DE102007042496A1 - Producing a vulcanizable rubber mixture, e.g. for tire treads, comprises dispersing a modified phyllosilicate filler in a polar rubber and mixing the resulting masterbatch with another rubber - Google Patents

Abstract

Producing a vulcanizable rubber mixture containing a modified phyllosilicate filler in an amount of up to 100 parts per hundred parts rubber comprises dispersing the filler in a polar rubber and mixing the resulting masterbatch with another rubber. Independent claims are also included for: (1) rubber mixture produced as above; (2) motor vehicle tire tread produced with the rubber mixture; (3) motor vehicle tire with a tread produced with the rubber mixture; (4) drive belt, seal and air spring produced using the rubber mixture.

Description

The Invention relates to rubber blends with layered silicate fillers, as for example for the Manufacture of vehicle tires or other technical rubber products can be applied and a process for their preparation and from the rubber products manufactured products.

modern Rubber products such as vehicle tires, drive belts and air springs represent technically very mature composite moldings, which consist of several Individual components with different physical properties and mix different formulations. there must be this composite body different, often contradictory requirements of which e.g. for tires as essential features possible low rolling resistance, i. low hysteresis, as high as possible Wet-slip resistance, i. high hysteresis and one possible high output strength, i. high strength and elongation at break, are known. Complicating the solution of this optimization the influence of material independent Factors such as internal air pressure, road surface roughness, Tread pattern, etc.

So suffice Rubber compounds suitable for Tire inner rubbers (main task: gas impermeability) are used i. A. does not meet the requirements for rubber compounds of tire treads be put. So have to the for Tire treads used rubber blends an optimization the mature. with regard to z. B downforce, sliding behavior, rolling resistance, Heat Build Up, Tear Resistance and allow cold flexibility. With treads, above all, a high slip resistance and a good grip when driving temperatures required. This high skid resistance can be achieved by increasing the Loss factor tan δ im relevant temperature range z. B. by the mixing of large amounts (> 100 phr) of high-energy dissipative carbon blacks, so-called racing blacks, respectively. Furthermore, it is advantageous if the tires are in driving operation present temperature range have the lowest possible Shore hardness.

It has not yet succeeded, the three material properties in so-called "magical Triangle of tire technology "independently to adjust to a maximum achievable Ni level, as two in each case The three main characteristics reciprocally coupled with each other seem to be.

The Properties of such elastomeric material from rubber compounds hang crucial from the micro and macro structure of the polymer network building network chains and the structure of the network. there These structures are inter alia of the type of networking, the Crosslinking density and the type, amount and dispersion of fillers and plasticizers, with technologically interesting material combinations can only be achieved by the addition of these additives.

seals which contain a vulcanized rubber mixture are in the different areas, such. B. the vehicle, the apparatus construction, in the home appliance industry and the Control technology used. They seal and / or encapsulate z. B. from against soiling and against the escape of fats and oils or serve as partitions and pressure intensifier in containers or devices with different pressures and / or different media. To accomplish this task there it seals in various forms, eg. B. as bellows, bellows, caps, Plugs, hose rings, sleeves, sealing rings, sealing membranes, Plates and tracks.

Drive belt, which contain a vulcanized rubber mixture are in the different areas, such. B. the vehicle, the apparatus construction, in the home appliance industry and the Materials handling, used and drive there a wide variety of aggregates. In order to optimally fulfill the required tasks, there are various Shapes of drive belts such. B. Timing belt, V-belt, V-ribbed belt and flat belts.

Also for technical rubber articles e.g. Transporters will be the different ones Requirements taken into consideration by design and selection of materials. Related to the elastomeric materials, the object is here with each other linked and opposing Optimize material properties. High wear resistance and tear propagation resistance and low energy dissipation under dynamic loading Products with high durability, with low energy consumption to operate.

Rubber mixtures are a variety of fillers, such. For example, carbon black, silica, aluminosilicates, kaolins, metal oxides or chalk added. The fillers not only contribute to the cheapening of rubber compounds, but also influence the egg due to their specific effect on the rubber properties of the unvulcanised rubber compound and the vulcanizates, the elastomers. Active fillers, also called reinforcing fillers, which include most of the carbon blacks, silica and most particulate silicates, generally improve a range of vulcanizate properties, such as tensile strength, modulus and tear resistance, while other properties, such as elongation at break and rebound resilience, are negative to be influenced. The activity of the filler is dependent on the particle size, the specific surface, the geometric shape of the surface and the chemical composition.

Usually Elastomer blends are high levels of silica and / or carbon black on filler for improving the strength and abrasion resistance, in particular for car tires, added.

It is known after the DE 100 14 664 A1 a sulfur-crosslinkable rubber mixture and crosslinked rubber mixtures and moldings obtainable therefrom which contain at least one diene polymer or copolymer, at least one finely divided acid-activated phyllosilicate as reinforcing filler and at least one coupler with groups reactive with the filler and by vulcanization at temperatures of more than 10 ° C, usually 160 ° C, are produced.

When fillers can smectic phyllosilicates, such as montmorillonite, or mixtures thereof, after previous acid activation be used. These phyllosilicates have a mica-like Three-layer structure with two tetrahedral layers and one in between lying octahedral layer. Between the negatively charged phyllosilicates are the interchangeable ones Interlayer cations (lithium, sodium, potassium, magnesium and / or Calcium). Characteristic of Most of the minerals in this group are cation exchange and the ability for intracrystalline swelling. The known phyllosilicates form a Füllstoffklasse, the phyllosilicates are not due to their polar surface with conventional Rubbers are compatible. Therefore, they must be modified before use be known by the hydrophilic surface the phyllosilicates by cation exchange with alkylammonium ions becomes organophilic. At the same time, organic molecules (predominantly quaternary Ammonium compounds) between the layers of silicates, so that the phyllosilicates form expanded stacks, in which between the silicate single layers the organic modifiers are stored.

Is known from the DE 100 59 236 B4 the use of a rubber composition for tire treads, wherein the rubber mixture of diene rubber used with fillers, plasticizers and other conventional additives, wherein 5 to 90 phr of phyllosilicates are included. These phyllosilicates are modified with alkylammonium ions and are free from swollen or polymerized guest molecules.

Out Such organically modified phyllosilicates can be Nanocomposites of polymers and phyllosilicates produce. A nanocomposite is defined as an interactive mixture of two phases, in this case polymer / organic phase and phyllosilicate / inorganic Phase, of which one phase is at least one dimension in the Magnitude a few nanometers.

An overview of nanocomposites based on polymers and phyllosilicates, their preparation, characterization and use can be found for. In the article "Polymer layered silicate naonocomposites" by M. Zanetti, S. Lomakin and G. Camino in Macromol. Mater. Closely. 279, pp. 1-9 ,

For the production of nanocomposites based on polymers and phyllosilicates Several methods are presented there: in situ polymerization, the intercalation of the polymer from a solution and direct incorporation of molten polymer. This procedure to lead that the individual layers of silicate be widened and possibly even completely leafed apart (exfoliated). The individual layers have a thickness of about 1 nm and are surrounded by polymer. The presence of nanocomposites in polymer materials it, the polymer products made therefrom with new and improved Equip features. The concept of nanocomposite based of phyllosilicates is mainly used in the field of thermoplastics used to their properties z. B. in terms of tensile strength to improve. For Thermoplastics are the four processes mentioned for the production of Nanocomposites applicable, whereas for rubbers the direct incorporation of the molten polymer due to the high viscosities in the conventional Processing temperature range is not possible. The other three Procedures are also for Rubber applicable, however, these processes are technological very expensive and always with the use of solvents connected in the further course of processing such nanocomposites z. For example the interference in a vulcanizable rubber mixture again i. A. complete must be removed.

Of the Use of phyllosilicates as nanoscale filler in elastomers leaves good reinforcing properties due to the high aspect ratio and the big one surface the phyllosilicates expect. However, the dispersion has followed exfoliation of the individual layers of the phyllosilicates or an intercalation of the polymer chains between the layer stacks in nonpolar rubbers due to lack of compatibility between Polymer and phyllosilicate not possible. This also applies to known modified phyllosilicates.

Around To achieve improved results here are different methods known.

Elastomer composites based on SBR and BR are produced by solution intercalation method. ( M. Ganter, et al., RCT 74 (2001) 221 ; S. Sadhu, et al., JAPS 92 (2004) 698 ). Y. Wang et al., JAPS 78 (2000) 1879 , compare the solution and emulsion intercalation for the production of SBR nanocomposites. KH Wie, et al., Polymer Engineering and Science (2006) 80 employ carboxylic acid-terminated butadiene oligomers as compatibilizers in polybutadiene rubber and show intercalated and partially exfoliated structures of the layered silicates in the polymer matrix.

task The present invention is rubber blends for elastomers with modified phyllosilicate fillers, in which the phyllosilicates are present in high concentration and well dispersed, these elastomer mixtures in a simple and inexpensive way and are producible.

The Invention is solved by the invention specified in the claims. advantageous Embodiments are the subject of the dependent claims.

The used in this specification phr (parts per hundred parts of rubber by weight) is the usual quantity in the rubber industry for mixtures. The dosage of the parts by weight of the individual substances is thereby always to 100 parts by weight of the total mass of all in the mixture related rubbers.

at the rubber mixtures of the invention and elastomer blends with modified layered silicate fillers are at least modified phyllosilicates in a first polar Rubber dispersed and are connected to the polar rubber before and these are together as a masterbatch with a second rubber mixed, with a maximum of 100 phr, preferably a maximum of 50 phr modified Layered silicates are included in the total mixture.

With the expression "lie connected with the rubber before "is In this case, it is meant that the phyllosilicates and the rubber via covalent and non-covalent bonds can be linked together.

advantageously, are up to 35 phr, like up to 15 phr modified phyllosilicates with quaternary Alkyl ammonium compounds modified montmorillonites used.

Farther is advantageously carboxylated as the first polar rubber Nitrile rubber XNBR, XHNBR or other carboxylated rubbers, Chloroprene CR, NBR, HNBR, AEM, HNR Halonitrile rubber, CM Chlorinated Polyethylene, CSM chlorosulfonated polyethylene, ACM acrylate rubber, EVA ethylene-vinyl acetate copolymer, FPM fluororubbers, MQ methyl silicone rubbers, MVQ vinyl silicone rubber, MPQ phenyl silicone rubber, MFQ polyfluorosilicone, MPVQ phenyl-vinyl-silicone rubber, AU, EU polyester-polyisocyanate prepolymers, CO, ECO epichlorohydrin rubber, TM polysulfide rubbers used.

From It is also an advantage if the second rubber is one with less polarity as the first rubber is used. So can styrene-butadiene polymer SBR, butadiene polymer BR, (poly) isoprene polymer IR, natural rubber NR, ethylene-propylene-diene rubber EPDM and / or Butadiene-styrene-isoprene copolymer used, the use However, the above-mentioned polar rubbers is also possible. at HNBR and NBR is e.g. the polarity by the ACN content (18-43 % By weight), so that here as the first rubber a polymer chosen with high ACN content and, as the second rubber, a low ACN content.

That is, the vulcanizable rubber mixture can be used as rubber components all known to those skilled in rubber types, such as. Natural rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer, butyl rubber, ethylene-propylene-diene rubber (EPDM), ethylene-propylene copolymer. It is preferred if the rubber mixture as the first rubber component at least one rubber with polar groups such as acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber Schuk (HNBR), hydrogenated acrylonitrile-butadiene rubber having side groups for improved low-temperature flexibility, carboxylated acrylonitrile-butadiene rubber XNBR, styrene-butadiene copolymers and graft polymers with other unsaturated polar monomers, silicone rubber, ethylene-vinyl acetate rubber, ethylene-acrylic Elastomers, rubbers having halogen atoms such as chloroprene rubber, fluororubber, epichlorohydrin rubber, alkylated chlorosulfonated polyethylene, chlorosulfonated polyethylene, chlorinated polyethylene.

It It has been shown that rubbers containing polar groups exfoliate and the attachment of the modified layered silicate to the rubber promote. additionally The rubbers with polar groups are characterized by a high resistance against oils and many chemicals out.

Preferably the rubbers with the polar groups are carboxylated Acrylonitrile butadiene rubber or chloroprene rubber. Next the resistance against oils and chemicals are characterized by its especially chloroprene rubber high abrasion resistance out. Carboxylated acrylonitrile-butadiene rubber additionally has good aging behavior and high hot air resistance.

In a preferred embodiment the second rubber is a nonpolar rubber. Preferred rubbers are: styrene-butadiene polymer SBR, butadiene polymer BR, natural rubber NR, ethylene-propylene-diene rubber EPDM and / or butadiene-styrene-isoprene copolymer. that is, It is according to the invention possible, Elastomer blends based on nonpolar rubbers with modified Layer silicate fillers indicate that the Schichtsili kate in high concentrations and well dispersed in nonpolar rubbers. In a another embodiment the second rubber is also a polar rubber, like one with a lower polarity as the first rubber, preferably one of the abovementioned type.

Also it is advantageous if 5-30 phr (parts per hundred parts of rubber) mixed with masterbatch in the second rubber.

Also It is advantageous if the associated with the polar rubber modified phyllosilicates statistically distributed in the second Rubber present.

The mixtures according to the invention also show the advantages on it being vulcanized by the presence the thin one Tile of the layered silicate have a good barrier effect for gases and liquids and a high resistance have against a wide variety of organic media. Additionally own the vulcanizates a good flame resistance.

The very thin Tile of the exfoliated phyllosilicate depend on the processing the mixture of (directional effect, anisotropy) and cause a two-dimensional Gain. The vulcanizate assumes anisotropic properties. With conventional, unmodified phyllosilicates may be such a two-dimensional reinforcement can hardly be achieved because the individual layers of silicate are not be exfoliated, but as larger accumulations present in the mixture.

By the solution according to the invention is it possible for the first time modified phyllosilicates as fillers finely distributed in one To obtain rubber, in particular a non-polar rubber. For this are the organically modified phyllosilicates in a polar Gum mixed and well distributed in the polar rubber. The masterbatch thus prepared is then in the second rubber mixed. Thus, the modified layered silicate in the entire rubber mixture finely distributed. The rubber mixture according to the invention has good physical and chemical properties. The mixing is so good that, for example, significantly increased strength values of the total mixture can be achieved.

The Inventive rubber mixture may be 1 to 100 phr modified layered silicate, wherein high amounts are used especially if one low Gas permeability the vulcanizate is sought. However, it is particularly preferred if the rubber mixture contains 2 to 25 phr of the phyllosilicate, because even these small amounts are sufficient in interaction with the co-networker, to vulcanizates with high level of voltage value, tear propagation resistance and elongation at break to obtain other desired ones Vulkanisateigenschaften also not be degraded.

Modified phyllosilicates used are those silicates whose layer stacks have been expanded by prior treatment, for example by organic modification with quaternary ammonium alkyl compounds. The surfaces of the thus treated sheet silicates are still un polar. However, this non-polarity is not sufficient to such phyllosilicates with conventional methods in z. B. introduce nonpolar but also polar rubber compounds and to disperse evenly. Only with the inventive solution, this is possible.

Advantageous It is also when other known additives and adjuvants the rubber mixtures be added.

So the rubber mixture can be used as further fillers z. B. finely divided, precipitated silica, Soot, aluminum oxides, Aluminosilicates, chalk, starch, Magnesium oxide, titanium dioxide or rubber gels. The total salary on filler can be up to 150 phr. Also short fibers z. As polyamide, Aramid or polyester can be added to the rubber mixture.

Furthermore, the rubber mixture according to the invention may contain customary additives in customary parts by weight. These additives include anti-aging agents, such as. N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine (6PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1, 2-dihydroquinoline (TMQ), zinc salts of 4- and 5-methylmercaptobenzimidazole and other substances such as, for example J. Schnetger, Encyclopedia of Rubber Technology, 2nd edition, Hüthig Book Verlag, Heidelberg, 1991, pp. 42-48 are known, silane coupling agents such. As organosilane polysulfides having two to eight sulfur atoms and vinyl silanes, processing aids and plasticizers such. As zinc oxide, fatty acids such as stearic acid, aromatic, naphthenic and / or paraffinic process oils, rapeseed oil and waxes, mastication aids such. B. 2,2'-Dibenzamidodiphenyldisulfid (DBD), flame retardants and lubricants.

Prefers will be at least one silane coupling agent with the modified layered silicate and the rubber, e.g. in situ. This leads to special good properties, e.g. the 100% modulus and other tensile and fracture parameters.

Becomes vulcanization in the presence of sulfur or sulfur donors, d. H. with a sulfur-based crosslinking system, wherein as sulfur donors, for example, thiuram derivatives such as tetrabenzylthiuram disulfide and dipentamethylene thiuram tetrasulfide, morpholine derivatives such as dimorpholyl disulfide, Dimorpholyl tetrasulfide and 2-morpholinodithiobenzothiazole As well as caprolactam disulfide can be used, the rubber mixture furthermore vulcanization-influencing substances such as vulcanization accelerators, vulcanization and vulcanization activators in conventional amounts to the required time and / or the required temperature of the To control vulcanization and the vulcanizate properties too improve. The vulcanization accelerators can be selected, for example from the following accelerator groups: thiazole accelerators such. B. 2-mercaptobenzothiazole, sulfenamide accelerators such as. B. benzothiazyl-2-cyclohexylsulfenamide, Guanidine accelerators such. B. diphenylguanidine, thiuram accelerator such as B. tetramethylthiuram disulfide, dithiocarbamate accelerator such as As Zinkdibenzyldithiocarbamat, amine accelerators such. B. Cyclohexylethylamine, thioureas such. B. ethylene thiourea (ETU), xanthate accelerators, disulfides. The accelerators can also be used in combination with each other, being synergistic Effects can result.

at the method according to the invention for the preparation of rubber mixtures with modified phyllosilicate fillers be at least modified phyllosilicates in a polar Rubber is mixed and dispersed therein and subsequently the modified layered silicate dispersed in the polar rubber together as a masterbatch a second, preferably nonpolar rubber admixed with the amount of modified layered silicate in the Total rubber mixture does not exceed 50 phr.

advantageously, be up to 50 phr, such as. B. up to 35 phr, such as up to 15 phr, z. B. 5 phr modified phyllosilicates mixed into the total mixture.

Also Advantageously, the admixture of the modified phyllosilicates at temperatures above the melting temperature of the first polar Rubbers and below the decomposition temperature of the modified Layered silicates performed.

Advantageous It is also when the masterbatch is in an amount of 5-30 phr (parts per hundred parts of rubber) is added.

It is also advantageous if the admixture of the masterbatch to the second rubber at temperatures above the melting temperature of the second rubber and below the decomposition temperatures perature of the masterbatch.

Also It is advantageous if the mixtures are produced in an internal mixer become.

And it is also advantageous if further known additional and Excipients for the masterbatch and / or the masterbatch rubber mixture be added.

Become now such modified phyllosilicates in a polar rubber mixed, so finds a good dispersion, advantageously a statistical distribution of modified phyllosilicates in polar rubber instead. Furthermore, network chains can be polar Rubber in the interstices the individual sheet silicates in the expanded sheet silicate stacks penetrate and thus further increase the layer spacing. This will on the one hand a good dispersion of the modified phyllosilicates in the reached polar rubber. This rubber compound with maximum 100 phr of modified phyllosilicates is hereinafter referred to as masterbatch for producing a rubber mixture with a second rubber used. It will be advantageous up to 30 phr of masterbatch second rubber added.

The good mixture of these two components is achieved by that now the modified phyllosilicate in the masterbatch as a compatibilizer between the different rubbers in the composite acts. In a preparation according to the invention of the nanocomposite, portions of the polar rubber thus always remain in the final product, by the compatibilizing effect of the phyllosilicate However, this does not have a detrimental effect, but it can be so even the strength of the composite can be increased.

During the overall preparation of the phyllosilicate rubber nanocomposite will therefore be neither additional Chemicals still solvent introduced into the mixture. The NanoClay masterbatch can be sold separately be produced and used in the production process or together mixed with other fillers be without an additional Process step needed would.

The rubber mixtures according to the invention can for the Production of a wide variety of products can be used. For example, vehicle tires, drive belts, hoses, air springs, elastomer-coated fabrics, vibration dampers, conveyor belts, gaskets, Called membranes and cuffs.

at the use of the rubber mixtures according to the invention in tires, the second rubber is a nonpolar rubber, in particular SBR, NR or BR used. The with the aid of the rubber mixtures according to the invention available Tires have good stiffness and abrasion resistance with good rolling resistance and handling. Furthermore, the show Tires good wet brake properties.

following the invention is based on embodiments explained in more detail.

there demonstrate

1 Tensile test on a sample of the layered silicate nanocomposite in comparison with the unreinforced starting materials

2 : 100% modulus of the elastomer blends with different masterbatch contents compared to the unreinforced starting materials

3 : 200% modulus of the elastomer blends with different masterbatch contents compared to the unreinforced starting materials

4 : 300% modulus of the elastomer blends with different masterbatch grades compared to the unreinforced starting materials

5 : Influence of the phyllosilicate content of the sample on its tensile strength.

6 : 6 shows G "for various rubber compounds shown in Table 3.

7 : 7 represents the G 'for various rubber compounds shown in Table 3.

8th : 8th shows tan δ for various rubber compounds shown in Table 3.

Example 1:

In an internal mixer (Haake Rheomix R600p) were at a temperature of 160 ° C and a speed of 50 rpm different proportions (10-60 phr) of organically modified with Distearyldimethylammoniumionen phyllosilicate Montmorillonite (Nanofil 15, Südchemie) in carboxylated nitrile rubber (XNBR, Lanxess Krynac X740).

The mixing ratios are listed in Table 1. Table 1: Mixing instructions for the XNBR masterbatch masterbatch Share XNBR Proportion of nanofilts 15 [G] [G] M-30 100 30 M-40 100 40 M-50 100 50 M-60 100 60

Of the resulting masterbatch of polar XNBR was on a rolling mill (Servitec Polymix 110L) along with the crosslinking chemicals Zinc oxide, stearic acid, Vulcacite CZ (CBS), Vulcacite D (DPG), sulfur in non-polar S-SBR (Lanxess) incorporated.

The mixing ratios are listed in Table 2: Table 2: Mixing instructions for nanocomposites mix number proportion of proportion of Share masterbatch S-SBR XNBR M-30 M-40 M-50 M-60 Zn stearin DPG CBS sulfur [G] [G] [G] [G] [G] O [G] [G] [G] [G] [G] Acid [g] SB-1 100 - 5 - - - 3 2 2 1.7 1.4 SB-2 100 - 10 - - - 3 2 2 1.7 1.4 SB-3 100 - 15 - - - 3 2 2 1.7 1.4 SB-4 100 - - 5 - - 3 2 2 1.7 1.4 SB-5 100 - - 10 - - 3 2 2 1.7 1.4 SB-5 100 - - 15 - - 3 2 2 1.7 1.4 SB-6 100 - - - - - 3 2 2 1.7 1.4 SB-7 100 - - - 5 - 3 2 2 1.7 1.4 SB-8 100 - - - 10 - 3 2 2 1.7 1.4 SB-9 100 - - - 15 - 3 2 2 1.7 1.4 SB-10 100 - - - - 5 3 2 2 1.7 1.4 SB-11 100 - - - - 10 3 2 2 1.7 1.4 SB-12 100 - - - - 15 3 2 2 1.7 1.4 SB-13 100 - - - - 20 3 2 2 1.7 1.4 SB-14 100 - - - - 30 3 2 2 1.7 1.4 SB-15 100 9:37 - - - - 3 2 2 1.7 1.4 SB-16 100 18.75 - - - - 3 2 2 1.7 1.4 SB-00 100 - - - - - 3 2 2 1.7 1.4 XNBR 00 - - - - - 3 2 2 1.7 1.4

In tensile tests, a good reinforcement of the elastomer mixture was found (see 1 - 4 ). The results of the tensile test are further shown in Table 3.

It it can be seen that from a total content of about 5 phr phyllosilicates no further reinforcement can be achieved. This proportion of modified phyllosilicates in the overall mix thus provides an optimum of gain in the System S-SBR / XNBR / Nanofil 15 represents.

Out the tensile test shows that without phyllosilicate admixture no synergistic Effects of mixing polar (XNBR) and nonpolar elastomer (S-SBR); the phyllosilicate introduced by the NanoClay XNBR masterbatch Apparently works as a compatibilizer in this mixture.

A comparison of the data shown in Table 3 for SB-00 and SB-15 shows a small improvement in tensile strength by addition of XNBR, the lowering of the 100% modulus and the 300% modulus do not affect the dynamic mechanical behavior. Table 4: Comparison of the properties of rubbers according to the invention with reference examples: SB-00 SB-15 SB-12 G "(0 ° C) (MPa) tan δ (60 ° C) Tg (G" _max ) (° C) G '(0 ° C) (MPa) 5.85 x 10 ⁵ 0.03 -19 1.94 x 10 ⁶ 6.57 x 10 ⁵ 0.04 -21.2 2.71 x 10 ⁶ 1.1 x 10 ⁶ 0.06 -20 3.81 x 10 ⁶

In contrast, a comparison of SB-12 and SB-15 shows a significant increase of σ 100% by 30% with a simultaneous increase of σ _B and ε _B. Usually, with increasing modulus σ 100%, the breaking strength and breaking elongation decrease markedly, but not so in the case of the mixtures according to the invention. This remaining high breaking strength is advantageous for abrasion, while the remaining high rigidity is advantageous for handling. It will continue to be seen in the comparisons between SB-12 and SB-15 from the graphs of G '', G 'and tan δ, see 6 to 8th , it is clear that the G '' value at T = 0 ° C is 15% higher with the same T _G without significant impairment of the tan δ at 60 ° C. These properties are particularly good for wet braking while the rolling resistance is not adversely affected.

Also in polar rubbers is achieved by the use of the polar masterbatch, the exfoliation favors. This can lead to a more effective filler network. a slight decrease in the ultimate strength and significant Increase in voltage values at low strains is observed. requirement for The high mechanical value level is the formation of a strong Polymer-filler interaction. Contribute to this, e.g. the carboxylate groups of the polymer in the masterbatch, the in-situ silanization of the excess, free hydroxyl groups of the filler and the resin system used, with the quaternary ammonium compounds used can react. This can explain that the material according to the invention i. A. opposing Material properties such as high reinforcement and high elongation at break or high tear propagation resistance and high elasticity combined together.

Thus, these materials are also well suited for conveyor belts and drive belts (wear resistance). In addition, with air springs and slugs, another side effect can be used meaningfully: The permeation of gases depends essentially on the degree of exfoliation and the orientation of the layer silicates, so that these materials in addition to the higher mechanical value level have a lower permeation to volatile substances.

Claims (28)

Vulcanisable rubber mixture containing modified phyllosilicate fillers, this rubber mixture comprising at least two different rubbers in which at least modified Phyllosilicates dispersed in a first polar rubber and combined with the polar rubber are present to form a masterbatch and this masterbatch is mixed with a second rubber, wherein a maximum of 100 phr, preferably not more than 50 phr of modified phyllosilicates are contained in the overall mixture. Vulcanisable rubber mixture according to claim 1, in the modified to 3 phr modified phyllosilicates are dispersed. Rubber mixture according to one of claims 1 or 2, when modified as layered silicates with quaternary alkyl ammonium compounds modified montmorillonites are used. Rubber mixture according to one of claims 1 to 3, in which the first polar rubber is a carboxylated rubber nitrile rubber XNBR, XHNBR, XSBR, or NBR or chloroprene CR. Rubber mixture according to one of claims 1 to 4, in which as the second rubber (poly) chloroprene CR, styrene-butadiene polymer SBR, butadiene polymer BR, (poly) isoprene polymer IR, natural rubber NR, HNBR, ethylene-propylene-diene rubber EPDM and / or butadiene-styrene-isoprene copolymer is used. Rubber mixture according to one of claims 1 to 5, which have 5-30 phr of masterbatch. Rubber mixture according to one of claims 1 to 6, in which the modified with the first polar rubber associated Layer silicates randomly distributed in the second rubber. Rubber mixture according to one of claims 1 to 7 in which further known additives and auxiliaries of the rubber mixture are added. Rubber mixture according to one of claims 1 to 8, in which the first polar rubber is a carboxylated nitrile rubber and the second rubber is a chloroprene rubber CR. Rubber mixture according to one of claims 1 to 8, in which the first polar rubber is carboxylated nitrile rubber XNBR and the second rubber is a nonpolar rubber. A rubber according to claim 10, wherein the second nonpolar Rubber is a styrene-butadiene rubber SBR, or an ethylene-propylene-diene rubber is EPDM. Rubber mixture according to one of claims 1 to 8, in which the first polar rubber is carboxylated hydrogenated Nitrile rubber XHNBR and the second rubber is HNBR rubber or an EPDM rubber. Process for the preparation of vulcanizable rubber mixtures with modified phyllosilicate fillers in which at least modified phyllosilicates mixed into a first polar rubber and be dispersed therein and in a subsequent second step the layered silicate dispersed and modified in the polar rubber is added as a masterbatch a second rubber, wherein the amount on modified layered silicate in the total rubber mixture a Value does not exceed 100 phr, in particular 50 phr. The method of claim 13, wherein 1 to 35 phr modified phyllosilicates based on the amount of total rubber be mixed. Method according to one of claims 13 or 14, in which the Admixture of the modified sheet silicates at temperatures above the melting temperature of the first polar rubber and below the Decomposition temperature of the modified phyllosilicates is performed. A method according to any one of claims 13 to 15, wherein the Masterbatch is added in an amount of 5-30 phr. A method according to any one of claims 13 to 16, wherein admixing the masterbatch to the second rubber at temperatures above the melting temperature of the second rubber and below the second rubber Decomposition temperature of the masterbatch is performed. Method according to one of claims 13 to 17, in which the Mixtures are prepared in an internal mixer. Method according to one of claims 13 to 18, the further known additives and auxiliaries for masterbatch and / or for mixing of masterbatch and second rubber. Tread for a vehicle tire made using a rubber compound according to one of the claims 1 to 12. Vehicle tires, in particular a pneumatic vehicle tire with a tread produced with a rubber mixture according to one of the claims 1 to 12. Drive belt using a rubber compound according to one of the claims 1 to 12 is made. Drive belt according to claim 22, characterized that the belt is a toothed belt or a V-ribbed belt. Seal made using a rubber compound according to one of the claims 1 to 12 is made. Seal according to claim 24, characterized that it is made in molds. Seal according to one of claims 24 or 25, characterized that they are in the form of a bellows or a membrane is. Air spring using a rubber compound according to one of the claims 1 to 12 is made. Rubber mixture obtainable according to a method according to one the claims 13 to 19.