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    • 专利摘要:
    RETICULABLE RUBBER MIXTURE WITH SULFUR. The present invention relates to a mixture of crosslinkable rubber with sulfur, particularly for motor vehicle tires, belts, belts and flexible tubes, which among others is characterized by an improved rolling resistance behavior. For this purpose, the rubber mixture contains at least the following components: - from 5 phr to 95 phr of at least one styrene butadiene rubber, functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups and whose styrene content is 0% by weight to 12% by weight and which in the non-vulcanized state has a glass transition temperature (Tg) of -75 ° C to -120 ° C according to the DSC method ; - from 5 phr to 95 phr of at least one additional rubber, and; - from 20 phr to 300 phr of at least one silica.
    公开号:BR112016004453B1
    申请号:R112016004453-3
    申请日:2014-09-04
    公开日:2020-12-08
    发明作者:Katharina Herzog；Carla Recker；Viktoria Pavon Sierra；Thomas Kramer；Thorsten Torbrügge；Norbert Müller；Norbert Kendziorra
    申请人:Continental Reifen Deutschland Gmbh；
    IPC主号:
    专利说明:

    [001] The present invention relates to a mixture of crosslinkable rubber with sulfur, particularly for tires for automatic vehicles, belts, belts and flexible tubes.
    [002] The composition of the tread rubber largely determines the driving properties of a tire, particularly a tire for automotive vehicles. In addition, rubber mixtures, mainly used in belts, belts and flexible tubes subject to high mechanical loads, are responsible for the stability and durability of these rubber articles.
    [003] Therefore, rubber mixtures for automotive tires, belts, belts and hoses are subject to very high requirements. By partially or completely replacing the carbon black charge with the silica charge in rubber mixtures in recent years eg. the driving properties of a tire have reached a higher level. However, conflicts of known objectives regarding tire properties continue to exist even in the case of tread mixes containing silica. Thus, improved wet grip and dry braking generally imply a worsening of rolling resistance, winter driving properties and abrasion wear behavior. These properties are an equally important quality criterion in the case of technical rubber articles such as straps, straps and flexible tubes.
    [004] More particularly, in the case of tires for automatic vehicles, numerous attempts have been made to positively influence the properties of the tire by varying the polymer components, loads and additives, particularly in the mixture for tread. In this case, attention is mainly focused on the rolling resistance and abrasion wear properties. In this case, it must be taken into account that an improvement in one of the tire's properties often implies a worsening of the other tire's property. In a given mixing system, for example, there are different known possibilities for optimizing rolling resistance.
    [005] In this case, they refer to the reduction of the load level, the replacement of the polymer system and the reduction of the glass transition temperature Tg of the rubber mixture. In this case, all of the above measures lead to a worsening of the abrasive wear properties and / or wet grip properties and / or the tear resistance properties of the mixture.
    [006] The term tire for automotive vehicles in the context of the present invention should mean tires for automotive vehicles, solid tires and tires for two-wheel vehicles.
    [007] In the technical field, the influence of the glass transition temperature of the rubber mixture used through the selection of suitable polymer systems is particularly discussed.
    [008] In this case, it is known that in the case of the same mixing components of two rubber mixtures the respective glass transition temperature is determined by the glass transition temperature of the polymer used / the polymers used. The higher the glass transition temperature of a polymer, the higher the glass transition temperature of the rubber mixture and the worse the rolling resistance behavior of the rubber mixture. Good indicators regarding the rolling resistance behavior of rubber mixtures are the return elasticities from 60 ° C to 70 ° C and the loss values by hysteresis, expressed by tan δ from 60 ° C to 70 ° C.
    [009] In the state of the art it is known that 1,4-polybutadiene rubber has a very low glass transition temperature of approx. -105 ° C, so this rubber is particularly suitable for improving the rolling resistance behavior of rubber mixtures. However, it is also known that this implies a significant worsening of the wet grip behavior of the rubber mixture.
    [0010] In addition, to influence tire properties, such as abrasion wear, wet grip behavior and rolling resistance, it is known to use different styrene butadiene co-polymers with different styrene and vinyl contents and with different modifications for rubber mixtures, in which case the above mentioned problem of conflict of objectives also occurs.
    [0011] From WO 2009007167 A1 it is known to use two different polymers with different glass transition temperatures for improving wet grip. Also for improving wet grip in EP 065982 A1, 20 phr to 80 phr of diene rubber, more specifically natural rubber, and 80 phr to 20 phr of butadiene styrene copolymer with a temperature of glass transition between -50 ° C and -25 ° C. The use of 10 phr to 50 phr of diene rubber, in this case styrene butadiene rubber, with a glass transition temperature below -45 ° C for improving the relationship between dry grip and wet grip is described in EP 1253170 A1. In US 6,812,822 B2, in turn, 5 phr to 40 phr of styrene butadiene copolymer with a glass transition temperature of -35 ° C or higher and 95 phr to 60 phr of diolefin rubber with a glass transition temperature are used -20 ° C or lower to improve the vibration-isolating properties of the rubber mixture.
    [0012] DE 40 01 822 C2 describes a rubber mass, comprising from 10 parts by weight to 100 parts by weight of a solution polymerized styrene butadiene rubber with a vinyl content of 20% by weight to 70% by weight and a styrene content of 54.5% by weight to 65% by weight and 0 parts by weight to 90 parts by weight of an emulsion polymerized styrene butadiene rubber with a glass transition temperature of at least -60 ° C and with a styrene content of 20% by weight to 65% by weight and at least 70 parts by weight of carbon black, which are mixed in this rubber mass. This rubber grease is particularly designed for use on high-performance tire bearing surfaces with a high hysteresis loss, high heat resistance and remarkable adhesion.
    [0013] DE 698 02 245 T2, in turn, describes a tire with a sulfur-vulcanizable composition, characterized by 50 phr to 90 phr of a rubber with a glass transition temperature in the range of -80 ° C and -110 ° C and 10 phr to 50 phr of at least one rubber with a glass transition temperature in the range of -79 ° C to +20 ° C and 15 phr to 50 phr of a resin, which is not a eraser. This mixture has improved laboratory properties, correlated with improved tire wear and a simultaneous improvement in grip and driving behavior.
    [0014] However, the improvement in adhesion behavior due to a higher hysteresis loss, that is to say the higher tan δ of 0 ° C implies a worsening of the rolling resistance properties and, therefore, of the damping during driving , which is evident eg. in DE 698 02 245 T2 due to the simultaneous increase of tan δ at 60 ° C in rubber mixtures containing ESBR and BR.
    [0015] In order to optimize the rolling resistance behavior or to optimize several other properties of rubber blends for use in tires without a worsening of the rolling resistance behavior, it is known to functionalize the used diene rubber, so that a connection occurs to the load (s).
    Thus, for example, EP 2357211 A1 discloses a rubber mixture, which contains at least one aliphatic and / or aromatic hydrocarbon resin, at least one filler and at least one functionalized diene rubber, whose functionalization is present throughout polymeric chain and / or at the end and allows connection to the loads. As functionalizations, hydroxyl groups are disclosed in Table 1 for the binding of polymers to silica.
    [0017] EP 2289990 A1 discloses a rubber mixture, which contains the same amounts of silica and carbon black as well as functionalized polymers, in which the use of 50 phr of polybutadiene functionalized with siloxy groups or others is disclosed. siloxy aldimine instead of 50 phr of a non-functionalized polybutadiene. A rubber mixture of this nature has improved rolling resistance indicators (Rebound 100 ° C) while showing poor wet grip properties (Rebound 23 ° C). The influence on the tire properties, particularly the additional tear properties, is not disclosed in EP 2289990 A1.
    [0018] EP 1963110 B1 discloses polymers modified with silane sulfide with a glass transition temperature of -23 ° C to -28 ° C, which in a rubber mixture allow to achieve reduced values for the tan delta loss factor ( tan δ) at 60 ° C and remaining properties well balanced.
    [0019] EP 1535948 B1 discloses a styrene butadiene rubber, which comprises polyorganosiloxane groups containing epoxy groups as functionalization, with three or more polymer chains being linked to a polyorganosiloxane group. In the case of combining this polymer with a non-functionalized butadiene rubber in the rubber mixture containing silica, improved rolling resistance, abrasion wear and wet grip properties are achieved.
    [0020] Therefore, based on the state of the art, the present invention aims to disclose a mixture of rubber, particularly for tires for automotive vehicles, belts, belts and flex-flex, characterized by a further improvement of behavior resistance to improvement and abrasion wear behavior, in which the additional physical properties remain at the same level or, more particularly, the properties of tear resistance and / or wet grip properties are also optimized. In addition, the rubber mixture should optionally show an improvement over winter driving properties and / or handling behavior.
    [0021] This objective is achieved through a mixture of rubber, which contains at least the following components:
    [0022] - from 5 phr to 95 phr of at least one butadiene stretch rubber, functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups and whose styrene content it is from 0% by weight to 12% by weight and which in the vulcanized state has a glass transition temperature (Tg) of -75 ° C to -120 ° C according to the DSC method;
    [0023] - from 5 phr to 95 phr of at least one additional rubber, and;
    [0024] -from 20 phr to 300 phr of at least one silica.
    [0025] Surprisingly it was found that the combination of a styrene butadiene rubber with the above characteristics with at least one additional rubber and from 20 phr to 300 phr of silica in the rubber mixture according to the present invention is characterized by an optimization the level of physical properties, particularly the rolling resistance behavior and abrasion wear properties. At the same time, the remaining properties of the tire remain at an equally high level or are even improved, particularly the wet grip behavior and / or the tear resistance properties and / or the dry braking behavior and / or the winter driving properties and / or handling behavior of the rubber mixture remain at an equally high level or are even improved.
    [0026] The indication phr (parts per hundred parts of rubber by weight) within the scope of the present invention in this case is the conventional quantitative indication for mixing recipes in the rubber industry. The dosage of parts by weight of the individual substances in the present invention refers to 100 parts by weight of the total mass of all high molecular weight and therefore rigid rubbers present in the mixture.
    [0027] As mentioned above, rubbers with a reduced glass transition temperature have been used in a rubber mixture in combination with a rubber with a high Tg, to adjust the glass transition temperature of the rubber mixture in order to improve rolling resistance. According to the present invention, these rubbers can be replaced by at least one styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups with a glass transition temperature ( Tg) between -120 ° C and -75 ° C, so surprisingly, a significant improvement in the abrasion wear behavior is also achieved.
    [0028] Whereas the Tg of styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups is generally below that of the functionalized styrene butadiene rubber used up to the At the moment, the proportion of styrene butadiene rubbers with a higher Tg can be simultaneously increased, in order to achieve the advantages of the so-called "high Tg styrene rubber".
    Therefore, according to the present invention, it is essential that the styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups used in the rubber mixture. functionalized.
    [0030] Functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups within the scope of the present invention means that the rubber along the polymer chain comprises several of these groups and / or at the end The chain of each polymeric chain comprises at least one phthalocyanine group and / or a hydroxyl group and / or an epoxy group and / or a silane sulfide group. In this case it is also possible that not all polymeric chains have a phthalocyanine group and / or a hydroxyl group and / or an epoxy group and / or a silane sulfide group. The weight ratio of functionalized polymer chains in this case is preferably from 30% by weight to 100% by weight, particularly preferably from 50% by weight to 100% by weight and more particularly preferably from 70% by weight to 100% by weight.
    [0031] Preferably the polymeric chains at the respective end of the chain are functionalized with at least one phthalocyanine group and / or a hydroxyl group and / or an epoxy group and / or a silane sulfide group.
    [0032] The functionalized styrene butadiene rubber is preferably produced by anionic polymerization. In this case, the active anionic polymeric chains react with one or more modifying compounds, whereby the functional group (s) are linked.
    [0033] According to a preferred embodiment of the invention the functionalized styrene butadiene rubber is functionalized with at least one hydroxyl group and / or with at least one silane sulfide group. By silane sulfide group in the context of the present invention is meant an organic group, which contains at least one sulfur atom and at least one substituted silyl SiR3 group.
    [0034] In this case, according to the present invention it is essential that the silane sulfide groups contain one or more sulfur atoms. In the case of the rubber mixture according to the present invention, it was found that with a functionalized styrene butadiene rubber, functionalized with at least one silane sulfide group, compared to a functionalized styrene butadiene rubber, functionalized with groups siloxy, siloxane, siloxyaldimine or aminosiloxane, although free of sulfur, whether or not they have sulfur atoms, improved physical properties can be achieved, such as particularly indicators relating to improved rolling resistance and / or improved abrasion wear behavior and / or improved tear resistance properties and / or improved handling properties, such as particularly higher stiffness, and / or improved wet grip properties.
    [0035] According to another preferred embodiment of the invention the functionalized styrene butadiene rubber is formed by the reaction of the active polymer chains during anionic polymerization with a silane sulfide modifier according to formula I: I) (R ' 'O) x (R) ySi-R'-S-SiR3
    [0036] wherein the R groups independently of one another are C1-C16-alkyl or benzyl groups; and
    [0037] R 'is a C1-C4-alkyl group; and
    [0038] R'is selected from C6-C18-aryl, C7-C50-alkylaryl, C1-C50-alkyl and C2-C50-dialkylether (ie -alkyl-O-alkyl-), in which each optional group is replaced with one or more groups, which is / are selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C6-C12-aryl, C7-C16-alkylaryl, di (C1-C7-hydrocarbil) amino, bis (tri (C1-C12-alkyl) silyl) amino, tris (C1-C7-hydrocarbyl) silyl and C1-C12-thioalkyl; and
    [0039] x is an integer selected from the numbers 1, 2 and 3; and
    [0040] y is an integer selected from the numbers 0, 1 and 2, and
    [0041] x + y = 3.
    [0042] It is assumed that the reaction of polymer chains with the silane sulfide modifier according to formula (I) generates a modified polymer according to formula (II): II) (D) z (R''O) x (R) ySi-R'-S-SiR3
    [0043] where D is an elastic polymer; and
    [0044] x is an integer selected from the numbers 0, 1 and 2; and
    [0045] y is an integer selected from the numbers 0, 1 and 2; and
    [0046] z is an integer selected from the numbers 1, 2 and 3; and
    [0047] x + y + z = 3;
    [0048] and R, R '' and R's are defined according to formula (I).
    [0049] A functionalized styrene butadiene rubber of this nature as is evident in formula II) is functionalized with silane sulfide groups.
    [0050] It is assumed that the polymer in case of contact with moisture at least partially generates a polymer modified according to formula (III): III) (D) z (HO) x (R) ySi-R'-S -SiR3
    [0051] where D is an elastic polymer; and
    [0052] x is an integer selected from the numbers 0, 1 and 2; and
    [0053] y is an integer selected from the numbers 0, 1 and 2; and
    [0054] z is an integer selected from the numbers 1, 2 and 3; and
    [0055] x + y + z = 3;
    [0056] and R and R's are defined according to formula (I).
    [0057] According to a preferred embodiment of the invention in formula (I) each R independently of one another is selected from C1-C5-alkyl groups and R 'is a C1-C5-alkyl group.
    [0058] According to another preferred embodiment of the invention the functionalized styrene butadiene rubber is formed by the reaction of the active polymer chains during anionic polymerization with at least one silane sulfide modifier according to formulas (1) and ( 2) as well as with at least one silane sulfide modifier according to formulas (3), (4), (5) and (6): (1) (R1O) 3Si-R4-S-SiR33 (2) ( R13O) 3Si-R9-N (SiR10R11R12) 2 (3) (R1O) x (R2) ySi-R4-S-SiR33 (4) (R13O) p (R14) qSi-R9-N (SiR10R11R12) 2

    [0059] in which R2, R3, R10, R11, R12, R14, R16, R17 and R18 independently of each other are selected from groups of C1-C16-alkyl and benzyl and in which the alkyl groups for the groups R10 , R11 and R12 and R16, R17 and R18 can be linked to each other in the form of a ring containing two silicon and nitrogen (N) atoms; and
    [0060] R1 and R13 independently of each other are selected from C1-C4-alkyl groups; and
    [0061] R4, R9 and R15 independently of each other are selected from C6-C18-aryl, C7-C50-alkylaryl, C1-C50-alkyl and C2-C50-dialkylether (that is - alkyl-O-alkyl-) , where each optional group is replaced with one or more groups, which is / are selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C6-C12-aryl, C7-C16-alkylaryl , di (C1-C7-hydrocarbyl) amino, bis (tri (C1-C12-alkyl) silyl) amino, tris (C1-C7-hydrocarbyl) silyl and C1-C12-thioalkyl; and
    [0062] R5, R6 and R7 independently of each other are selected from hydrogen (-H), C1-C16-alkyl and C6-C12-aryl; and
    [0063] R8 is selected from C1-C16-alkyl and C6-C12-aryl; and
    [0064] R19, R20 and R21 independently of each other are selected from hydrogen and C1-C16-alkyl; and
    [0065] x and p respectively are an integer selected from the numbers 1 and 2; and
    [0066] y and q respectively are an integer selected from the numbers 1 and 2; and
    [0067] x + y = 3, and
    [0068] p + q = 3.
    [0069] According to a particularly preferred embodiment of the invention, the functionalized styrene butadiene rubber is obtained by reacting the active polymer chains during anionic polymerization with at least one silane sulfide modifier according to formula IV): IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3
    [0070] The compound according to formula IV) is an example of the silane sulfide modifier according to formula (3). With a modified styrene butadiene rubber of this nature, particularly good improvements are achieved regarding the rolling resistance and / or abrasion wear behavior of the rubber mixture according to the present invention.
    [0071] According to a particularly preferred embodiment of the invention, the functionalized styrene butadiene rubber is obtained by the reaction of the active polymer chains during anionic polymerization with a silane sulfide modifier according to formula IV) and with the formula V):
    [0072] IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3
    [0073] V) (MeO) 3Si- (CH2) 2-S-SiMe2C (Me) 3
    [0074] The compound according to formula V) is an example of the silane sulfide modifier according to formula (1). With a modified styrene butadiene rubber of this nature, particularly good improvements are achieved regarding the rolling resistance and / or abrasion wear behavior of the rubber mixture according to the present invention. The polymerized styrene butadiene rubber in solution in the non-vulcanized state has a glass transition temperature of -75 ° C to -120 ° C (minus 75 ° C to minus 120 ° C), preferably from -75 ° C to - 110 ° C, particularly preferably from -80 ° C to -110 ° C, more particularly preferably from -80 ° C to -100 ° C and, therefore, can be considered as a styrene butadiene rubber with a glass transition temperature relatively reduced. Therefore, this styrene butadiene rubber in the rubber mixture according to the present invention replaces the diene rubbers known in the art with a reduced glass transition temperature, particularly butadiene rubber (= BR, polybutadiene), simultaneously improving the rolling resistance behavior.
    [0075] Furthermore, according to the present invention it is essential that the functionalized styrene butadiene rubber used in the rubber mixture has a styrene content from 0% by weight to 12% by weight. This means that in the case of 0% by weight of styrene, we are facing a butadiene rubber.
    [0076] According to a preferred embodiment of the invention the styrene content of the styrene butadiene rubber is from 0% by weight to 2% by weight, particularly preferably 0% by weight.
    [0077] According to another preferred embodiment of the invention the styrene content of the styrene butadiene rubber is 0.1% by weight to 12% by weight, particularly preferably from 5% by weight to 12% by weight, more particularly preferably from 9% by weight to 11% by weight.
    [0078] The solution-polymerized styrene butadiene rubber preferably has a vinyl content in relation to the butadiene ratio of 1% by weight to 30% by weight, preferably 1% by weight to 15% by weight, particularly preferably 5 % by weight to 12% by weight and more particularly preferably from 7% by weight to 12% by weight, even more particularly preferably from 7% by weight to 11% by weight. Therefore, a reduced glass transition temperature of the polymer is achieved.
    [0079] The determination of the styrene content and the vinyl content of the proportion of butadiene of the polymers discussed in the scope of the present invention is carried out by means of 13C-NMR (solvent agent deuterochloroform CDCl3; NMR: ing. "Nuclear magnetic resonance ") and by comparison with infrared spectrometry data (IR; Nicolet FT-IR spectrometer, 25 mm diameter x 5 mm KBr window, 80 mg sample in 5 mL of 1,2-dichlorobenzene). The determination of the glass transition temperature (Tg) of the polymers (particularly of the functionalized styrene butadiene rubbers) is carried out on the basis of differential scanning calorimetry (ing. Dynamic Scanning Calorimetry, DSC according to DIN 53765: 1994-03 or ISO 11357-2: 1999-03, DSC calibrated with low temperature device, calibration according to the type of device and the manufacturer's instructions, sample in aluminum container and with aluminum cover, cooling to lower temperatures at -120 ° C to 10 ° C / min).
    [0080] The above functionalized styrene butadiene rubber preferably has a Mooney viscosity (ML 1 +4, 100 ° C according to ASTM D 1646 (2004)) from 20 Mooney units to 200 Mooney units (MU = mooney units), particularly preferably from 25 to 150, more particularly preferably from 25 to 100.
    [0081] The preferred molar mass distribution of the functionalized styrene butadiene rubber, Mw / Mn, is between 1.2 and 3.0.
    [0082] When Mw / Mn is less than 1.2, a worse processability of the polymer and of the rubber mixture according to the present invention is generated as well as a worse distribution of the components, particularly a worse dispersion of loads of the rubber mixture. When Mw / Mn is greater than 3.0, the proportion of reduced molar mass components is too high, which results in a higher hysteresis and, therefore, a worse rolling resistance behavior of the rubber mixture.
    [0083] The functionalized styrene butadiene rubber referred to above in the rubber mixture according to the present invention is used in amounts of 5 phr to 95 phr, preferably from 20 phr to 95 phr, particularly preferably from 40 phr to 95 phr, more particularly preferably from 60 phr to 95 phr, even more preferably in quantities of 70 phr to 90 phr.
    [0084] Styrene butadiene rubber functionalized with phthalocinanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups according to a preferred embodiment has a styrene content of 0% in weight and a vinyl content of 1% by weight to 15% by weight, particularly preferably from 7% by weight to 12% by weight.
    [0085] The styrene butadiene rubber functionalized with phthalocinanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with used silane sulfide groups can be polymerized in solution or polymerized in emulsion. Preferably it is a styrene butadiene rubber polymerized in an S (S) BR solution with a styrene content of 0% by weight to 12% by weight.
    [0086] Furthermore, the rubber mixture according to the present invention contains from 5 phr to 95 phr, preferably from 5 phr to 80 phr, particularly preferably from 5 phr to 60 phr, more particularly preferably from 5 phr at 40 phr, even more particularly preferably from 10 phr to 30 phr of at least one additional rubber.
    [0087] At least one additional rubber in this case is selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or butadiene rubber and / or styrene butadiene rubber polymerized in solution and / or emulsified butadiene styrene rubber and / or liquid rubbers with an average weight molar mass Mw greater than 20000 g / mol and / or halobutyl rubber and / or polynorbornene and / or isobutylene and / or boron crack ethylene propylene diene and / or nitrile rubber and / or chloroprene rubber and / or acrylic rubber and / or fluorinated rubber and / or silicone rubber and / or polysulfide rubber and / or epichlorohydrin rubber and / or styrene terpolymer butadiene isoprene and / or hydronyl acrylonitrile butadiene rubber and / or isoprene butadiene copolymer and / or hydrated styrene butadiene rubber.
    [0088] Particularly nitrile rubber, hydrated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene propylene diene rubber are used in the production of technical rubber articles, such as belts, belts and flexible tubes.
    [0089] Preferably in the case of the additional rubber it is at least one diene rubber, selected from the group consisting of synthetic polyisoprene and natural polyisoprene (NR) and styrene butadiene and polybutadiene rubber (BR).
    [0090] In this case, in the case of natural polyisoprene and synthetic polyisoprene, it is possible to deal with all types known to the person skilled in the art.
    [0091] Preferably, in the case of additional diene rubber it is at least one natural polyisoprene. Therefore, a particularly good processability (by extrusion, mixing, etc.) of the rubber mixture according to the present invention is achieved. The styrene butadiene rubber of the group of additional diene rubbers within the scope of the present invention is a styrene butadiene rubber known in the prior art and can therefore be used in admixture with the polymerized styrene butadiene rubber in solution ( SSBR) according to the present invention, which is functionalized with phthalocyanine groups and / or with hydroxy groups and / or with epoxy groups and / or with silane sulfide groups and whose styrene content is 0% by weight at 12 % by weight and that in the non-vulcanized state has a glass transition temperature Tg of -75 ° C to -120 ° C according to the DSC method.
    [0092] According to another preferred improvement of the invention the rubber mixture contains from 5 phr to 95 phr of at least one natural polyisoprene and / or from 5 phr to 95 phr of at least one synthetic polyisoprene, preferably from 5 phr to 20 phr of at least one natural polyisoprene and / or 5 phr to 20 phr of at least one synthetic polyisoprene.
    [0093] According to a preferred embodiment of the invention the rubber mixture contains from 5 phr to 15 phr of at least one natural and / or synthetic polyisoprene in combination with 85 phr to 95 phr of the rubber mixture of functionalized styrene butadiene as described above with a Tg of -100 ° C to -87 ° C, where this in this embodiment particularly preferably has a styrene content of 0% by weight to 2% by weight, more particularly preferably 0 % by weight. A rubber mixture of this nature compared to a rubber mixture which has the same amount of butadiene rubber with a Tg of -105 ° C according to the state of the art, has improved abrasion wear properties and resistance behavior improved bearing, the remaining properties of the tire are not significantly worsened and / or remain the same. In particular, wet grip behavior and tear resistance properties remain acceptable for use in a tire tread for automotive vehicles.
    [0094] According to another preferred embodiment of the invention the rubber mixture contains from 45 phr to 55 phr of at least one carbon black, preferably a carbon black of type N339, from 40 phr to 50 phr of silica as well as from 5 phr to 15 phr of at least one natural and / or synthetic polyisoprene in combination with 85 phr to 95 phr of the functionalized styrene butadiene rubber as described above with a Tg of -100 ° C to -87 ° C , in which in this embodiment it particularly preferably has a styrene content of 0% by weight to 2% by weight, more particularly preferably 0% by weight. A rubber mixture of this nature compared to a rubber mixture that has the same amount of butadiene rubber with a Tg of -105 ° C according to the state of the art, has improved abrasion wear properties, resistance behavior improved rolling, and equal and / or higher stiffness as an indicator of equal and / or improved handling behavior, with the remaining tire properties not being significantly worsened and / or remaining the same. More particularly, wet grip behavior and tear resistance properties remain at an acceptable level for use in automotive tire treads.
    [0095] According to another preferred embodiment of the invention the rubber mixture contains from 30 phr to 45 phr of at least one natural polyisoprene and / or from 55 phr to 70 phr of at least one synthetic polyisoprene , with natural polyisoprene being particularly preferred, in combination with 55 phr to 70 phr of the functionalized styrene butadiene rubber as described above with a Tg of -100 ° C to -87 ° C, where this in this embodiment particularly preferably presents a styrene content of 0% by weight to 2% by weight, more particularly preferably 0% by weight. According to this embodiment of the invention the rubber mixture compared to the state of the art has improved rolling resistance and wet braking properties and improved abrasion and dry braking wear properties. Preferably in this embodiment of the invention, 5 phr to 10 phr of a carbon black, preferably of the N121 type, are used in combination with 70 phr to 80 phr of a silica. Furthermore, preferably in this embodiment of the invention no additional rubber is contained.
    [0096] According to a preferred improvement of the invention the rubber mixture contains from 30 phr to 50 phr of the functionalized styrene butadiene rubber as described above with a Tg of -100 ° C to -87 ° C, where this in this embodiment it particularly preferably has a styrene content of 0% by weight to 2% by weight, more particularly preferably 0% by weight, and from 5 phr to 10 phr of natural polyisoprene and from 40 phr to 60 phr at least one additional styrene butadiene rubber. A rubber mixture of this nature has particularly advantageous abrasion and wet grip properties, without disadvantages in terms of rolling resistance.
    [0097] According to another preferred embodiment of the invention the rubber mixture contains from 5 phr to 95 phr, particularly preferably from 5 phr to 65 phr and more particularly preferably from 10 phr to 55 phr, from at least one solution-polymerized styrene butadiene rubber, functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups and whose styrene content is from 0% by weight to 12% in weight and that in the non-vulcanized state it has a glass transition temperature Tg of -75 ° C to -120 ° C according to the DSC method, and from 5 phr to 70 phr, particularly and preferably from 35 phr to 70 phr and more particularly and preferably from 45 phr to 55 phr, of at least one additional diene rubber. Particularly preferably in this preferred embodiment of the present invention, in the case of at least one additional diene rubber, these are two different diene rubbers. Particularly and preferably the two different diene rubbers are styrene butadiene rubber and natural polyisoprene. With a polymer system composition of this nature it is possible to adjust the glass transition temperature Tg of the rubber mixture to the same state of the art, with improved rolling resistance indicators and improved abrasion wear behavior without this. imply a worsening of the remaining tire properties of the rubber blend compared to the state of the art.
    [0098] According to another preferred embodiment of the invention the rubber mixture contains from 5 phr to 15 phr of at least one natural and / or synthetic polyisoprene in combination with 85 phr to 95 phr of the butadiene styrene mixture functionalized with silane sulfide groups as described above with a Tg of -87 ° C to -80 ° C, where this in this embodiment particularly preferably has a styrene content of 9% by weight to 11% by weight, more particularly preferably 10% by weight. A rubber mixture of this nature compared to a rubber mixture that has the same amount of butadiene rubber with a Tg of -105 ° C according to the state of the art, has an improved rolling resistance behavior, being that the remaining properties of the tire are not significantly worsened and / or remain the same. More particularly, wet grip behavior and tear resistance properties remain at an acceptable level for use in tire treads for automotive vehicles.
    [0099] According to another preferred embodiment of the invention the rubber mixture contains from 15 phr to 25 phr of at least one natural and / or synthetic polyisoprene in combination with 24 phr to 34 phr of a styrene rubber butadiene polymerized in solution according to the state of the art with a glass transition temperature of -40 ° C to +10 ° C (minus 40 ° C to plus 10 ° C), preferably from -30 ° C to -20 ° C (minus 30 ° C to minus 20 ° C), (SSBR of high Tg) as well as 46 phr to 56 phr of the styrene butadiene rubber functionalized with silane sulfide groups as described above with a Tg of -87 ° C at - 80 ° C, in which in this embodiment particularly preferably it has a styrene content of 9% by weight to 11% by weight, more particularly 10% by weight.
    [00100] A rubber mixture of this nature replaces a rubber mixture according to the state of the art with the same glass transition temperature, compared to the state of the art due to the use of styrene butadiene rubber. above described with a Tg of -87 ° C to -80 ° C simultaneously the amount of high Tg SSBR can be increased, which leads to a simultaneous improvement of the rolling resistance behavior and abrasion wear properties , where the remaining properties of the tire remain at approximately the same level.
    [00101] According to another preferred embodiment of the invention the rubber mixture contains from 10 phr to 70 phr of a styrene butadiene rubber polymerized in solution according to the state of the art with a glass transition temperature of - 40 ° C to +10 ° C (high TBR SSBR) as well as 10 phr to 70 phr of styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with sulfide groups silane, particularly preferably with silane sulfide groups, with a Tg of -120 ° C to -75 ° C, preferably from -110 ° C to -75 ° C, particularly preferably from -110 ° C to - 80 ° C, more particularly preferably from -87 ° C to -80 ° C, where this in this embodiment preferably has a styrene content of 1% by weight to 12% by weight, particularly preferably from 9% by weight to 11% by weight , even more particularly preferably from 10% by weight to 11% by weight. In addition, the rubber mixture may contain at least one additional diene rubber, particularly natural and / or synthetic polyisoprene.
    [00102] A rubber mixture of this nature replaces a rubber mixture according to the state of the art with the same glass transition temperature, and compared to the state of the art due to the use of the functional butadiene styrene rubber above described with a Tg of -120 ° C to -75 ° C, preferably from -110 ° C to -75 ° C, particularly preferably from - 110 ° C to -80 ° C, more particularly preferably from -87 ° C to - 80 ° C simultaneously, the amount of high Tg SSBR can be increased, which leads to a simultaneous improvement of rolling resistance behavior and abrasion wear properties, where the remaining tire properties remain approximately at same level.
    [00103] The rubber mixture according to the present invention contains from 20 phr to 300 phr, preferably from 20 phr to 150 phr, particularly preferably from 40 phr to 150 phr and more particularly preferably from 80 phr to 110 phr of at least one silica.
    [00104] In addition to the silica, the rubber mixture according to the present invention may also contain polar and / or non-polar charges, such as e.g. carbon black.
    [00105] In the case of silicas, the silicas known to the person skilled in the art may be used, which are suitable as fillers for rubber mixtures for tires. However, particularly preferably, finely distributed, precipitated silica is used, which has a nitrogen surface (BET surface) (according to DIN ISO 9277 and DIN 66132) of 35 m2 / g to 350 m2 / g, preferably 35 m2 / g to 260 m2 / g, particularly preferably from 100 m2 / g to 260 m2 / g and more particularly preferably from 130 m2 / g to 235 m2 / g, and a CTAB surface (according to ASTM D 3765) of 30 m2 / g to 400 m2 / g, preferably from 30 m2 / g to 250 m2 / g, particularly preferably from 100 m2 / g to 250 m2 / g and more particularly preferably from 125 m2 / g to 230 m2 / g. Silicas of this nature, e.g. in rubber mixtures for tire treads lead to particularly good physical properties of vulcanized. In addition, they can lead to advantages in mixing processing due to a reduction in mixing time and the maintenance of product properties, which leads to improved productivity. As silicas they can be used e.g. any of the type Ultrasil® VN3 (trade name) from EVONIK as also highly dispersible silicas, the so-called HD silicas (eg Zeosil® 1165 MP from Rhodia).
    [00106] Preferably, a coupling agent is used, in the form of silane or an organic silicon compound. In this case, one or more silane coupling agents can be used in combination with each other. Therefore, the rubber mixture can contain a mixture of different silanes. The silane coupling agents react with the silanol surface groups of the silica or with other polar groups during mixing of the rubber or rubber mixture (in situ) or before adding the charge to the rubber in the direction of a preliminary treatment (preliminary modification ). In this case, as silane coupling agents, all silane coupling agents can be used for use in rubber mixtures known to the person skilled in the art. Coupling agents of this nature known in the art are bifunctional organo-silanes, which have at least one alkoxy, cycloalkoxy or phenoxy group as the initial group on the silicon atom and as another functionality they present a group, which may eventually be formed after the split. a chemical reaction with the polymer double bonds. In the case of the latter group, it can be treated, for example. of the following chemical groups: -SCN, -SH, -NH2 or -Sx- (with x = 2 to 8).
    [00107] Thus, as silane coupling agents they can be used e.g. 3-mercaptopropyltriethoxysilane, 3-thiocyanate-propyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfide with 2 to 8 sulfur atoms, e.g. 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD) or also mixtures of sulfides with 1 to 8 sulfur atoms with different levels of different sulfides. In this case, TESPT can also be added as a mixture with industrial carbon black (trade name X50S® from Evonik).
    [00108] Preferably a mixture of silane is used, which contains 40% by weight to 100% by weight of disulfide, particularly preferably from 55% by weight to 85% by weight of disulfide and more particularly preferably 60% by weight to 80% by weight of disulfide.
    [00109] Also blocked mercaptosilanes, such as are known e.g. WO 99/09036, can be used as a silane coupling agent. Silanes, as described in WO 2008/083241 A1, WO 2008/083242 A1, WO 2008/083243 A1 and WO 2008/083244 A1, can also be used. They can be used eg. silanes, marketed under the designation NXT in different variants of the firm Momentive, USA, or those, which are marketed under the designation VP Si 363® by the firm Evonik Industries. The amount of the coupling agent is preferably 0.1 phr to 20 phr, particularly preferably 1 phr to 15 phr.
    [00110] According to a preferred embodiment of the invention the rubber mixture contains 80 phr to 110 phr silica. Therefore, particularly good abrasion wear properties and good tear resistance properties and improved dry braking properties are generated. According to this preferred embodiment, in addition, preferably from 2 phr to 15 phr, particularly preferably from 2 phr to 10 phr, carbon black is preferably contained in the rubber mixture.
    [00111] According to a particularly advantageous embodiment of the invention, the rubber mixture contains from 40 phr to 60 phr of at least one carbon black. As a result, a particularly high improvement in abrasion wear properties is generated compared to the state of the art, with stiffness being simultaneously increased, so the handling behavior is further improved. At the same time, this rubber mixture shows a particularly high improvement in rolling resistance properties. Therefore, with this embodiment of the invention, the conflict of objectives between rolling resistance, abrasion wear and handling properties is more intensely disaggregated compared to the state of the art.
    [00112] As carbon blacks, all types of carbon black known to the person skilled in the art are suitable. According to one embodiment, carbon black has an iodine index, according to the ASTM D 1510 standard, also called an iodine adsorption index, between 30 g / kg and 250 g / kg, preferably between 30 g / kg and 180 g / kg, particularly preferably between 40 g / kg and 180 g / kg and more particularly preferably between 40 g / kg and 130 g / kg, and a DBP index according to ASTM D 2414 of 80 mL / 100 g to 200 ml / 100 g, preferably from 100 ml / 100 g to 200 ml / 100 g, particularly preferably from 115 ml / 100 g to 200 ml / 100 g.
    [00113] The DBP index according to the ASTM D 2414 standard determines the specific absorption volume of a carbon black or a white charge by means of dibutyl phthalate. The use of a type of carbon black of this nature in the rubber mixture, particularly for automotive vehicle tires, ensures a good compromise between abrasion wear resistance and heat generation which, in turn, influences rolling resistance. ecologically relevant. In this case, preferably only one type of carbon black is used in the rubber mixture, and different types of carbon black can also be mixed in the rubber mixture.
    [00114] Furthermore, it is possible that the rubber mixture contains carbon nanotubes (carbon nanotubes (CNT) including discrete CNTs, the so-called hollow carbon fibers (HCF) and modified CNTs containing one or more functional groups, such as hydroxyl groups , carboxy and carbonyl).
    [00115] Graphite and graphene as well as so-called "carbon-silica double phase fillers" are also possible as fillers.
    [00116] The rubber mixture may also contain other polar charges, such as, for example, aluminosilicates, sugar, starch, magnesium oxide, titanium dioxide or rubber gels.
    [00117] Furthermore, the rubber mixture may also contain from 0 phr to 70 phr, preferably from 0.1 phr to 60 phr, more preferably from 0.1 phr to 50 phr, of at least one plasticizer. These include all plasticizers known to the person skilled in the art such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as e.g. MES (mild extraction solvate) or TDAE (treated distillate aromatic extract), or Rubber-to-Liquid (RTL) oils or Biomass-to-Liquid (BTL) oils or artificial rubbers or plasticizing resins or liquid polymers (such as BR liquids), whose average molar mass (determination by GPC = gel permeation chromatography, based on BS ISO 11344: 2004) is between 500 g / mol and 20000 g / mol. When liquid polymers are used in the rubber mixture according to the present invention as a plasticizer, they are not considered as rubber when calculating the composition of the polymer matrix.
    [00118] In the case of using mineral oil it is preferably selected from the group consisting of DAE (Destillated Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Destillated Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.
    [00119] In addition, the rubber mixture according to the present invention may contain conventional additives in conventional parts by weight. These additives include a) Aging protection agents, such as e.g. N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine (6PPD), N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-ditholyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ); b) Activators, such as eg zinc oxide and fatty acids (eg stearic acid); c) Waxes; d) Resins, particularly adhesive resins; e) Auxiliary chewing agents, such as e.g. 2,2'-dibenzamidodiphenyldisulfide (DBD), and; f) Auxiliary processing agents, such as e.g. fatty acid salts, such as e.g. zinc soaps, and esters of fatty acids and their derivatives.
    [00120] Particularly, in the case of the use of the rubber mixture according to the present invention for the internal components of a tire or of a technical rubber article, which have a direct contact with existing reinforcements, generally the rubber mixture is also A suitable adhesive system is added, often in the form of adhesive resins.
    [00121] The quantitative part of the total amount of additional additives is from 3 phr to 150 phr, preferably from 3 phr to 100 phr and particularly preferably from 5 phr to 80 phr. The total quantitative part of the additional additives also contains from 0.1 phr to 10 phr, preferably from 0.2 phr to 8 phr, particularly preferably from 0.2 phr to 4 phr, of zinc oxide (ZnO). In this case, all types of zinc oxide known to the person skilled in the art can be treated, such as e.g. granules or ZnO powder. The conventionally used zinc oxide generally has a BET surface of less than 10 m2 / g. However, a zinc nano oxide with a BET surface of 10 m2 / g to 60 m2 / g can also be used.
    [00122] Vulcanization is carried out in the presence of sulfur or sulfur donors with the aid of vulcanization accelerators, in which some vulcanization accelerators can simultaneously act as sulfur donors. The sulfur or the sulfur donor as well as one or more accelerators are added to the rubber mixture in the last mixing step in the amounts mentioned above. In this case, the accelerator is selected from the group consisting of thiazole-type accelerators and / or mercapto-type accelerators and / or sulfenamide-type accelerators and / or thiocarbamate-type accelerators and / or thiurame-type accelerators and / or thiophosphate-type accelerators and / or thiourea-type accelerators and / or xanthogenate-type accelerators and / or guanidine-type accelerators. It is preferred to use a sulfenamide type accelerator, selected from the group consisting of N-cyclohexyl-2-benzothiazolsulfenamide (CBS) and / or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and / or benzothiazil- 2-sulfenmorpholide (MBS) and / or N-terc.butyl-2-benzothiazilsulfenamide (TBBS).
    [00123] Additional crosslinking systems can also be used in the rubber mixture, as obtainable under the trade name Vulkuren®, Duralink® or Perkalink®, or crosslinking systems as described in WO 2010/049261 A2. This system contains a vulcanization agent, which cross-links with a functionality greater than four, and at least one vulcanization accelerator. The vulcanizing agent, which cross-links with functionality greater than four, for example has the general formula A): A) G [CaH2a-CH2-SbY] c
    [00124] where G represents a polyvalent cyclic hydrocarbon group and / or a polyvalent heterohydrocarbon group and / or a polyvalent siloxane group, containing from 1 to 100 atoms; where Y independently selected from an active rubber group, contains sulfur-containing functionality, and; where a, b and c are integers, for which independently the following is valid: a equal to 0 to 6; b equals 0 to 8, and; c equals 3 to 5.
    [00125] The active rubber group is preferably selected from a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a hydrocarbon group and a sodium thiosulfonate group (colored saline group). Consequently, very good abrasion and tear resistance properties of the rubber mixture according to the present invention are achieved.
    [00126] Within the scope of the present invention, sulfur and sulfur donors, including sulfur donor silanes such as TESPT, and vulcanization accelerators as described above and vulcanization agents, which crosslink with a functionality greater than four, as described in WO 2010/049261 A2, such as e.g. a vulcanizing agent according to formula A), as well as the Vulkuren®, Duralink® and Perkalink® systems are briefly designated as vulcanizing agents.
    [00127] The rubber mixture according to the present invention preferably contains at least one vulcanization agent selected from the group containing sulfur and / or sulfur donors and / or vulcanization accelerators and / or vulcanization agents, which remove with functionality greater than four. Therefore, vulcanized rubber products can be produced from the rubber mixture according to the present invention, particularly for use in automotive vehicle tires.
    [00128] The rubber mixture according to the present invention preferably contains at least one vulcanizing agent selected from the group consisting of sulfur and / or sulfur donors and / or vulcanization accelerators and / or vulcanizing agents, which crosslink with functionality greater than four. Therefore, vulcanized rubber products can be produced from the rubber mixture according to the present invention, particularly for use in automotive vehicle tires.
    [00129] In addition, the rubber mixture may also contain vulcanization retardants.
    [00130] In accordance with an advantageous improvement of the invention, several accelerators are used. A sulfamide accelerator, particularly preferably CBS, is preferred in combination with the DPG guanidine accelerator (diphenylguanidine). In this case the amount of DPG is from 0 phr to 5 phr, preferably from 0.1 phr to 3 phr, particularly preferably from 0.5 phr to 2.5 phr, more particularly preferably from 1 phr to 2.5 phr.
    [00131] Another objective of the present invention lies in the fact that it discloses a tire for automotive vehicles, characterized by an improved rolling resistance behavior and an improved abrasion wear behavior. This objective is achieved by the fact that the automotive vehicle tire contains the rubber mixture according to the present invention as described above in at least one component. In this case, all embodiments related to the components and the respective characteristics mentioned above are valid.
    [00132] Preferably, in the case of the component it is a tread. As is known to the person skilled in the art, the tread contributes to a relatively high part of the rolling resistance of the tire and to the abrasion of the tire.
    [00133] Furthermore, the invention also aims to optimize the wear behavior of tires for automotive vehicles and technical rubber articles, such as, for example. straps, belts and flexible tubes, without other significantly relevant properties for use being significantly negatively influenced.
    [00134] This objective is achieved by the use of the aforementioned rubber mixture for the production of tires for automotive vehicles, particularly for the production of a tire tread and / or a tire body mixture and for the production of rubber artifacts, such as e.g. straps, straps and flexible tubes. In this case, as a body mixture, rubber mixtures are designated for the internal components of a tire.
    [00135] As internal tire components are essentially designated the squeegee, the side wall, the inner web (inner layer), the nuclear profile, the strap, the shoulder, the strap profile, the carcass, the reinforcement of the bead , the bead profile and the connecting thread.
    [00136] The production of the rubber mixture according to the present invention is carried out according to the conventional process in the rubber industry, in which first a base mixture is produced with all components in addition to the vulcanization system. canization (sulfur and substances that influence vulcanization) in one or several mixing steps. The finished mixture is produced by adding the vulcanization system to the last mixing step. The finished mixture continues to be processed eg. by means of an extrusion procedure and is molded accordingly.
    [00137] For use in tires for automotive vehicles the mixture is preferably molded in the form of a tread and is applied during the production of the tire for raw automotive vehicles as known. However, the tread can also be rolled over a flat tire in the form of a thin rubber mixture strip. In the case of treads divided into two parts (upper part: cover and lower part: base) the rubber mixture according to the present invention can be used both for the cover and also for the base.
    [00138] The production of the rubber mixture according to the present invention for use as a body mixture in tires for automotive vehicles is carried out as described above for the tread. The difference lies in the molding after the extrusion procedure. The forms obtained in this way of the rubber mixture according to the present invention for one or more different body mixtures subsequently serve for the assembly of a flat tire. For the use of the rubber mixture according to the present invention in belts and belts, particularly in conveyor belts, the extruded mixture is molded correspondingly and simultaneously or subsequently frequently provided with reinforcements, e.g. synthetic fibers or steel strands. Therefore, a multilayer structure is generally generated, consisting of one and / or several layers of rubber mixture, one and / or several layers of equal and / or different reinforcements and one and / or several additional layers of the and / or another rubber mixture.
    [00139] For the use of the rubber mixture according to the present invention in flexible tubes, so-called sulfur crosslinking is not preferred, but a peroxide crosslinking is preferred. The production of flexible tubes is carried out according to the process described in the rubber technology manual, Dr. Gupta Verlag, 2001, chapter 13.4.
    [00140] Next, the invention is explained in more detail based on examples of realization and comparison, which are summarized in Tables 1 to 3. The mixtures marked with "E" are mixtures according to the present invention, while the mixtures marked with "V" are mixtures for comparison. In the case of the various mixing examples presented in the Table, the quantitative indications used are parts by weight, which refer to 100 parts by weight of total rubber (phr) or 100 parts by weight of silica (phf).
    [00141] The production of the mixture was carried out under conventional conditions in three stages in a laboratory tangential mixer. Samples of various mixtures were produced by optimal vulcanization under pressure at 160 ° C and with these samples the material properties typical of the rubber industry were determined. For the aforementioned tests of the samples the following test procedures were used:
    [00142]. Shore A hardness (Shore A unit, abbreviated ShA) at room temperature (TA) according to DIN 53 505
    [00143]. Return elasticity (abbreviated return) at room temperature (RT) and 70 ° C according to DIN 53 512
    [00144]. Stress values at elongation of 50%, 100% and 300% (module 50, module 100 or module 300 at room temperature (TA) according to DIN 53 504
    [00145]. Tensile strength and elongation at ambient temperature according to DIN 53 504
    [00146]. Abrasion wear at room temperature according to DIN 53 516 or DIN ISO 4649
    [00147]. Glass transition temperature Tg of the rubber mixture from the tan δ loss factor (delta tangens) from the dynamic-mechanical measurement according to DIN 53 513 (temperature sweep, temperature sweep).
    [00148] The determination of the molar mass (average weight molar mass Mw and numerical average molar mass Mn) of the polymers was performed by means of gel permeation chromatography (GPC with tetrahydrofuran (THF) as eluant at 40 ° C , calibrated with EasiCal PS-1 standard polystyrene; molecular exclusion chromatography by size; ing. SEC = size exclusion chromatography). The determination of Mooney viscosities (ML 1 + 4, 100 ° C) of the polymers used was carried out in accordance with the ASTM D 1646 (2004) standard. Table 1
    Substances used in Table 1:
    [00149] a) BR: polybutadiene, high cis, N-catalyzed butadiene rubber, non-functionalized, Tg = -105 ° C, Europrene® NEOCIS BR 40, Polimeri firm
    [00150] b) SSBR: styrene content = 10.4% by weight; vinyl proportion = 8.6% by weight; block styrene content = 5%; Tg = -83 ° C; Mw = 515249 g / mol; Mn = 356031 g / mol; Mooney viscosity = 64.1; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3
    [00151] c) SSBR: styrene content = 10.5% by weight; vinyl proportion = 8.8% by weight; block styrene content = 9%; Tg = -83 ° C; Mw = 475141 g / mol; Mn = 343274 g / mol; Mooney viscosity = 65.5; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3 and V) (MeO) 3Si- (CH2) 2-S-SiMe2C (Me) 3
    [00152] d) SSBR: styrene content = 0% by weight; proportion of wine = 8% by weight; Tg = -94 ° C; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3 and V) (MeO) 3Si- (CH2) 2-S-SiMe2C (Me) 3
    [00153] e) Silica: ULTRASIL® VN3, Evonik firm
    [00154] f) Silane Si 261®, Evonik firm
    [00155] g) Accelerator: DPG (diphenylguanidine) and CBS (N-cyclohexyl-2-benzothiazolsufenamide)
    [00156] As is evident in Table 1, the rubber mixtures E1, E2 and E3 according to the present invention surprisingly show a higher return elasticity at 70 ° C than V1, although the glass transition temperatures Tg of E1 , E2 and E3 respectively are higher than those of V1. Higher return elasticity at 70 ° C is an indicator of improved rolling resistance behavior. At the same time, the remaining physical properties remain at approximately the same level. Therefore, with the rubber mixture according to the present invention due to the use in the tread it is possible to further improve the rolling resistance of tires for automotive vehicles based on the state of the art without this implying a worsening of the other properties of the tire . Table 2

    Substances used in Table 2:
    [00157] a) SSBR: styrene content = 21% by weight; proportion of villa = approx. 61% by weight, Tg = -25 ° C, functionalized with hydroxyl groups, Nipol® NS 616, Nippon Zeon
    [00158] b) SSBR: styrene content = 15% by weight, proportion of vinyl = approx. 25% by weight, Tg = -65 ° C, functionalized with hydroxyl groups, Nipol® NS 612, Nippon Zeon
    [00159] c) SSBR: styrene content = 10.4% by weight; vinyl proportion = 8.6% by weight; block styrene content = 5%; Tg = -83 ° C; Mw = 515249 g / mol; Mn = 356031 g / mol; Mooney viscosity = 64.1; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3
    [00160] d) SSBR: styrene content = 10.5% by weight; vinyl proportion = 8.8% by weight; block styrene content = 9%; Tg = -83 ° C; Mw = 475141 g / mol; Mn = 343274 g / mol; Mooney viscosity = 65.5; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3 and V) (MeO) 3Si- (CH2) 2-S-SiMe2C (Me) 3
    [00161] e) SSBR: styrene content = 0% by weight; proportion of wine = 8% by weight; Tg = -94 ° C; modified with IV) (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3 and V) (MeO) 3Si- (CH2) 2-S-SiMe2C (Me) 3
    [00162] f) Silica: ULTRASIL® VN3, Evonik firm
    [00163] g) Si 261® silane, Evonik firm
    [00164] h) Accelerator: DPG (diphenylguanidine) and CBS
    [00165] As shown in Table 2, the rubber mixes E4, E5 and E6 at the same glass transition temperature (of the rubber mix) as the respective comparison mix V2 have improved abrasion wear and rolling resistance properties (see return elasticities at 70 ° C). Therefore, due to the targeted combination of the functionalized styrene butadiene rubber with a styrene content from 0% by weight to 12% by weight and a glass transition temperature of -120 ° C to -75 ° C and rubbers with a temperature of relatively high glass transition (high TBR SSBR) in the rubber mixtures according to the present invention it is possible to increase the proportion of high Tg rubber and therefore simultaneously improve the abrasion wear and rolling resistance properties of the mixture rubber. At the same time, the remaining physical properties remain at approximately the same level.
    权利要求:
    Claims (10)
    [0001]
    1. Mixture of crosslinkable rubber with sulfur, characterized by the fact that it comprises at least the following components: - from 5 phr to 95 phr of at least one butadiene stretch rubber, which is functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups and whose styrene content is from 0% by weight to 12% by weight and which in the non-vulcanized state has a glass transition temperature (Tg) of -75 ° C to -120 ° C according to the DSC method, and - from 5 phr to 95 phr of at least one additional rubber, and - from 20 phr to 300 phr of at least one silica.
    [0002]
    Mixture of sulfur-crosslinkable rubber according to claim 1, characterized from 5 phr to 20 phr of natural polyisoprene and / or 5 phr to 20 phr of synthetic polyisoprene.
    [0003]
    3. Mixture of crosslinkable rubber with sulfur, according to claim 1 or 2, characterized by the fact that the styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with sulfide groups silane has a vinyl proportion of 7% by weight to 12% by weight.
    [0004]
    4. Mixture of cross-linked rubber with sulfur, according to any one of claims 1 to 3, characterized by the fact that it contains from 10 phr to 70 phr of a functionalized styrene butadiene rubber with a Tg of -75 ° C to -120 ° C, and 10 phr to 70 phr of a styrene butadiene rubber polymerized in solution with a Tg of -40 ° C to +10 ° C, functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulphide groups.
    [0005]
    5. Mixture of crosslinkable rubber with sulfur, according to claim 4, characterized by the fact that the functionalized styrene butadiene rubber is functionalized with a Tg of -75 ° C to -120 ° C with silane sulfide groups.
    [0006]
    Mixture of sulfur-crosslinkable rubber according to any one of claims 1 to 4, characterized in that the styrene butadiene rubber functionalized with phthalocyanine groups and / or with hydroxyl groups and / or with epoxy groups and / or with silane sulfide groups it has a glass transition temperature (Tg) of -80 ° C to -110 ° C, according to the DSC method.
    [0007]
    7. Automotive vehicle tire, characterized by the fact that it contains a mixture of crosslinkable rubber with sulfur, as defined in any one of claims 1 to 6, in at least one component.
    [0008]
    8. Tire for automotive vehicles, according to claim 7, characterized by the fact that the component is a tread and / or a sidewall.
    [0009]
    9. Use of a rubber mixture, as defined in any of claims 1 to 6, characterized by the fact that for the production of a tire for automotive vehicles.
    [0010]
    10. Use of a rubber mixture, as defined in any one of claims 1 to 6, characterized by the fact that it is for the production of a belt, a belt or a flexible tube.
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    同族专利:
    公开号 | 公开日
    ES2612554T3|2017-05-17|
    US9856368B2|2018-01-02|
    CN105579507B|2017-09-08|
    EP2853558B1|2016-11-09|
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    US20160194485A1|2016-07-07|
    WO2015043902A1|2015-04-02|
    CN105579507A|2016-05-11|
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    法律状态:
    2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-10-06| B09A| Decision: intention to grant|
    2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13186373.0|2013-09-27|
    EP13186373.0A|EP2853558B1|2013-09-27|2013-09-27|Sulfur crosslinkable rubber composition|
    PCT/EP2014/068786|WO2015043902A1|2013-09-27|2014-09-04|Sulfur-crosslinkable rubber mixture|
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