 emissions. By better separating the technically important values ​​of these two rubbers compared to rubber compositions containing industrial carbon black, the lignin-based compositions disclosed herein are highly advantageous for use in rubber articles used under dynamic deformation, for example, for use in compounds for tire carcasses to improve tire rolling resistance, or for use in technical rubber articles.

Claims

1. A vulcanizable rubber composition, A vulcanization system VS comprising at least sulfur and / or at least one sulfur donor, A rubber comprising at least one type of rubber that can be crosslinked with sulfur and / or a sulfur donor, provided that, if at least one type of halobutyl rubber is present, it is present in the rubber composition in an amount of <70 phr, The first filler F1 is an organic filler of which at least one type of organic filler can be obtained from lignin-containing biomass having a Claesson lignin content of at least 60% by mass relative to its dry matter content, and It contains organic filler F1, Unlike carbon black, Range of 0.20 to 0.45 Bq / g carbon 14 It contains C, >24.0~150m 2 Having a BET surface area in the range of / g, It is present in the rubber composition in an amount ranging from 1 to <140 phr. The amount of any carbon black optionally present in the rubber composition as at least one type of second filler F2 is <40 phr. The amount of any organosilane optionally present in the rubber composition, having at least one hydrolyzable group and at least one sulfur atom, is <7 phr. The vulcanizable rubber compositions VK1V2, VK1B1, VK2B1, VK2B2, VK2B3, VK2B4 and VK2B5 disclosed in the experimental section of international application PCT / EP2022 / 076858 are excluded. A rubber composition excluding the vulcanizable rubber composition VKV3 disclosed in the experimental section of international application PCT / EP2022 / 073490 (published as international publication 2023 / 025808).

2. The rubber composition according to claim 1, characterized in that the organic filler F1 has an STSA surface area that is different from its BET surface area by at most 20%, preferably at most 15%, more preferably at most 10%, even more preferably at most 7.5%, and even more preferably at most 6.5 or 5.0%.

3. The rubber composition according to claim 1 or 2, wherein the amount of any carbon black optionally present in the rubber composition as at least one type of second filler F2 is in the range of 0 to <39 phr, preferably 0 to 35 phr, more preferably 0 to 30 or 0 to <30 phr, even more preferably 0 to ≤29 phr, even more preferably 0 to 25 phr, even more preferably 0 to 20 or ~15 phr, even more preferably 0 to 10 or ~5 phr, and even more preferably the rubber composition does not contain or is essentially free of any carbon black as the second filler F2.

4. The rubber composition according to any one of claims 1 to 3, characterized in that, if carbon black is present as filler F2, the relative mass ratio of organic filler F1 to carbon black is in the range of 49:1 to 1:2, preferably 40:1 to 1:1.75, more preferably 30:1 to 1:1.50, even more preferably 25:1 to 1:1.25, even more preferably 20:1 to 1:1, and even more preferably 15:1 to >1:1, or the rubber composition does not contain or essentially contains any carbon black as filler F2.

5. The rubber composition according to any one of claims 1 to 4, wherein the amount of any organosilane having at least one hydrolyzable group and at least one sulfur atom optionally present in the rubber composition is <5 phr, preferably the rubber composition does not contain or is essentially free of any organosilane having at least one hydrolyzable group and at least one sulfur atom, and more preferably the rubber composition does not contain or is essentially free of any type of organosilane.

6. The rubber composition according to any one of claims 1 to 5, characterized by containing at least one organic filler F1 in an amount ranging from 1 to 139 or 138 phr, preferably 5 to 130 or 115 phr, particularly preferably 10 to 100 or 80 phr, even more preferably 15 to 70 phr, most preferably 15 to 60 phr or 20 to 55 phr.

7. The rubber composition according to any one of claims 1 to 6, characterized in that the organic filler F1 is a particulate carbon material that can be obtained from lignin-containing biomass, preferably lignin-containing phytomass, and the lignin-containing biomass has a Claesson lignin content of preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass, particularly preferably at least 80% by mass, and particularly particularly at least 85% by mass, relative to its dry matter content.

8. The rubber composition according to any one of claims 1 to 7, characterized in that the organic filler F1 is a lignin-based filler, preferably the organic filler F1 is present in a form that can be obtained by hydrothermal treatment of lignin-containing biomass, and the hydrothermal treatment is carried out at a temperature preferably in the range of >100°C to <300°C, particularly preferably >150°C to <250°C.

9. Organic filler F1, >20 or >22 or >23 or 24 to <150m 2 / g, preferably 20 or >22 or >23 or 24-130m 2 / g, particularly preferably 25-120m 2 / g, more specifically preferably 30 to 110m 2 / g, especially 40-100m 2 / g, most preferably 40 to <100m 2 STSA surface area in the range of / g, and / or 25 to 120 m 2 in the range of / g, particularly preferably 30 to 110 m 2 in the range of / g, most preferably 40 to 100 m 2 BET surface area in the range of / g, and / or d99 values ​​of <25 μm, preferably <20 μm, particularly preferably <18 μm, more specifically preferably <15 μm, even more preferably <12 μm, even more preferably <10 μm, even more preferably <9 μm, and even more preferably <8 μm The rubber composition according to any one of claims 1 to 8, wherein the d99 value is preferably determined by laser diffraction in accordance with ISO 13320:2009.

10. Organic filler F1, each Oxygen content in the range of >8% to <30% by mass, preferably >10% to <30% by mass, particularly preferably >15% to <30% by mass, most preferably >20% to <30% by mass, relative to ash-free and water-free fillers, and / or Carbon content in the range of >60% to <90% by mass, preferably >60% to <85% by mass, particularly preferably >60% to <82% by mass, and most preferably >60% to <80% by mass, relative to ash-free and water-free fillers. A rubber composition according to any one of claims 1 to 9, characterized by having [a certain property].

11. The sulfur-crosslinkable rubber is a diene rubber selected from the group consisting of diene rubber, preferably natural rubber (NR), synthetic natural rubber, particularly isoprene rubber (IR), ethylene propylene diene monomer rubber (EPDM), styrene butadiene rubber (SBR), solution polymerized styrene butadiene rubber (SSBR), emulsion polymerized styrene butadiene rubber (ESBR), particularly 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 selected from natural rubber, styrene butadiene rubber or solution polymerized styrene butadiene rubber, and mixtures thereof, and / or Sulfur and / or at least one sulfur donor are present in the rubber composition in an amount ranging from 0.25 to 10 phr, preferably 0.25 to 7 phr, particularly preferably 0.5 to 5 phr, and most preferably 1 to 3 phr. A rubber composition according to any one of claims 1 to 10, characterized by the above.

12. In a spatially separated form, Part A) is a rubber composition according to any one of claims 1 to 11, wherein Part A) does not contain sulfur and / or at least one sulfur donor of the vulcanizing VS according to any one of claims 1 to 11, Part B) comprises at least sulfur and / or at least one sulfur donor, the vulcanization system VS according to claim 1 or 11 A kit of parts including [specific components].

13. A vulcanizable rubber composition that can be obtained by vulcanizing a vulcanizable rubber composition according to any one of claims 1 to 11, or by vulcanizing a vulcanizable rubber composition that can be obtained by combining and mixing both parts A) and B) of the parts kit according to claim 12.

14. Use of the vulcanizable rubber composition according to any one of claims 1 to 11, the kit of parts according to claim 12, or the vulcanizable rubber composition according to claim 13, for use in the production of tires, preferably pneumatic tires and solid tires, for use in the production of tire components preferably selected from base components, i.e., components under the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, and / or for use in the production of technical rubber articles preferably selected from drive belts, straps / belts, molded parts, e.g., buffers / cushions, bearings / mounts, especially liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses.

15. A tire, preferably a pneumatic tire or a solid tire, a tire component, or preferably a technical rubber article, which is produced by using the vulcanizable rubber composition according to any one of claims 1 to 11, the parts kit according to claim 12, or the vulcanizable rubber composition according to claim 13, wherein, preferably, in the case of a tire component, these are selected from the base components, i.e., components under the tread, shoulder strip (wing), cap ply, belt, bead and / or bead reinforcement, and preferably, in the case of a rubber article, for example preferably a technical rubber article, these are preferably selected from the drive belt, strap / belt, molded parts, e.g., buffers / cushions, bearings / mounts, in particular liquid-filled mounts, conveyor belts, profiles, seals, rings and / or hoses.

16. Use of the organic filler F1 as defined in any one of claims 1 to 15 to increase the dynamic stiffness, particularly the complex modulus G*, decrease the tanδ value, or both, of a vulcanizable rubber composition that can be obtained from a vulcanizable rubber composition containing the organic filler F1, preferably from the vulcanizable rubber composition according to any one of claims 1 to 11.

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