A rubber mixture containing polyethyleneimine and at least one processing aid containing at least one fatty acid.

Abstract

The present invention relates to a rubber mixture comprising at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, at least one crosslinking agent from the group of sulfur and sulfur donors, at least one vulcanization accelerator containing polyethyleneimine, and at least one processing aid containing at least one fatty acid, wherein the total content of diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less, the manufacture and use of the rubber mixture, and vulcanized products that can be obtained therefrom after vulcanization, particularly in the form of tires, parts of tires, or industrial rubber articles.

Description

Technical Field

[0001] In each case, the present invention relates to a rubber mixture containing at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organosilanes, at least one crosslinking agent from the group of sulfur and sulfur donors, at least one vulcanization accelerator containing polyethyleneimine, and at least one processing aid containing at least one fatty acid, to its production and use, and to a vulcanizate obtainable therefrom after vulcanization, in particular in the form of a tire, a part of a tire or an industrial rubber article.

Background Art

[0002] By vulcanizing natural rubber, new materials have been obtained whose unique property profiles have substantially contributed to the development of modern technology. At the beginning of the 20th century, the accelerating effect of basic organic compounds on vulcanization was discovered.

[0003] Thus, for example, aniline and other nitrogen-containing organic compounds, such as hexamethylenetetramine or thiocarbanilide, are used as accelerators.

[0004] Sulfur is often used for crosslinking rubber mixtures. Crosslinking of rubber using a sulfur accelerator system generally allows for a wide variation in processing and product properties, such as an induction period (scorch time) which ideally should not be too short and a high preferably reaction rate, by using different accelerators and their combinations, thereby resulting in the advantage of a short full vulcanization time. To control the induction time and vulcanization time, so-called secondary accelerators can be added to the rubber mixture.

[0005] Guanidine accelerators count among the best-known secondary accelerators. These are retarder accelerators that can be used to adapt the initial (scorch) and / or full vulcanization time.

[0006] The modulus curve, an indicator of the progress of vulcanization in rubber mixtures containing guanidine accelerators, is typically characterized by a slow increase and a relatively late arrival at a maximum value. When used alone, these accelerators usually result in a relatively unfavorable flow time / heating time ratio and very severe unvulcanization in the rubber vulcanized product. To avoid these drawbacks, they are often used in combination with primary accelerators, such as sulfenamide accelerators.

[0007] As described in (Patent Document 1), accelerators are generally added together with sulfur in the final mixing step of a method for producing a rubber mixture. This document discloses the production and vulcanization of a rubber mixture containing diphenylguanidine (DPG), a guanidine accelerator, as well as rubber, silica, silane, and sulfur.

[0008] Beyond its pure function as an accelerator, DPG can also perform other functions. In mixtures where silica is used as a filler and further reinforced by the use of silane, it promotes the reaction between silane and silica, improves the dispersion of the filler, prevents a continuous increase in the rheometer curve (marching modulus) which undesirably hinders the realization of a vulcanization plateau, and improves the scorching properties of the mixture. In these applications, DPG is used together with silica and silane in the first mixing step in a method for producing rubber mixtures, as described, for example (Patent Document 2).

[0009] These properties are important because the accelerated reaction between silica and silane and improved filler dispersion allow for shorter mixing times in a closed kneader, thereby improving mixing efficiency. Furthermore, improved filler dispersion improves the trade-off between rolling resistance and wet braking, namely the combination of low rolling resistance and good wet braking characteristics, thereby improving the wear characteristics of the vulcanized mixture. Good scorch properties of the mixture are important to prevent the mixture from forming high-viscosity partially vulcanized regions during manufacturing (mixing and extrusion), which can cause defects in the heated final product.

[0010] A major challenge in the development of tire rubber mixtures is improving the trade-off between rolling resistance, wet braking, and wear. Preferably, the tan delta (tanδ) of the loss factor at 60°C at a measurement frequency of 10 Hz is used as an indicator of rolling resistance. Preferably, the tan delta at 0°C at a measurement frequency of 10 Hz is considered an indicator of wet braking, and DIN wear is considered an indicator of wear resistance. The Payne effect serves as an indicator of the filler dispersion characteristics.

[0011] (Patent Document 3) discloses the combined use of functionalized rubber and a trimethylolpropane-fatty acid mixture in a rubber mixture to improve rolling resistance and wet grip. However, these rubber compounds contained DPG as a vulcanization accelerator.

[0012] It is well known to those skilled in the art that guanidine accelerators release volatile organic amine compounds under vulcanization conditions. For example, DPG, the most widely used accelerator, desorbs aniline during vulcanization. Because it is desirable to avoid the release of these organic amines, particularly aniline, new accelerators are needed.

[0013] Polyethyleneimine is described as a substitute for DPG (Patent Document 4), but in that document, it is added only in the final mixing stage.

[0014] (Patent Document 5) discloses the use of polyethyleneimine in the first mixing step of a method for producing rubber mixtures containing SBR / NR and SBR / BR, which have silica as a filler and Si69(registered trademark) as a silane. However, in this case, a decrease in the abrasion resistance of the stored vulcanized product is observed. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] European Patent No. 2858831B1 [Patent Document 2] U.S. Patent Application Publication No. 2005 / 0016651A1 [Patent Document 3] International Publication No. 2010136345A1 Pamphlet [Patent Document 4] European Patent No. 3186307B1 [Patent Document 5] Japanese Patent No. 6655949 [Overview of the Initiative] [Problems that the invention aims to solve]

[0016] The present invention aims to provide a rubber mixture that has fewer toxicity issues and does not release volatile organic amines during vulcanization, and which has application-related properties, preferably Mooney viscosity, Mooney scorch behavior, filler dispersibility, more preferably wet braking, rolling resistance and abrasion resistance, that are as good as, preferably better than, those of the corresponding guanidine-containing rubber mixture / vulcanized product. It is preferable that further application-related properties, such as tensile strength and elongation at break, are as good as, preferably better than, those of the corresponding guanidine-containing rubber mixture / vulcanized product. [Means for solving the problem]

[0017] Surprisingly, it was found that in each case, by using polyethyleneimine together with at least one processing aid containing at least one fatty acid in a rubber mixture containing at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, and at least one crosslinking agent from the group of sulfur and sulfur donors, it is possible to obtain a rubber mixture that achieves this objective, particularly considering equivalents containing guanidine, and especially DPG.

[0018] Therefore, the present invention relates to a rubber mixture, - At least one rubber, - At least one hydroxyl-containing oxide filler, - At least one reinforcing additive from the group of sulfur-containing organic silanes, - At least one crosslinking agent from the group consisting of sulfur and sulfur donors, - At least one vulcanization accelerator containing polyethyleneimine, - At least one processing aid containing at least one fatty acid and The present invention relates to a rubber mixture containing diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide, wherein the total content of diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less. [Modes for carrying out the invention]

[0019] rubber The rubber mixture according to the present invention comprises at least one rubber.

[0020] This could be, for example, natural rubber (NR) and / or synthetic rubber.

[0021] Preferred polar and non-polar synthetic rubbers are: BR - Polybutadiene, ABR - Butadiene / C1-C4 Alkyl Acrylate Copolymer CR - Polychloroprene, IR - Polyisoprene, SBR - Styrene / butadiene copolymer having a styrene content of 1-60% by weight, preferably 20-50% by weight. IIR - Isobutylene / isoprene copolymer, NBR - Butadiene / acrylonitrile copolymer having an acrylonitrile content of 5-60%, preferably 10-50% by weight. HNBR - Partially or fully hydrogenated NBR rubber, EPDM - Ethylene / Propylene / Diene Copolymer SIBR - Styrene-isoprene-butadiene rubber, ENR - Epoxy natural rubber, SNBR - Acrylonitrile-styrene / butadiene rubber, HNBR - Hydrogenated acrylonitrile / butadiene rubber, XNBR - Carboxylated acrylonitrile / butadiene rubber, HXNBR - Hydrogenated carboxylated acrylonitrile / butadiene rubber That is the case.

[0022] At least one synthetic rubber may or may not be functionalized.

[0023] The rubber mixture according to the present invention may include at least one functionalized synthetic rubber. The above relating to non-functionalized synthetic rubber also applies to functionalized synthetic rubber, except that the rubber is in a functionalized form.

[0024] In relation to the present invention, functionalized synthetic rubber should be understood to mean synthetic rubber in which the main chain and / or terminal groups are substituted with one or more functional groups, preferably selected from carboxyl groups, mercaptan groups, alkoxysilane groups, siloxane groups, hydroxyl groups, ethoxy groups, epoxy groups, amino groups, phthalocyanine groups, silane-sulfide groups, and metal atom-containing groups, particularly preferably selected from mercaptan groups, alkoxysilane groups, and hydroxyl groups, and very particularly preferably selected from mercaptan groups and alkoxysilane groups.

[0025] In relation to the present invention, the non-functionalized synthetic rubber does not contain the aforementioned substitutions by functional groups.

[0026] The rubber mixture according to the present invention preferably comprises at least one functionalized synthetic rubber, and particularly preferably comprises at least one functionalized synthetic rubber selected from the group consisting of polar and non-polar functionalized synthetic rubbers.

[0027] At least one functionalized synthetic rubber is preferably selected from the group consisting of functionalized SBR, functionalized BR, and functionalized IR rubber, and particularly preferably selected from functionalized SBR and functionalized BR rubber.

[0028] The rubber mixture according to the present invention preferably comprises at least one functionalized SBR rubber and / or a functionalized BR rubber, and particularly preferably comprises at least one functionalized SBR rubber and at least one functionalized BR rubber.

[0029] In one preferred embodiment, at least one rubber is selected from the group consisting of natural rubber and synthetic rubber, preferably at least one functionalized synthetic rubber, particularly preferably selected from the group consisting of functionalized SBR, functionalized BR, and functionalized IR rubber, and very particularly preferably at least one functionalized synthetic rubber selected from functionalized SBR and functionalized BR rubber.

[0030] At least one functionalized SBR rubber is preferably substituted in the main chain and / or terminal groups with one or more functional groups, particularly selected from mercaptan groups, alkoxysilane groups, and hydroxyl groups, and especially preferably two or more functional groups, which are mercaptan groups and alkoxysilane groups. The at least one functionalized SBR rubber is preferably Trinseo's SPRINTAN® SLR 3402.

[0031] Functionalized SBR rubber can be solution-polymerized styrene-butadiene rubber (SSBR) or emulsion-polymerized styrene-butadiene rubber (ESBR), and a mixture of at least one functionalized SSBR and at least one functionalized ESBR can also be used.

[0032] The molecular weight (Mw) of the styrene-butadiene copolymer can be a wide range of values. Styrene-butadiene copolymers having an Mw of 250,000 to 600,000 g / mol, and particularly preferably an Mw of 350,000 to 500,000 g / mol, are preferred.

[0033] At least one functionalized BR rubber is preferably substituted in the main chain and / or terminal groups with one or more functional groups selected from mercaptan groups, alkoxysilane groups, and hydroxyl groups, particularly preferably alkoxysilane groups. The at least one functionalized BR rubber is preferably Zeon's NIPOL® BR 1261.

[0034] The molecular weight of the butadiene polymer can be a wide range of values. Butadiene polymers having an Mw of 250,000 to 5,000,000 g / mol are preferred.

[0035] Polybutadiene with a cis content of 90% by weight or more is called a high-cis type, and polybutadiene with a cis content of less than 90% by weight is called a low-cis type. An example of a low-cis polybutadiene is Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20% to 50% by weight. In relation to the present invention, high-cis type functionalized BR rubber is preferred.

[0036] The rubber mixture according to the present invention preferably comprises at least one functionalized synthetic rubber having a strength of 0 to 100 phr, particularly preferably 50 to 100 phr, and very preferably 70 to 100 phr.

[0037] The rubber mixture according to the present invention preferably contains at least one functionalized SBR and at least one functionalized BR rubber in an SBR:BR weight ratio of 100:0 to 0:100, particularly preferably 90:10 to 10:90, very particularly preferably 90:10 to 30:70, and especially preferably 80:20 to 50:50.

[0038] The rubber mixture according to the present invention preferably comprises at least one non-functionalized synthetic rubber and / or at least one natural rubber in a value of 0 to 100 phr, particularly preferably 0 to 50 phr, and very particularly preferably 0 to 30 phr.

[0039] filler At least one hydroxyl-containing oxide filler is preferably selected from the group consisting of silica, synthetic silicates, and natural silicates.

[0040] The content of hydroxyl-containing oxide filler in the rubber mixture according to the present invention is preferably 0.1 to 250 phr (parts per handred resin), particularly preferably 20 to 200 phr, very particularly preferably 25 to 180 phr, and most preferably 30 to 160 phr.

[0041] Suitable oxide fillers containing hydroxyl groups are preferably from the following group: - Silica, especially 5 to 1000, preferably 20 to 400 m 2 Silica having a specific surface area (BET) of / g and preferably a primary particle size of 100 to 400 nm, wherein the silica may optionally exist as a mixed oxide with another metal oxide, such as an oxide of Al, Mg, Ca, Ba, Zr, or Ti. - Synthetic silicates, e.g., 20-400m 2 Synthetic silicates having a specific surface area (BET) of / g and preferably a primary particle size of 10 to 400 nm, such as aluminum silicate, alkaline earth metal silicates, such as magnesium silicate or calcium silicate, and - Natural silicates, such as kaolin and other natural silicas, A mixture of those.

[0042] The above BET surface area is determined in accordance with DIN ISO 9277. The primary particle size shown is based on measurements using instruments for particle analysis with scattered light. The particle size calculation is based on Mie theory (DIN / ISO 13320), which describes the interaction between light and matter.

[0043] It is preferable that silica can be obtained by precipitation of a silicate solution or by flame hydrolysis of silicon halide.

[0044] The rubber mixture according to the present invention is 5 to 1000 m 2 / g, preferably 20-400m 2 It is preferable to include at least one hydroxyl-containing oxide filler from the group of silica having a specific surface area (BET) within the range of / g in an amount of 0.1 to 250 phr, preferably 20 to 200 phr, particularly preferably 25 to 180 phr, and very preferably 30 to 160 phr.

[0045] The rubber mixture according to the present invention may contain at least one carbon black as a filler.

[0046] In a preferred embodiment, the rubber mixture according to the present invention comprises at least one carbon black as a filler.

[0047] The rubber mixture of the present invention preferably contains at least one carbon black in an amount of 0.1 to 120 phr, particularly preferably 0.1 to 100 phr, very particularly preferably 1 to 70 phr, and most preferably 2 to 40 phr.

[0048] It can be obtained by lamp black, furnace black, or gas black method, and in quantities of 20-200 m 2 Carbon black having a specific surface area (BET) within the range of / g is preferred, such as SAF, ISAF, IISAF, HAF, FEF, or GPF carbon black. The rubber mixture of the present invention is preferably 20 to 200 m 2It contains at least one carbon black having a specific surface area (BET) within the range of / g.

[0049] It is preferable that the rubber mixture according to the present invention contains at least one of the aforementioned silicas and at least one of the aforementioned carbon blacks as fillers.

[0050] It is particularly preferable that the rubber mixture according to the present invention contains at least one of the aforementioned silicas in an amount of 25 to 180 phr, preferably 30 to 160 phr, and at least one of the aforementioned carbon blacks in an amount of 1.0 to 70 phr, preferably 2.0 to 40 phr, as fillers.

[0051] The total amount of carbon black and silica-based filler in the rubber mixture according to the present invention is preferably 26 to 250 phr, and particularly preferably 32 to 200 phr.

[0052] <Crosslinking agents and vulcanization accelerators> The rubber mixture according to the present invention comprises at least one crosslinking agent from the group consisting of sulfur and sulfur donors, and at least one vulcanization accelerator containing polyethyleneimine.

[0053] Crosslinking agent The rubber mixture according to the present invention preferably comprises at least one crosslinking agent from the group consisting of sulfur and sulfur donors.

[0054] Sulfur can be used in basically soluble or insoluble forms. It is particularly preferable that the rubber mixture according to the present invention contains at least one sulfur donor and / or sulfur, very preferably sulfur.

[0055] Examples of suitable sulfur donors include dimorpholyl disulfide (DTDM), 2-morpholinodithiobenzothiazole (MBSS), caprolactam disulfide, dipentamethylenethuram tetrasulfide (DPTT), tetramethylthiuram disulfide (TMTD), and tetrabenzylthiuram disulfide (TBzTB).

[0056] The rubber mixture according to the present invention generally contains at least one crosslinking agent from the group consisting of sulfur and sulfur donors in an amount of 0.1 to 20 phr, preferably 0.5 to 10 phr, particularly preferably 1.0 to 8 phr, and most preferably 1 to 4 phr.

[0057] The rubber mixture according to the present invention may also contain zinc oxide.

[0058] The preferred rubber mixture according to the present invention is 2 to 100 m 2 / g, preferably 2-70mg 2 It contains zinc oxide having a BET surface area of ​​1 / g. The BET surface area of ​​zinc oxide can be measured in accordance with DIN ISO 9277.

[0059] Zinc oxide is generally present in the rubber mixture according to the present invention in an amount of 0 to 20 phr, preferably 0.1 to 10 phr, and particularly preferably 1 to 5 phr.

[0060] vulcanization accelerator The rubber mixture according to the present invention comprises at least one vulcanization accelerator containing polyethyleneimine.

[0061] In relation to the present invention, the term polyethyleneimine (PEI) should be understood to mean a homopolymer of ethyleneimine / a copolymer of ethyleneimine and one or more comonomers, in which the ratio of repeating units derived from ethyleneimine based on the total mass of the polymer in each case is at least 50% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, particularly preferably at least 95% by weight, and very particularly preferably at least 98% by weight. The term polyethyleneimine also includes mixtures of homopolymers and / or copolymers of ethyleneimine having different molecular weights, degrees of branching, comonomers, etc.

[0062] Such homopolymers or copolymers typically have a weight-average molecular weight Mw of over 200, preferably 300 to 3,000,000, particularly preferably 400 to 800,000, very particularly preferably 500 to 100,000, more preferably 600 to 30,000, and most preferably 700 to 7,000.

[0063] The polyethyleneimine used in the rubber mixture according to the present invention may be linear or branched, and a mixture of linear and branched polyethyleneimine can also be used.

[0064] In one preferred embodiment, a polyethyleneimine having a branched structure containing not only primary amino groups but also secondary and tertiary amino groups is used.

[0065] The mixture according to the present invention may further comprise at least one carrier suitable for absorbing and / or adsorbing polyethyleneimine.

[0066] The advantage of supported polyethyleneimines is improved metering and / or dispersibility. Such supported compounds are also commonly known as "dry liquids."

[0067] At least one of the carriers may be inert, organic, or inorganic.

[0068] Suitable carriers include, for example, light-colored inorganic fillers such as mica, kaolin, siliceous soil, silica, chalk, and talc.

[0069] The mixture according to the present invention may or may not contain at least one of these carriers.

[0070] In the mixture according to the present invention, polyethyleneimine may be absorbed and / or adsorbed on at least one carrier, or it may not be absorbed and / or adsorbed on at least one carrier.

[0071] At least one support is preferably selected from the group consisting of natural and synthetic silicates, and more particularly from the group consisting of neutral, acidic, and basic silica, aluminum oxide, zinc oxide, and mixtures thereof. It is especially preferable that at least one support is selected from the group consisting of neutral, acidic, and basic silica.

[0072] In one preferred embodiment, the mixture according to the present invention comprises at least one carrier selected from the group consisting of neutral, acidic, and basic silica on which polyethyleneimine is absorbed and / or adsorbed.

[0073] The weight percentage ratio of silica, in particular, to the carrier polyethyleneimine can take on a relatively wide range of values.

[0074] The weight percentage ratio of the carrier, particularly silica to polyethyleneimine, is preferably 90:10 to 10:90, particularly preferably 90:10 to 10:60, and very preferably 15:10 to 10:15.

[0075] The ethylenediamine-ethyleneimine copolymer / polyethyleneimine homopolymer usable in the present invention is, for example, one having CAS numbers 25987-06-8 and 9002-98-6, preferably one having CAS number 25987-06-8.

[0076] Polyethyleneimine is particularly preferably absorbed onto silica and / or adsorbed onto silica. LANXESS's polyethyleneimine Rhenocure® DR / S is most preferred.

[0077] The rubber mixture according to the present invention preferably contains a vulcanization accelerator polyethyleneimine in an amount of 0.01 to 10 phr, particularly preferably 0.1 to 5 phr, and very particularly preferably 0.2 to 2.5 phr.

[0078] Furthermore, the rubber mixture according to the present invention may or may not contain one or more additional vulcanization accelerators in addition to polyethyleneimine.

[0079] The at least one further vulcanization accelerator is preferably mercaptobenzothiazole, thiocarbamate, dithiocarbamate, thiuram, thiazole, sulfenamide, thiazole sulfenamide, xanthate, bicyclic or polycyclic amine, thiophosphate, dithiophosphate, caprolactam, thiourea derivative, guanidine, cyclic disulfane, and amine, particularly zinc diamine diisocyanate, hexamethylenetetramine, and 1,3-bis(citraconimidomethyl)benzene The rubber mixture is selected from the group of , very preferably from the group of sulfenamides, and particularly preferably from N-cyclohexylbenzothiazole sulfenamide (CAS number: 95-33-0), and the total content of diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very preferably 0.01 phr or less.

[0080] The rubber mixture according to the present invention generally contains at least one listed vulcanization accelerator containing polyethyleneimine in an amount of 0.01 to 20 phr, preferably 0.1 to 10 phr, and particularly preferably 0.2 to 5 phr.

[0081] The rubber mixture according to the present invention preferably contains polyethyleneimine and at least one vulcanization accelerator comprising N-cyclohexylbenzothiazole sulfenamide.

[0082] The total amount of crosslinking agent and vulcanization accelerator in the rubber mixture is preferably 0.51 to 20 phr, particularly preferably 1.1 to 18 phr, and most preferably 1.2 to 9 phr.

[0083] The guanidine-containing compound may be present in small amounts or not at all in the mixture according to the present invention.

[0084] In connection with the present invention, the total content of diphenylguanidine (DPG), di-o-tolylguanidine (DOTG) and 1-(o-tolyl)biguanide in the rubber mixture according to the present invention is preferably 0.4 phr or less, particularly preferably 0.2 phr or less, very particularly preferably 0.1 phr or less, and most preferably 0.01 phr or less.

[0085] In the mixture according to the present invention, the total content of diphenylguanidine (DPG), substituted diphenylguanidine, another organic guanidine derivative (where the guanidine functional group is substituted with one or more C1-C8 alkyl groups, C2-C8 alkenyl groups, C6-C8 aryl groups, C7-C 10 aralkyl groups and / or C1-C8 heteroalkyl groups) and 1-(o-tolyl)biguanide is more preferably 0.4 phr or less, particularly preferably 0.2 phr or less, very particularly preferably 0.1 phr or less, and most preferably 0.01 phr or less.

[0086] Most preferably, the total content of guanidine-containing compounds in the mixture according to the present invention is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less.

[0087] In connection with the present invention, the term substituted diphenylguanidine should preferably be understood to mean diphenylguanidine in which at least one phenyl ring is substituted, preferably both phenyl rings are substituted. A very wide range of substituents are possible as substituents. Substituted or unsubstituted C1-C 20 -alkyl, substituted or unsubstituted C2-C containing one or more double bonds 20 -alkenyl, substituted or unsubstituted C2-C containing one or more triple bonds 20 -alkynyl, substituted or unsubstituted C3-C 20 -aryl, substituted or unsubstituted heteroaryl having 5 to 20 members and containing one or more heteroatoms, substituted or unsubstituted C3-C 14-Cycloalkyl groups, substituted or unsubstituted heterocycloalkyl groups having 3 to 8 members and containing one or more heteroatoms, and substituents on a phenyl ring selected from the group consisting of heteroatoms are preferred.

[0088] Processing aids The rubber mixture according to the present invention comprises at least one processing aid containing at least one fatty acid.

[0089] At least one fatty acid is preferably, - Fatty acids C where n=10~30 n H 2n O2, especially preferably C with n=12-22 n H 2n O2, and very preferably C = 10, 12, 14, 16, and 18. n H 2n O2, most preferably n=16 or n=18 C n H 2n O2, and - Fatty acid C where x is an even number between 2 and 10 and n is between 10 and 30. n H 2n-x O2, particularly preferably an even number x = 2 or greater and 10 or less, and n = 12 to 22 C n H 2n-x O2, very preferably an even number x=2 or 4, and n=16 or n=18 C n H 2n-x O2, most preferably x=2 and n=16 or 18 C n H 2n-x O2, or C where x=4 and n=18 n H 2n-x O2 Selected from.

[0090] The above-mentioned at least one fatty acid is preferably present in the at least one processing aid in an amount of 40-85% by weight, particularly preferably 55-80% by weight, where the weight percentage is based on the total amount of the at least one processing aid.

[0091] Of the above amounts of at least one fatty acid, preferably at least 80% by weight, particularly preferably at least 90% by weight, and very particularly preferably at least 95% by weight, based on the total amount of at least one fatty acid, is fatty acid C, where n=10-30. n H 2n O2, especially preferably C with n=12-22 n H 2n O2, and very preferably C = 10, 12, 14, 16, and 18. n H 2n O2, most preferably n=16 or n=18 C n H 2n It can consist of at least one fatty acid selected from O2.

[0092] A preferred rubber mixture according to the present invention contains not only at least one fatty acid, but also at least one alcohol, preferably n=10-26 C n H 2n O and 1,1,1-trimethylolpropane (TMP), particularly preferably n=10-24 C n H 2n O and 1,1,1-trimethylolpropane, very preferably n=10, 12, 14, 16, 18, 20, 22, 24 C n H 2n O and 1,1,1-trimethylolpropane, most preferably n=18 C n H 2n It also includes at least one processing aid, which also includes at least one alcohol selected from 0 and 1,1,1-trimethylolpropane.

[0093] At least one alcohol is preferably present in the at least one processing aid in an amount of 5 to 50% by weight, particularly preferably 8 to 25% by weight, the weight percentage value being based on the total amount of the at least one processing aid.

[0094] A preferred rubber mixture according to the present invention comprises at least one processing aid, which includes not only at least one fatty acid and optionally at least one alcohol, but also at least one ester, preferably selected from stearyl dodecanoate, stearyl myristylate, stearyl palmitate, docosyl palmitate, stearyl stearate, eicosyl stearate, tetradecyl stearate, docosyl stearate, and docosyl arachidate, particularly preferably selected from stearyl dodecanoate, stearyl myristylate, stearyl palmitate, docosyl palmitate, and stearyl stearate, and most preferably at least one ester selected from stearyl palmitate and stearyl stearate.

[0095] At least one ester is preferably present in an amount of 5 to 20% by weight, particularly preferably 8 to 15% by weight, in at least one processing aid, the weight percentage being based on the total amount of at least one processing aid.

[0096] The preferred rubber mixture according to the present invention comprises at least one processing aid, which includes not only at least one fatty acid and optionally at least one alcohol and optionally at least one ester, but also polyethylene glycol, preferably having a molecular weight of 3,000 to 10,000 g / mol, particularly preferably 5,000 to 7,000 g / mol, and most preferably 6,000 g / mol.

[0097] Polyethylene glycol is present in at least one processing aid in an amount preferably 1 to 10% by weight, and particularly preferably 1 to 5% by weight, with the weight percentage value being based on the total amount of at least one processing aid.

[0098] In addition to the aforementioned compounds, at least one processing aid may contain further additives, such as LDPE polyethylene, sodium hydroxide, and butylhydroxy, preferably in an amount of 4 to 8% by weight, the weight percentage of which is based on the total amount of at least one processing aid.

[0099] At least one processing aid is preferably present in the rubber mixture according to the present invention in an amount of 0.1 to 30 phr, particularly preferably 0.5 to 25 phr, very particularly preferably 1 to 15 phr, and most preferably 5 to 15 phr.

[0100] In one particularly preferred embodiment, the rubber mixture according to the present invention comprises at least one processing aid in an amount of 0.1 to 30 phr, preferably 0.5 to 25 phr, particularly preferably 1 to 15 phr, and very particularly preferably 5 to 15 phr, wherein the at least one processing aid is - At least one fatty acid, - Fatty acids C where n=10~30 n H 2n O2, and - Fatty acid C where x is an even number between 2 and 10, and n is between 10 and 30. n H 2n-x O2 At least one fatty acid selected from, - C where n = 10 to 26 n H 2n At least one alcohol selected from O and 1,1,1-trimethylolpropane (TMP), - At least one ester selected from stearyl dodecanoate, stearyl myristate, stearyl palmitate, docosyl palmitate, stearyl stearate, eicosyl stearate, tetradecyl stearate, docosyl stearate, and docosyl arachidate, - Polyethylene glycol and Includes.

[0101] In one very particularly preferred embodiment, the rubber mixture according to the present invention comprises at least one processing aid in an amount of 0.1 to 30 phr, preferably 0.5 to 25 phr, particularly preferably 1 to 15 phr, and very particularly preferably 5 to 15 phr, wherein the at least one processing aid is - 40-85% by weight, preferably 55-80% by weight, - Fatty acids C where n=10~30 n H 2n O2, and - Fatty acid C where x is an even number between 2 and 10, and n is between 10 and 30. n H 2n-x O2 At least one fatty acid selected from, where at least 80% by weight, preferably at least 90% by weight, and very preferably at least 95% by weight, based on the total amount of at least one fatty acid, is fatty acid C, with n=10-30. n H 2n O2, preferably C with n=12-22 n H 2n O2, particularly preferably C = 10, 12, 14, 16, and 18 n H 2n O2, and very preferably C, where n=16 or n=18. n H 2n At least one fatty acid, selected from O2, - C, which is 5-50% by weight, preferably 8-25% by weight, with n=10-26 n H 2n At least one alcohol selected from O and 1,1,1-trimethylolpropane (TMP), - 5 to 20% by weight, preferably 8 to 15% by weight, of at least one ester selected from stearyl dodecanoate, stearyl myristate, stearyl palmitate, docosyl palmitate, stearyl stearate, eicosyl stearate, tetradecyl stearate, docosyl stearate, and docosyl arachidate, - 1 to 10% by weight, preferably 1 to 5% by weight of polyethylene glycol and It contains the following, where the weight percentage value is based on the total amount of at least one processing aid.

[0102] Reinforcement additives The rubber mixture according to the present invention comprises at least one reinforcing additive from the group of sulfur-containing organic silanes.

[0103] A preferred sulfur-containing organosilane is a bifunctional sulfur-containing organosilane that contains at least one alkoxy, cycloalkoxy, or phenoxy group on a silicon atom and also contains a group selected from -SCN, -SH, or -Sx- (where x = 2 to 8) as another functional group.

[0104] Sulfur-containing silanes having alkoxysilyl are particularly preferred, and sulfur-containing organic silanes having trialkoxysilyl are very particularly preferred.

[0105] The rubber mixture according to the present invention most preferably comprises one or more sulfur-containing silanes from the group consisting of bis(triethoxysilylpropyl)tetrasulfan, bis(triethoxysilylpropyl)disulfan, and 3-(triethoxysilyl)-1-propanthol.

[0106] Liquid sulfur-containing silane can be absorbed onto a carrier for better metering and / or dispersibility (dry liquid). The content of sulfur-containing silane in these "dry liquids" is preferably 30 to 70 parts by weight, and particularly preferably 40 to 60 parts by weight, per 100 parts by weight of dry liquid.

[0107] The rubber mixture according to the present invention generally contains at least one reinforcing additive from the group of sulfur-containing organic silanes in a concentration of 0.1 to 20 phr, preferably 0.5 to 15 phr, and particularly preferably 1.0 to 10 phr.

[0108] Rubber additive The rubber mixture according to the present invention may further contain one or more rubber additives. Examples of suitable rubber additives include aging stabilizers, binders, heat stabilizers, light stabilizers, flame retardants, processing aids, impact modifiers, plasticizers, tackifiers, foaming agents, dyes, pigments, waxes, extenders, organic acids such as stearic acid, retarders, and vulcanization return stabilizers.

[0109] The rubber mixture according to the present invention may contain one or more aging stabilizers. Suitable aging stabilizers include amine-based aging stabilizers, such as diaryl-p-phenylenediamine (DTPD), octylated diphenylamine (ODPA), phenyl-α-naphthylamine (PAN), phenyl-β-naphthylamine (PBN), preferably those based on phenylenediamine, such as N,N'-dicyclohexyl-p-phenylenediamine (CCPD), N-isopropyl-N'-phenyl-p-phenylenediamine, and N-1,3-dimethylbutyl-N'-phenyl-p-phenyl Examples include diamine (6PPD), N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine (7PPD), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), and phosphites such as tris(nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), methyl-2-mercaptobenzimidazole (MMBI), and zinc methylmercaptobenzimidazole (ZMMBI), as well as mixtures thereof. It is particularly preferable that at least one aging stabilizer is selected from the group consisting of N,N'-dicyclohexyl-p-phenylenediamine (CCPD) and N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD).

[0110] Processing aids should be active between rubber particles and should counteract frictional forces during mixing, plasticization, and molding. Processing aids that may be present in the rubber mixture according to the present invention include any lubricant common in the processing of plastics, such as hydrocarbons, such as oils, such as process oils, paraffins and PE waxes, fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids, such as fatty acids and montanic acid, oxidized PE waxes, aromatically modified alicyclic hydrocarbon resins, metal salts of carboxylic acids, carboxamides, and carboxylic acid esters, such as carboxylic acid esters having alcohols such as ethanol, fatty alcohols, glycerol, ethanediol, and pentaerythritol, and long-chain carboxylic acids as acid components.

[0111] To reduce flammability and decrease smoke generation during combustion, the rubber mixture of the present invention may contain a flame retardant. Examples of compounds used for this purpose include antimony trioxide, phosphate esters, chloroparaffin, aluminum hydroxide, boron compounds, zinc compounds other than ZnO, molybdenum trioxide, ferrocene, calcium carbonate, or magnesium carbonate.

[0112] Further plastics may be added to the rubber mixture of the present invention before crosslinking, which may function, for example, as polymer processing aids or impact modifiers. These plastics are preferably selected from the group consisting of ethylene, propylene, butadiene, styrene, vinyl acetate, vinyl chloride, glycidyl acrylate, glycidyl methacrylate, and homopolymers and copolymers based on acrylates and methacrylates having alcohol components of branched or unbranched C1-C10 alcohols, and are particularly preferably polyacrylates, polymethyl methacrylates, methyl methacrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, ethylene-vinyl acetate copolymers, chlorinated polyethylene, ethylene-propylene copolymers, and ethylene-propylene-diene copolymers having the same or different alcohol groups from the group consisting of C4-C8 alcohols, particularly butanol, hexanol, octanol, and 2-ethylhexanol.

[0113] Well-known binders are based on resorcinol, formaldehyde, and silica, and are so-called RFS direct bonding systems. These direct bonding systems can be used in any desired amount of the rubber mixture according to the present invention at any point in time of incorporation into the rubber mixture according to the present invention.

[0114] The rubber mixture according to the present invention may further comprise at least one vulcanization retarder.

[0115] The rubber mixture according to the present invention preferably comprises at least one vulcanization retarder. Examples of such retarders include sulfenamide retarders based on acidic compounds such as phthalic acid, phthalic anhydride, benzoic acid, or salicylic acid, and vulcanization retarders from the group of N-nitroso compounds based on diphenylamine or trimethyldihydroquinoline.

[0116] At least one vulcanization retarder is particularly preferably selected from the group consisting of sulfenamide retarders, very preferably selected from N-cyclohexylthiophthalimide and N-phenyl-N-(trichloromethylsulfenyl)benzenesulfonamide, and most preferably N-cyclohexylthiophthalimide.

[0117] At least one vulcanization retarder is present in the rubber mixture according to the present invention in an amount preferably 0.01 to 10 phr, particularly preferably 0.05 to 5 phr, very particularly preferably 0.1 to 1 phr, and most preferably 0.1 to 0.5 phr.

[0118] The rubber additive present in the mixture according to the present invention is preferably different from other components of the rubber mixture according to the present invention, such as at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, at least one crosslinking agent from the group of sulfur and sulfur donors, at least one vulcanization accelerator containing polyethyleneimine, and at least one processing aid.

[0119] Rubber additives may be added to the rubber mixture according to the present invention in typical amounts, which are also determined by the intended use of the vulcanized product produced therefrom. Typical amounts are, for example, 0.1 to 30 phr.

[0120] However, if the rubber auxiliary agent is partially common with one of the other components of the rubber mixture according to the present invention, for example, at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, at least one crosslinking agent from the group of sulfur and sulfur donors, at least one vulcanization accelerator and / or at least one processing aid containing polyethyleneimine, then the rubber auxiliary agent is preferably present in the rubber mixture according to the present invention only in an auxiliary amount relative to the general and preferred amounts reported with respect to the other components.

[0121] - At least one functionalized synthetic rubber with a hardness of 50 to 100 phr, preferably a functionalized BR rubber and / or functionalized SBR rubber with a hardness of 70 to 100 phr. - At least one natural rubber and / or unfunctionalized synthetic rubber with a rating of 0 to 50 phr, preferably 0 to 30 phr. - At least one hydroxyl-containing oxide filler of 20-200 phr, - At least one reinforcing additive with a value of 0.5 to 15 phr, comprising a sulfur-containing organic silane, preferably a bifunctional sulfur-containing organic silane containing at least one alkoxy, cycloalkoxy, or phenoxy group on a silicon atom and a group selected from -SCN, -SH, or -Sx- (where x = 2 to 8) as another functional group, particularly preferably a sulfur-containing silane having an alkoxysilyl, and very particularly preferably a sulfur-containing organic silane having a trialkoxysilyl, - At least one carbon black with a strength of 0.1 to 120 phr, preferably 0.1 to 100 phr. - At least one crosslinking agent from the group consisting of sulfur donors and sulfur, with a concentration of 0.5 to 10 phr. - Zinc oxide of 0.1 to 10 phr, - At least one vulcanization accelerator containing polyethyleneimine in a concentration of 0.1 to 10 phr, - At least one processing aid containing at least one fatty acid in a concentration of 0.1 to 30 phr, preferably 0.5 to 25 phr, particularly preferably 1 to 15 phr, and very particularly preferably 5 to 15 phr. The rubber mixture of the present invention containing the above is particularly preferred, and the total content of diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less.

[0122] The further preferred ranges of individual components described above also apply to these preferred mixtures.

[0123] <Method for manufacturing rubber compounds> The present invention further provides a method for producing a rubber mixture according to the present invention, characterized in that each component is mixed in a mixing process.

[0124] This preferably involves mixing at least one rubber in the general and preferred amounts described above, at a temperature in the range of 50°C to 180°C, particularly preferably 60°C to 170°C, in the presence of at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, at least one vulcanization accelerator containing polyethyleneimine, and at least one processing aid, and optionally, further rubber additives.

[0125] The rubber mixture of the present invention is prepared in conventional methods using known mixing equipment, such as rollers, closed-type kneaders, downstream mixing roller mills, and mixing extruders for 1 to 1000 seconds. -1 It is manufactured at the following shear rate.

[0126] The production of the rubber mixture according to the present invention is preferably carried out by a three-step mixing process.

[0127] In the first mixing stage, it is preferable that rubber, fillers, and optionally further rubber additives, preferably aging stabilizers, and the vulcanization accelerator polyethyleneimine are first mixed into the rubber in a closed kneader.

[0128] In the method for producing a rubber mixture according to the present invention, it is preferable that at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, polyethyleneimine, and at least one processing aid, and optionally further rubber additives, are mixed in a first mixing step.

[0129] The mixing temperature inside the closed-type kneader can reach a maximum value of 180°C. The temperature in the first mixing stage is preferably 130°C to 180°C, and particularly preferably 140°C to 170°C.

[0130] This is followed preferably by a second step of so-called post-kneading, preferably at 130-180°C, and particularly preferably at 160°C. Post-kneading may be carried out, for example, in a closed-type kneader.

[0131] In the third mixing step, it is preferable that at least one crosslinking agent from the group of sulfur and sulfur donors, optionally at least one further vulcanization accelerator, and optionally further rubber additives are added to the rubber mixture obtained in the second mixing step. The temperature in the third mixing step is preferably 50 to 130°C, and particularly preferably 60 to 120°C.

[0132] The addition of polyethyleneimine may be carried out at any point during mixing, preferably during the first mixing stage, at a temperature in the range of 130°C to 180°C, preferably 140°C to 170°C.

[0133] In one particularly preferred embodiment of the method for producing a rubber mixture according to the present invention, - First, at least one rubber, at least one hydroxyl-containing oxide filler, at least one reinforcing additive from the group of sulfur-containing organic silanes, polyethyleneimine, and at least one processing aid, and optionally further rubber additives, are preferably mixed at 130°C to 180°C, and Next, at least one crosslinking agent from the group of sulfur and sulfur donors, optionally at least one further vulcanization accelerator, and optionally further rubber additives are preferably added to the resulting rubber mixture at 50 to 130°C.

[0134] <Method for manufacturing vulcanized rubber> The present invention further relates to a method for producing a rubber vulcanized product, characterized in that the rubber mixture according to the present invention is heated to a temperature of 120°C to 200°C, preferably 140°C to 180°C.

[0135] The method for producing a rubber vulcanized product according to the present invention can be carried out over a wide pressure range, preferably within a pressure range of 10 to 200 bar.

[0136] The present invention further provides a rubber vulcanized product that can be obtained by vulcanizing a rubber mixture according to the present invention.

[0137] <Molded articles> The rubber vulcanized products of the present invention are suitable for the manufacture of any type of molded articles, such as tire components, industrial rubber articles, such as damping elements, roller coatings, conveyor belt coatings, power transmission belts, rotating cups, seals, golf ball cores, and footwear soles. They are particularly suitable for the manufacture of tires and tire components, such as tire treads, sub-treads, carcasses, tire sidewalls, reinforcing sidewalls for run-flat tires, and apex mixtures. The tire treads also include treads for summer, winter, and all-season tires, as well as treads for passenger car, truck, and light truck tires.

[0138] Preferred molded articles are tires and tire parts (tire components) containing the rubber vulcanized product according to the present invention.

[0139] <Use> The present invention further provides the use of at least one processing aid containing polyethyleneimine in an amount particularly of 0.01 to 10 phr, particularly preferably 0.1 to 5 phr, very particularly preferably 0.2 to 2.5 phr, and at least one fatty acid in an amount particularly of 0.1 to 30 phr, particularly preferably 1 to 15 phr, very particularly preferably 5 to 15 phr, in a sulfur crosslinkable rubber mixture, a vulcanized product that can be obtained therefrom, and a molded product that can be obtained therefrom, to address, preferably improve, the trade-off between rolling resistance and wet braking.

[0140] The descriptions and preferred ranges given with respect to components present in and optionally present in the rubber mixtures according to the present invention apply, in particular, to the disclosed methods and uses, as well as to vulcanized products, molded articles and binding mixtures.

[0141] The descriptions and preferred scopes set forth above apply equally to the rubber mixtures, vulcanized products, molded articles, methods and uses according to the present invention, regardless of whether they are disclosed in the plural (e.g., multiple rubber mixtures) or singular (e.g., rubber mixtures) with respect to the foregoing.

[0142] The present invention will be described below with reference to the following examples, but is not limited thereto. [Examples]

[0143] [Table 1]

[0144] Processing aid A: C is n=12, 16, and 18 n H 2n Saturated fatty acids containing O2, and C with x=4 and n=18. n H 2n-x A mixture of 61.35% by weight of unsaturated fatty acids containing O2 (where n=18 C n H 2n A mixture comprising: an O2 content exceeding 60% by weight based on the total amount of fatty acids; a 17.9% by weight alcohol mixture containing 1,1,1-trimethylolpropane (TMP) (where the proportion of TMP exceeds 60% by weight based on the total amount of alcohol); a 12.8% by weight fatty acid ester mixture (where the stearyl stearate content exceeds 35% by weight based on the total amount of fatty acid esters); and a 7.95% by weight mixture of other components (where the polyethylene glycol content exceeds 30% by weight based on the total amount of other components).

[0145] Manufacturing of rubber vulcanized products A reference rubber mixture not according to the present invention was prepared based on International Publication No. 2010136345A1, which is a conventional rubber mixture containing DPG. Examples 1 and 2, and Examples 3 and 4 of the present invention, were prepared according to the formulations specified in Table 2. The difference between Example 1 and the reference mixture is that the vulcanization accelerator DPG was replaced with polyethyleneimine. In Example 2, the retarder Vulkalent® G (CTP) was added to Example 1. In Examples 3 and 4 of the present invention, processing aid A was added to Example 2.

[0146] The rubber mixture was manufactured in the following steps. [First mixing stage]: First, add NIPOL® BR1261 and SPRINTAN® SLR 3402 to a closed-type kneader and mix for approximately 30 seconds. Add half of ZEOSIL® 1165MP and SI® 75, then mix for about 60 seconds. Add half of ZEOSIL® 1165MP, CORAX® N 234 and PALMERA® A9818, Vulkanox® 4020, Vulkanox® HS, Antilux® 654, Vivatec 500, Escorez 5600, Rhenocure® DR / S or RHENOGRAN® DPG-80, and processing aid A, then mix for about 60 seconds, then invert. Mix until the temperature reaches 160°C, then mix at 160°C for 4 minutes.

[0147] After the first mixing stage was complete, the mixed batch was sent to a downstream roller mill to be formed into sheets, strips, or pellets, which were then stored at room temperature for 24 hours. The processing temperature was 70°C.

[0148] [Second mixing stage]: Following this, the mixture was mixed in a closed-type kneader until it reached a temperature of 160°C (so-called post-mixing).

[0149] After the second mixing stage was completed, the mixed batch was sent to a downstream roller mill to be formed into sheets, strips, or pellets, which were then stored at room temperature for 24 hours.

[0150] [Third mixing stage]: Sulfur, zinc oxide, and the vulcanization accelerator Rhenogran® CBS-80 were added in a closed-type kneader at 100°C for 2 minutes.

[0151] After the third mixing stage was completed, the mixed batch was formed into sheets, strips, or pellets using a roller mill and stored at room temperature for 24 hours. The processing temperature was 70°C.

[0152] The rubber mixtures 3 and 4 of the present invention show no speckling on the surface, and therefore the mixing of the additives used is considered to be good.

[0153] [Table 2]

[0154] Technical Test The following technical tests were performed on vulcanized products prepared at 160°C from the rubber mixtures of Examples 1-4 and the reference mixture. The measured values ​​are reported in Table 3.

[0155] The following test methods were used to test the test specimens.

[0156] <Moony Viscosity Measurement> Measurements were performed using a shear disk viscometer in accordance with ASTM D 1646. Viscosity can be directly determined from the force with which rubber and rubber mixtures withstand processing. In a Mooney shear disk viscometer, a grooved disk is surrounded on the top and bottom by the test material and rotates at approximately 2 revolutions per minute in a heatable chamber. The force required for this rotation is measured as torque, which corresponds to the respective viscosity. The sample is generally preheated to 100°C for 1 minute, and the measurement takes a further 4 minutes, during which time the temperature is maintained constant. Viscosity is reported along with the respective test conditions, e.g., ML(1+4)100°C (Mooney viscosity, rotor size L, preheating time and test time in minutes, test temperature).

[0157] <Mooney Scorch Measurement> The Mooney-Scorch test is a standardized test for characterizing the behavior of partial vulcanization of rubber samples at elevated temperatures. It determines the time it takes for viscosity to increase by a specified value. Measurements are performed using a shear disk viscometer in accordance with ASTM D 1646.

[0158] <Rheometer (vulcameter) used and scorching / complete vulcanization time> MDR (Moving Direometer) vulcanization profiles and related analytical data are measured in an MDR 2000 Monsanto rheometer in accordance with ASTM D5289-95.

[0159] The partial vulcanization time (t10) is the time required for 10% of the rubber to crosslink. The selected temperature was 160°C.

[0160] The complete vulcanization time (t95) is the time required for 95% of the rubber to crosslink. The selected temperature was 160°C.

[0161] The value of delta S' is the difference between the maximum and minimum values ​​of the rheometer curve, i.e., S max -S min It is calculated from.

[0162] <Measurement of elongation at break, tensile strength, and 300 modulus> These measurements were carried out in accordance with DIN 53504 (tensile test, rod S2, 5 measurements).

[0163] <Measurement of Shore A hardness> Measurement of Shore hardness (Shore A) at 23 °C in accordance with DIN 53505 (3 replicates).

[0164] <Rebound resilience> Measurement of rebound resilience at 23 °C and 60 °C in accordance with DIN 53512 (3 replicates).

[0165] <Measurement of DIN abrasion> The simplest method for measuring abrasive wear is the so-called DIN abrasion in accordance with ASTM D5963. A test piece made of the elastomer to be tested is passed over a specified friction path (40 m) on a wear test sheet on a rotating cylinder with a constant contact force and a constant speed (40 min -1 ). Next, the reduction of the material is determined in units of mm 3 .

[0166] <Measurement of loss factor> The loss factor tanδ was determined by dynamic attenuation in accordance with DIN 53513 at measurement frequencies of 0 °C, 60 °C, and 10 Hz.

[0167] <Measurement of Payne effect>: Amplitude sweep from 0.5% to 15% (varying deformation amplitude) at 60 °C and 10 Hz. The Payne effect is the difference between G’ at 0.5% amplitude and G’ at 15% amplitude.

[0168]

Table 3

[0169] conclusion In the rubber mixtures of Examples 1-4, DPG in the reference mixture was replaced with polyethyleneimine. Polyethyleneimine was added along with silica and silane in the first mixing stage. Example 1 shows that adding polyethyleneimine instead of DPG results in Mooney viscosity being much higher than the reference in the first and especially third mixing stages. Mooney scorch behavior also deteriorates. Example 2 shows that adding the retarder Vulkalent® G (CTP) improves Mooney scorch behavior compared to Example 1, but does not have a favorable effect on Mooney viscosity. The addition of processing aid A in Examples 3 and 4 of the present invention resulted in a significant decrease in Mooney viscosity compared to Examples 1 and 2 and the reference mixture. Surprisingly, the complete vulcanization time (t95) and Mooney scorch behavior were also further improved. The mixtures of Examples 1 and 2 heated to 60°C show an improvement in the Payne effect when polyethyleneimine is used instead of DPG in the reference vulcanizer. This value, an indicator of filler dispersion, can be further improved by the addition of processing aid A, as shown in Examples 3 and 4 of the present invention. Surprisingly, compared to Examples 1 and 2, and the reference mixture, an improvement in the trade-off between wet braking and rolling resistance is also evident in Examples 3 and 4 of the present invention, from the increase in the tandelta value at 0°C and the unchanged value at 60°C. At the same time, the wear resistance of the vulcanized products of the present invention in Examples 3 and 4 is increased, as is evident from the decrease in the DIN wear value. In Example 4 of the present invention, the addition of 1 phr of polyethyleneimine (compared to 0.5 phr in Example 3) causes the mixture to achieve Mooney viscosity and Mooney scorch values ​​equivalent to the reference DPG after the third mixing stage, and in fact, a better Mooney viscosity value after the first mixing stage. At the same time, the rolling resistance performance is even higher than in Example 3.

Claims

1. A rubber mixture, - At least one rubber, - At least one hydroxyl-containing oxide filler, - At least one reinforcing additive from the group of sulfur-containing organic silanes, - At least one crosslinking agent from the group consisting of sulfur and sulfur donors, - At least one vulcanization accelerator containing polyethyleneimine, and - At least one processing aid containing at least one fatty acid A rubber mixture containing the above, wherein the total content of diphenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and 1-(ortho-tolyl)biguanide in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less.

2. The rubber mixture according to claim 1, characterized in that the at least one rubber is selected from the group consisting of natural rubber and synthetic rubber, preferably at least one functionalized synthetic rubber, and particularly preferably at least one functionalized synthetic rubber selected from the group consisting of functionalized SBR, functionalized BR, and functionalized IR rubber, and very particularly preferably at least one functionalized synthetic rubber selected from functionalized SBR and functionalized BR rubber.

3. The rubber mixture according to claim 1 or 2, characterized in that the at least one hydroxyl-containing oxide filler is selected from the group consisting of silica, synthetic silicate, and natural silicate, and is present in the rubber mixture in an amount of 0.1 to 250 phr, preferably 20 to 200 phr, particularly preferably 25 to 180 phr, and very particularly preferably 30 to 160 phr.

4. The aforementioned at least one fatty acid, - Fatty acid C where n = 10 to 30 ｎ H ２ｎ O ２ , preferably C where n = 12 to 22 ｎ H ２ｎ O ２ , particularly preferably C where n = 10, 12, 14, 16, and 18 ｎ H ２ｎ O ２ , very particularly preferably C where n = 16 or n = 18 ｎ H ２ｎ O ２ , and - Fatty acid C where x is an even number between 2 and 10, and n is between 10 and 30. ｎ H ２ｎ－ｘ O ２ Preferably, x is an even number between 2 and 10, and n is between 12 and 22. ｎ H ２ｎ－ｘ O ２ C is particularly preferably an even number x = 2 or 4, and n = 16 or n = 18. ｎ H ２ｎ－ｘ O ２ , very preferably x = 2 and n = 16 or 18 C ｎ H ２ｎ－ｘ O ２ C where x = 4 and n = 18 ｎ H ２ｎ－ｘ O ２ A rubber mixture according to any one of claims 1 to 3, characterized by being selected from among.

5. The rubber mixture according to any one of claims 1 to 4, characterized in that the at least one fatty acid is present in the at least one processing aid in an amount of 40 to 85% by weight, preferably 55 to 80% by weight, and the weight percentage value is based on the total amount of the at least one processing aid.

6. At least one processing aid in an amount of 0.1 to 30 phr, preferably 0.5 to 25 phr, particularly preferably 1 to 15 phr, and very particularly preferably 5 to 15 phr, - 40 to 85% by weight, preferably 55 to 80% by weight, - Fatty acid C where n = 10 to 30 ｎ H ２ｎ O ２ , and - Fatty acid C where x is an even number between 2 and 10, and n is between 10 and 30. ｎ H ２ｎ－ｘ O ２ At least one fatty acid selected from, wherein at least 80% by weight, preferably at least 90% by weight, and very preferably at least 95% by weight, based on the total amount of the at least one fatty acid, is fatty acid C with n = 10 to 30. ｎ H ２ｎ O ２ Preferably, C = 12 to 22 ｎ H ２ｎ O ２ C is particularly preferably n = 10, 12, 14, 16, and 18. ｎ H ２ｎ O ２ C is very preferably n=16 or n=18. ｎ H ２ｎ O ２ At least one fatty acid selected from, - 5 to 50% by weight, preferably 8 to 25% by weight, with n = 10 to 26 C ｎ H ２ｎ At least one alcohol selected from O and 1,1,1-trimethylolpropane (TMP), - 5 to 20% by weight, preferably 8 to 15% by weight, of at least one ester selected from stearyl dodecanoate, stearyl myristate, stearyl palmitate, docosyl palmitate, stearyl stearate, eicosyl stearate, tetradecyl stearate, docosyl stearate, and docosyl arachidate, and - 1 to 10% by weight, preferably 1 to 5% by weight of polyethylene glycol A rubber mixture according to any one of claims 1 to 5, characterized in that it contains at least one processing aid containing, and the weight percentage value is based on the total amount of the at least one processing aid.

7. The rubber mixture according to any one of claims 1 to 6, characterized by containing the vulcanization accelerator polyethyleneimine in an amount of 0.01 to 10 phr, particularly preferably 0.1 to 5 phr, and very particularly preferably 0.2 to 2.5 phr.

8. The rubber mixture according to any one of claims 1 to 7, characterized in that the total content of the guanidine-containing compound in the rubber mixture is 0.4 phr or less, preferably 0.2 phr or less, particularly preferably 0.1 phr or less, and very particularly preferably 0.01 phr or less.

9. - At least one functionalized synthetic rubber with a hardness of 50 to 100 phr, preferably a functionalized BR rubber and / or functionalized SBR rubber with a hardness of 70 to 100 phr. - At least one natural rubber and / or non-functionalized synthetic rubber with a content of 0 to 50 phr, preferably 0 to 30 phr. - At least one hydroxyl-containing oxide filler in a quantity of 20 to 200 phr, - At least one reinforcing additive in a quantity of 0.5 to 15 phr, comprising a sulfur-containing organic silane, preferably a bifunctional sulfur-containing organic silane containing at least one alkoxy, cycloalkoxy, or phenoxy group on a silicon atom and a group selected from -SCN, -SH, or -Sx- (where x = 2 to 8) as another functional group, particularly preferably a sulfur-containing silane having an alkoxysilyl, and very particularly preferably a sulfur-containing organic silane having a trialkoxysilyl, - At least one carbon black in a concentration of 0.1 to 120 phr, preferably 0.1 to 100 phr, - At least one crosslinking agent from the group consisting of sulfur donors and sulfur, in a quantity of 0.5 to 10 phr. - 0.1 to 10 phr of zinc oxide, - At least one vulcanization accelerator containing polyethyleneimine in an amount of 0.1 to 10 phr, and - At least one processing aid containing at least one fatty acid in an amount of 0.1 to 30 phr, preferably 0.5 to 25 phr, particularly preferably 1 to 15 phr, and very particularly preferably 5 to 15 phr. The rubber mixture according to claim 1, characterized by containing the following:

10. The rubber mixture according to any one of claims 1 to 9, characterized by containing at least one vulcanization retarder, preferably selected from the group consisting of sulfenamide retarders, most preferably selected from N-cyclohexylthiophthalimide and N-phenyl-N-(trichloromethylsulfenyl)benzenesulfonamide, and most preferably N-cyclohexylthiophthalimide, in an amount preferably 0.01 to 10 phr, particularly preferably 0.05 to 5 phr, very particularly preferably 0.1 to 1 phr, and most preferably 0.1 to 0.5 phr.

11. A method for producing the rubber mixture of the present invention according to any one of claims 1 to 10, characterized in that each of the above components is mixed in a mixing process.

12. In the method for producing the rubber mixture, - First, the at least one rubber, the at least one hydroxyl-containing oxide filler, the at least one reinforcing additive from the group of sulfur-containing organic silanes, the vulcanization accelerator polyethyleneimine, and the at least one processing aid, and optionally, further rubber additives are mixed, preferably at 130°C to 180°C, and The method according to claim 11, characterized in that, subsequently, at least one crosslinking agent from the group of sulfur and sulfur donors, and optionally at least one further vulcanization accelerator and optionally at least further rubber auxiliaries are added to the obtained rubber mixture, preferably at 50 to 130°C.

13. A vulcanized product that can be obtained by vulcanizing a rubber mixture according to any one of claims 1 to 10.

14. A molded article containing one or more rubber vulcanized products as described in claim 13, preferably an industrial rubber article and a tire.

15. Use of at least one processing aid containing polyethyleneimine, preferably in an amount of 0.01 to 10 phr, particularly preferably 0.1 to 5 phr, very particularly preferably 0.2 to 2.5 phr, and at least one fatty acid, preferably in an amount of 0.1 to 30 phr, particularly preferably 1 to 15 phr, very particularly preferably 5 to 15 phr, in a sulfur crosslinkable rubber mixture, a vulcanized product that can be obtained therefrom, and a molded product that can be obtained therefrom, to address, or preferably improve, the trade-off between rolling resistance and wet braking.

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