EP3258006A1 - Method for producing a reinforcing support, reinforcing support and vehicle tyre - Google Patents

Method for producing a reinforcing support, reinforcing support and vehicle tyre Download PDF

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Publication number
EP3258006A1
EP3258006A1 EP17169840.0A EP17169840A EP3258006A1 EP 3258006 A1 EP3258006 A1 EP 3258006A1 EP 17169840 A EP17169840 A EP 17169840A EP 3258006 A1 EP3258006 A1 EP 3258006A1
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EP
European Patent Office
Prior art keywords
blocked
polyamide
free
reinforcement
mixture
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Granted
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EP17169840.0A
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German (de)
French (fr)
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EP3258006B1 (en
Inventor
Nermeen Nabih
Thomas Kramer
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Continental Reifen Deutschland GmbH
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Continental Reifen Deutschland GmbH
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D06M2101/08—Esters or ethers of cellulose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

Definitions

  • the invention relates to a method for producing a reinforcement layer for elastomeric products and to a reinforcement layer produced by the method. Furthermore, the invention relates to a vehicle tire which contains at least one reinforcement layer according to the invention.
  • Strength supports for reinforcing various elastomeric products are well known.
  • the reinforcements are usually surrounded by at least one rubber mixture, which is also called Kunststoff fürsmischung.
  • One problem is that the reinforcements and the surrounding rubber mixture have different strengths.
  • RFL dips resorcinol-formaldehyde latex
  • blocked isocyanate and / or epoxy compounds in combination with RFL dips are used to further activate the strength carriers.
  • the WO 2005/026239 A1 discloses the use of polyisocyanates and RFL without epoxy compounds.
  • the present invention is based on the object to provide a method for producing a reinforcement layer comprising textile reinforcement, whereby the reinforcement layer produced have the same or even improved adhesion between reinforcements and rubberizing mixture and also should be dispensed with environmentally and harmful substances.
  • Another object of the present invention is a reinforcement layer comprising textile reinforcement, which was prepared by the inventive method.
  • a further object on which the invention is based is to provide a vehicle tire which has improved or at least the same structural durability, wherein environmentally and harmful substances are to be dispensed with in at least one reinforcement layer. It should thus be created at least one environmentally friendly alternative.
  • a vehicle tire comprising in at least one component at least one reinforcement layer according to the invention, which was prepared by the method according to the invention.
  • the reinforcement layer according to the invention or the reinforcement layer of the vehicle tire according to the invention has improved adhesion between the reinforcements and the surrounding rubber mixture, the adhesion level being comparable to the standard RFL dip treated reinforcements.
  • the vehicle tire is preferably a pneumatic vehicle tire.
  • the textile reinforcements in step a) are pretreated by immersion in at least one first bath, wherein the first bath contains at least one blocked polyisocyanate and is free of free resorcinol and free formaldehyde and their precondensates.
  • the textile reinforcements are still ungummed before and after this process step.
  • the first bath is preferably an aqueous dispersion containing, in addition to water and the blocked polyisocyanate, at least one epoxy compound such as glycerol triglyceride ether and / or bisphenol A diglycidyl ether and / or 2,3-epoxybutyl azide formate and / or sorbitol polyglycidyl ether, may contain.
  • the first bath contains at least one epoxy compound, preferably glycerol triglyceride ether, which is known, for example, under the trade name Grilbond® G 1701. Dipping in the reinforcement in this first bath is carried out in a manner known to those skilled in the art. Such a treatment step is also referred to as pre-dip.
  • the first bath is free of free resorcinol and free formaldehyde and their precondensates, ie it contains 0 to 0.01 wt .-%, but preferably 0 wt .-%, of such substances.
  • blocked polyisocyanates are understood as meaning substances which have three or more terminal isocyanate groups which are blocked only by a protective group and are available for further chemical reactions after / during the removal of the protective group.
  • the isocyanates can then be present as a mixture of different molecules with different functionalities, wherein the average number of terminal isocyanate groups corresponds to the average functionality.
  • the blocked polyisocyanate has a functionality of greater than or equal to 3, more preferably 3 to 5, most preferably 3 to 4, for example, in particular 3.3.
  • the blocked polyisocyanate is preferably selected from the group consisting of blocked 1,6-hexamethylene diisocyanate trimer (HDI) and its blocked higher homologues as well as blocked toluene diisocyanate trimer and its blocked higher homologues as well as blocked isophorone diisocyanate trimer and its blocked higher homologs.
  • HDI blocked 1,6-hexamethylene diisocyanate trimer
  • the blocked polyisocyanate is blocked 1,6-hexamethylene diisocyanate trimer or blocked toluene diisocyanate trimer, more preferably 1,6-hexamethylene diisocyanate trimer. Since the 1,6-hexamethylene diisocyanate trimer is formed formally by condensation of three 1,6-hexamethylene diisocyanate molecules on one isocyanate group of the diisocyanates, the 1,6-hexamethylene diisocyanate trimer has three (remaining) terminal isocyanate groups ,
  • the protecting groups of the blocked polyisocyanate (s) may be any protecting group known to those skilled in the art.
  • the protective groups of the blocked polyisocyanate (s) are preferably selected from the group consisting of ketoximes, such as preferably methyl ethyl ketoxime (MEKO), and / or pyrazole derivatives, such as preferably 3,5-dimethylpyrazole (DMP), and / or esters, as preferred malonic acid ester or caprolactam or alkylated phenols.
  • the protective group is preferably methyl ethyl ketoxime and / or 3,5-dimethylpyrazole.
  • the blocked polyisocyanate in process step a) Methyl ethyl ketoxime blocked 1,6-hexamethylene diisocyanate trimer or 3,5-dimethylpyrazole blocked 1,6-hexamethylene diisocyanate trimer.
  • the reinforcements in process step b) are dried at 120 to 180 ° C.
  • the temperature must not be too high, so that there is no deprotection of the blocked isocyanates, to an undesirable To prevent side reaction with the evaporating (residual) water.
  • the duration of the drying step b) is preferably 30 to 120 seconds.
  • the dried reinforcements are heated in process step c) to 160 to 230 ° C to deprotect the isocyanates.
  • the heating time in step c) is preferably 30 to 120 seconds.
  • the reinforcements in process step d) are treated by being dipped in at least one second bath, the second bath containing at least one malein-functionalized polymer and being free of free resorcinol and free formaldehyde and their precondensates.
  • a maleic-functionalized polymer is a polymer which carries maleic groups as functional groups by reaction with maleic acid and / or maleic anhydride.
  • a maleic-functionalized polymer is, for example, under the trade name Ricobond ® 7004 Cray Valley available as an aqueous dispersion.
  • the second bath is preferably an aqueous dispersion which preferably contains at least one VP latex (vinyl pyridine latex, typically 15% vinyl pyridine, 15% styrene and 70% butadiene) in addition to water and the malein functionalized polymer.
  • the aqueous dispersion consists of 90 to 99.9 wt .-% of water, VP latex and said maleic polymer.
  • the aqueous dispersion here preferably comprises 40 to 90% by weight of water and 5 to 40% by weight of VP latex and 1 to 10% by weight of the said maleic polymer.
  • the VP latex is likewise preferably used as aqueous dispersion, the above quantities being based on anhydrous VP latex, or the water content contained in the VP latex dispersion already having been added to the total amount of water of the aqueous dispersion.
  • malein-functionalized polymers by reaction with amines imide functionalities and thus maleimide polymers. Since not all malein groups have to be converted into imide groups, For example, the resulting maleimide polymer has both maleic and imide groups.
  • the maleic polymer used preferably has a molecular weight of 5,000 to 20,000 g / mol, particularly preferably 5,000 to 15,000 g / mol, very particularly preferably 7,000 to 13,000 g / mol, again very particularly preferably 10,500 to 13,000 g / mol. With such a molecular weight of the maleic polymer, sufficient adhesion to the strength member results, and the workability of the dispersion is good.
  • the maleic-functionalized polymer described above is a polybutadiene.
  • the second bath according to step d) is free of free resorcinol and free formaldehyde and their precondensates, i. it contains 0 to 0.01 wt .-%, but preferably 0 wt .-%, of such substances.
  • the combination of the dipping containing the maleic polymer according to step d) with said pre-dip containing polyisocyanates according to step a) leads to improved adhesion results of reinforcing agents to the respective surrounding rubberizing mixture, wherein the advantages in particular in a polyamide, preferably nylon, and a polyester, preferably PET, as textile reinforcing materials in comparison to a pretreatment with blocked diisocyanates known from the prior art.
  • a sufficient level of adhesion is achieved, which is dispensed with environmentally and harmful substances.
  • the reinforcements in process step e) are dried at 120 to 155 ° C. Again, this step is to first remove water so that it does not lead to side reactions in subsequent reactions.
  • the duration of the drying step e) is preferably 30 to 120 seconds.
  • the dried reinforcements are heated to 210 to 250 ° C. in process step f). This serves to react the deprotected substances from the first bath in step a) with the substances from the second bath in step d).
  • the heating time in process step f) is 30 to 120 seconds.
  • the strength carriers treated by method steps a) to f) are gummed according to the invention in step g) with at least one gumming mixture, i. jacketed.
  • the gum mixture for this purpose contains at least one diene rubber selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or butadiene rubber and / or styrene-butadiene rubber, and 20 to 90 phr of at least one filler selected from the group consisting of carbon black and / or silica.
  • the gum mixture may contain polyisoprene (IR, NR) as the diene rubber.
  • IR, NR polyisoprene
  • These may be both cis-1,4-polyisoprene and 3,4-polyisoprene.
  • preference is given to the use of cis-1,4-polyisoprenes having a cis-1,4 content of> 90% by weight.
  • a polyisoprene can be obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls.
  • natural rubber is such a cis-1,4-polyisoprene
  • the cis-1,4-content in natural rubber is greater than 99% by weight.
  • the rubber mixture contains polybutadiene (BR) as the diene rubber, these may be either cis-1,4- or vinyl-polybutadiene (about 10-90% by weight vinyl content).
  • BR polybutadiene
  • Preference is given to the use of cis-1,4-polybutadiene with a cis-1,4 content greater than 90 wt .-%, which z.
  • styrene-butadiene copolymers can be used as further diene rubbers.
  • the styrene-butadiene copolymers may be solution-polymerized styrene-butadiene copolymers (S-SBR) having a styrene content, based on the polymer, of about 10 to 45% by weight and a vinyl content (content of 1.2 bound butadiene, based on the total polymer) of from 10 to 70% by weight, which can be prepared using, for example, lithium alkyls in organic solvent.
  • S-SBR can also be coupled and end-group modified.
  • E-SBR emulsion-polymerized styrene-butadiene copolymers
  • S-SBR emulsion-polymerized styrene-butadiene copolymers
  • the styrene content of the E-SBR is about 15 to 50% by weight, and the types known in the art obtained by copolymerization of styrene and 1,3-butadiene in aqueous emulsion can be used.
  • the diene rubbers used in the mixture can also be used in a partially or completely functionalized form become.
  • the functionalization can be carried out with groups that can interact with the fillers used, in particular with OH-bearing fillers. It may be z.
  • the gum mixture preferably contains from 25 to 100 phr, particularly preferably from 50 to 100 phr, again particularly preferably from 70 to 100 phr of natural polyisoprene and / or synthetic polyisoprene, in which case natural polyisoprene is preferred.
  • the gumming mixture contains 100 phr of at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR), whereby a mixture of NR and IR is conceivable.
  • NR natural polyisoprene
  • IR synthetic polyisoprene
  • the gumming mixture contains 25 to 85 phr of at least one natural and / or synthetic polyisoprene and 15 to 50 phr of at least one butadiene rubber and / or 15 to 50 phr of at least one styrene-butadiene rubber.
  • these rubbers particularly in reinforcing layers of vehicle tires, very good physical properties of the rubberizing mixture are manifested in terms of processability, durability and tear properties while achieving a sufficient level of adhesion.
  • the term phr (parts per hundred parts of rubber by weight) used in this document is the quantity used in the rubber industry for mixture formulations.
  • the dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • the mass of all rubbers present in the mixture adds up to 100.
  • the gum mixture may contain as fillers carbon blacks and / or silicic acids, the fillers may be used in combination and the total amount of carbon black and silica is 20 to 90 phr. Preferably 30 to 90 phr, more preferably 50 to 70 phr of at least one carbon black are used.
  • the gumming mixture contains 50 to 100 phr of at least one natural and / or synthetic polyisoprene and 30 to 90 phr of at least one carbon black. This results in a particularly good structural durability of the reinforcement layer produced, especially when used in vehicle tires.
  • further fillers such as aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gels may be included.
  • CNT carbon nanotubes
  • HCF hollow carbon fibers
  • Graphite and graphene as well as so-called "carbon-silica dual-phase filler” are conceivable as filler.
  • the gum mixture is preferably free of these further fillers, ie it preferably contains 0 to 0.001 phr of these further fillers.
  • Zinc oxide is not considered a filler in the present invention.
  • carbon black When carbon black is used in the gum mixture, it is preferably those types having an STSA surface area (in accordance with ASTM D 6556) of more than 30 m 2 / g, preferably 30 to 120 m 2 / g. These can be easily incorporated and ensure low heat build-up.
  • the gumming mixture contains at least one carbon black which has an iodine adsorption number according to ASTM D 1510 of 40 to 110 g / kg and an STSA surface (according to ASTM D 6556) of 40 to 120 m 2 / g.
  • a carbon black which has an iodine adsorption number according to ASTM D 1510 of 40 to 110 g / kg and an STSA surface (according to ASTM D 6556) of 40 to 120 m 2 / g.
  • a possible preferred type of carbon black is, for example, carbon black N326 having an iodine adsorption number according to ASTM D 1510 of 82 g / kg and an STSA surface (according to ASTM D 6556) of 76 m 2 / g.
  • Another possible preferred type of carbon black is, for example, carbon black N660 having an iodine adsorption number according to ASTM D 1510 of 36 g / kg and an STSA surface (according to ASTM D 6556) of 34 m 2 / g.
  • silicas are present in the mixture, these may be the silicas customary for tire rubber mixtures. It is particularly preferred when a finely divided, precipitated silica is used which has a CTAB surface area (according to ASTM D 3765) of 30 to 350 m 2 / g, preferably from 120 to 250 m 2 / g.
  • CTAB surface area according to ASTM D 3765
  • silicic acids it is possible to use both conventional silica such as VN3 (trade name) from Evonik and highly dispersible silicas, so-called HD silicas (eg Ultrasil 7000 from Evonik). Silicas are preferably used in amounts of less than 15 phr.
  • plasticizers from 0 to 70 phr, preferably from 0.1 to 60 phr, of at least one plasticizer may be present in the gum mixture.
  • plasticizers known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as, for example, MES (mild extraction solvate) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid.
  • MES mill extraction solvate
  • TDAE treated distillate aromatic extract
  • RTL rubber-to-liquid oils
  • mineral oil this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.
  • the vulcanization is carried out in the presence of sulfur and / or sulfur donors, with some sulfur donors can also act as a vulcanization accelerator.
  • Sulfur or sulfur donors are added in the last mixing step in the amounts customary by the skilled person (0.4 to 8 phr, sulfur, preferably in amounts of 0.4 to 4 phr) of the gum mixture.
  • the vulcanization can also be carried out in the presence of very small amounts of sulfur in combination with sulfur-donating substances.
  • the gum mixture may contain vulcanization-affecting substances such as vulcanization accelerators, vulcanization retarders and vulcanization activators in conventional amounts in order to control the time and / or temperature of vulcanization required and to improve the vulcanizate properties.
  • the vulcanization accelerators may be selected, for example, from the following groups of accelerators: thiazole accelerators such as. B. 2-mercaptobenzothiazole, sulfenamide accelerators such as. B. benzothiazyl-2-cyclohexylsulfenamid (CBS), guanidine accelerators such as. N, N'-diphenylguanidine (DPG), dithiocarbamate accelerators such as. Zinc dibenzyldithiocarbamate, disulfides, Thiophosphates.
  • the accelerators can also be used in combination with each other, which can result in synergistic effects.
  • the preparation of the gum mixture is carried out in a conventional manner, wherein first of all a masterbatch containing all constituents except for the vulcanization system (sulfur and vulcanization-affecting substances) is prepared in one or more mixing stages followed by the addition of the curing system is produced. Subsequently, the mixture is processed further.
  • a masterbatch containing all constituents except for the vulcanization system sulfur and vulcanization-affecting substances
  • step g) The gumming of the reinforcement in step g) also takes place in a manner known to those skilled in the art.
  • the textile reinforcements preferably comprise polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN) and / or polybutylene terephthalate (PBT) and / or polycarbonate (PC) and / or cellulose and / or cellulose esters and / or m-aramid and / or p-aramid and / or a mixture of m-aramid and p-aramid and / or a polyamide which is selected from the group consisting of polyamide 46 (PA 4.6) and / or polyamide 410 (PA 4.10) and / or polyamide 6 (PA 6 ) and / or polyamide 66 (PA 6.6 polyhexamethylene adipamide) and / or polyamide 612 (PA 6.12) and / or polyamide 1010 (PA 10.10) and / or polyamide 1212 (PA 12.12).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • the textile reinforcements particularly preferably comprise polyethylene terephthalate (PET) and / or cellulose and / or cellulose esters and / or polyamide 66 (PA 6.6 polyhexamethylene adipamide).
  • PET polyethylene terephthalate
  • PA 6.6 polyhexamethylene adipamide PA 6.6 polyhexamethylene adipamide
  • the textile reinforcement are preferably cords having at least one twisted yarn.
  • all known in the prior art subtleties (titer in the unit dtex) and twisting of the cords and yarns are conceivable. It is expedient if the denier of each yarn is between 200 and 5000 dtex and if the twist of the yarns and cords is between 100 and 800 t / m.
  • the textile reinforcing materials preferably have the stated properties already before process step a), ie they are first twisted and then treated with process steps a) to f). In the event that the textile reinforcing elements are embedded as a tissue in the rubberizing mixture, preferably after twisting and before the treatment according to the process steps a) to f), as known to those skilled in a weaving step.
  • the reinforcing members are cords of a respective yarn, with which a twisted yarn represents a cord in each case.
  • the strength carriers are cords of at least two, more preferably two, yarns.
  • the reinforcement layer according to the invention or that of the vehicle tire according to the invention cords from different numbers of yarns as reinforcement.
  • the reinforcement layer according to the invention can be used in all components of a vehicle tire, which contain reinforcements, resulting in the above-mentioned advantages in terms of substances and the production and sufficient adhesion.
  • These components are, in particular, the carcass ply and / or the belt (in the belt layer or layers) and / or the belt bandage and / or the bead reinforcement.
  • nylon cords made of two nylon yarns having a thickness of 940 dtex (940 x 2) were passed through a pre-dip containing 95.54 wt .-% water and 0.75 wt .-% Grilbond ® G 1701 and 3 , 71% by weight of Acrafix PCI (DMP-blocked HDI trimer, solids content about 31.5% by weight). Subsequently, the cords were dried for 30 to 120 seconds at 165 ° C and then heated to 225 ° C. These cords were dipped through another dip bath containing 54% by weight of water and 42.4% by weight of VP latex (40% by weight of VP polymer in water, ie 17% by weight of VP).
  • Acrafix PCI DMP-blocked HDI trimer, solids content about 31.5% by weight
  • Latex in the dip and 3.6% by weight of RICOBOND 7004, Cray Valley (30% by weight of maleic polymer in water: mean value from manufacturer's information 25 to 35% by weight). It was then dried again at 140 ° C. for 30 to 120 seconds and then heated to 235 ° C.
  • Comparative Example 1 Nylon cords as textile reinforcement, Pre-dip containing caprolactam blocked MDI, dip containing maleic polymer
  • the cords of Comparative Example 1 was prepared analogously to E1, except that instead of Acrafix PCI (DMP blocked HDI-trimer) Crrilbond ® IL-6 (caprolactam-blocked MDI) was used.
  • the pre-dip containing 96.71 wt .-% water and 2.54 wt .-% ® Grilbond IL-6 and 0.75 wt .-% Grilbond ® G 1,701th
  • the process step of drying involving hot drawing was undisturbed, ie, as known to those skilled in the art. This serves to improve the properties, such as elongation at break, elongation at break and heat shrinkage of the cord by targeted stretching on the to set the desired level. wherein the tension applied to the cord is varied between tension and relaxation.
  • Adhesive tests, so-called peel tests, according to ISO 36: 2011 (E) with evaluation in accordance with DIN ISO 6133 without aging were carried out with the differently treated cords.
  • the strength carrier cords were rubberized with an uncured gum mixture having the composition according to Table 1 (according to process step g)) and then vulcanized.
  • the gumming takes place by placing the cords on or between calendered thin rubber sheets of the gumming compound and then compressing the entire specimen in the heating press. Then, the force for peeling off the mixture from the cords was determined (adhesion), and the coverage of the cords with mixture after peeling was optically determined. 5 means complete coverage, 0 means no rubber remains on the cord.
  • the breaking force, the elongation at 45 N, the shrinkage at 180 ° C and the residual shrinkage based on ASTM D 855 were determined.
  • Table 2 Components of the gum mixture ingredients Quantity (phr) NR / IR 70 BR / SBR 30 Soot N660 50 Processing oil / adhesive resin 5 Other additives a) 8th Resin from resorcinol and formaldehyde donor 5 Sulfur and accelerator 3.3 a) anti-aging agent, ZnO, stearic acid
  • the reinforcement layer produced by means of the method according to the invention shows, as can be seen in Table 2, a comparable or even improved durability, since the adhesion of the reinforcements to the rubber coating mixture is improved. Furthermore, in the example of the invention, the disadvantages associated with resorcinol and formaldehyde are avoided.
  • Cords made of polyester, each made of two polyester yarns (polyethylene terephthalate PET) with a thickness of 1440 dtex (1440 x 2) were obtained by a pre-dip containing 96.71% by weight of water and 0.75% by weight of Crrilbond® G wt .-% EDOLAN ® XCIB (MEKO blocked HDI-trimer) immersed 1701 and 2.54. Subsequently, the cords were dried for 30 to 120 seconds at 160 ° C and then heated to 235 ° C. These dried cords were dipped through another dip bath containing 54% by weight of water and 42.4% by weight of VP latex (40% by weight VP polymer in water) and 3.6% by weight.
  • VP latex 50% by weight VP polymer in water
  • E3 The cords according to Inventive Example 3 (E3) were prepared analogously E2 prepared with the exception that instead of EDOLAN ® XCIB (MEKO a blocked HDI-trimer) (MEKO blocked TDI) 2.54 wt .-% Baygard EDW ® was used.
  • Comparative Example 2 (V2): polyester cords as textile reinforcements, pre-dip containing caprolactam blocked MDI, dip containing maleic polymer
  • the cords according to Comparative Example 2 were prepared analogously to E2 with the exception that was used instead of of EDOLAN ® XCIB (MEKO a blocked HDI-trimer) 2.54 wt .-% Grilbond IL-6 (caprolactam-blocked MDI).
  • the drying step which involves hot drawing, was unaffected by the maleimide polymer, i. as known to the skilled person. This serves to adjust the properties, such as elongation at break, elongation at break and heat shrinkage of the cord by targeted stretching to the desired level. wherein the tension applied to the cord is varied between tension and relaxation.
  • the cords of Examples E2 and E3 and V2 were gummed analogously to Examples E1 and V1 with a gumming mixture according to Table 2 and then the adhesion and coverage as well as the rigidity were tested as described above. Furthermore, the breaking force, the elongation at 45 N, the shrinkage at 180 ° C and the residual shrinkage based on ASTM D 855 were determined.
  • a vehicle tire according to the invention preferably a pneumatic vehicle tire, which contains at least one reinforcement layer produced according to the invention in at least one component, is distinguished by a durability comparable to the prior art, with the activation of adhesion in the dips being based on the use of free resorcinol and formaldehyde as well as resorcinol-formaldehyde Pre-condensates can be dispensed with.

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Abstract

Die Erfindung betrifft ein Verfahren zur Herstellung einer Festigkeitsträgerlage aus textilen Festigkeitsträgern für elastomere Erzeugnisse, wobei das Verfahren u.a. das Tauchen der textilen Festigkeitsträger in wenigstens einem ersten Bad, welches wenigstens ein geblocktes Polyisocyanat enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, und das Tauchen der textilen Festigkeitsträger in wenigstens einem zweiten Bad, welches wenigstens ein Malein-funktionalisertes Polymer enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, umfasst. Des Weiteren betrifft die Erfindung eine mit dem Verfahren hergestellte Festigkeitsträgerlage sowie einen Fahrzeugreifen, der wenigstens eine erfindungsgemäße Festigkeitsträgerlage enthält.The invention relates to a method for producing a reinforcing layer of textile reinforcing materials for elastomeric products, wherein the method u.a. the immersion of the textile reinforcement in at least a first bath containing at least one blocked polyisocyanate and is free of free resorcinol and free formaldehyde and their precondensates, and the dipping of the textile reinforcement in at least one second bath containing at least one malein-functionalized polymer and free of free resorcinol and free formaldehyde and their precondensates. Furthermore, the invention relates to a reinforcement layer produced by the method and to a vehicle tire which contains at least one reinforcement layer according to the invention.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer Festigkeitsträgerlage für elastomere Erzeugnisse sowie eine durch das Verfahren hergestellte Festigkeitsträgerlage. Des Weiteren betrifft die Erfindung einen Fahrzeugreifen, der wenigstens eine erfindungsgemäße Festigkeitsträgerlage enthält.The invention relates to a method for producing a reinforcement layer for elastomeric products and to a reinforcement layer produced by the method. Furthermore, the invention relates to a vehicle tire which contains at least one reinforcement layer according to the invention.

Festigkeitsträger zur Verstärkung verschiedener elastomerer Erzeugnisse sind hinreichend bekannt. Hierbei sind die Festigkeitsträger üblicherweise von mindestens einer Kautschukmischung umgeben, die auch Gummierungsmischung genannt wird. Eine Problematik besteht darin, dass die Festigkeitsträger und die umgebende Gummierungsmischung unterschiedliche Festigkeiten aufweisen. Insbesondere bei andauernder mechanischer und dynamischer Beanspruchung, wie beispielsweise bei der Anwendung in einem Fahrzeugreifen im Fahrbetrieb, ist daher eine ausreichende Haftung zwischen Festigkeitsträger und umgebender Gummierungsmischung notwendig.
Im Stand der Technik ist bekannt, die Festigkeitsträger vor der Gummierung für eine ausreichende Haftung zu aktivieren (Haftungsaktivierung), wobei üblicherweise sogenannte RFL-Dips (Resorcin-Formaldehyd-Latex) verwendet werden, durch die die Festigkeitsträger getaucht werden.
Ferner werden u.a. geblockte Isocyanat- und/oder Epoxy-Verbindungen in Kombination mit RFL-Dips eingesetzt, um die Festigkeitsträger weiter zu aktivieren. Die WO 2005/026239 A1 offenbart beispielsweise die Verwendung von Polyisocyanaten und RFL ohne Epoxy-Verbindungen.Strength supports for reinforcing various elastomeric products are well known. Here, the reinforcements are usually surrounded by at least one rubber mixture, which is also called Gummierungsmischung. One problem is that the reinforcements and the surrounding rubber mixture have different strengths. In particular, with ongoing mechanical and dynamic stress, such as when used in a vehicle tire while driving, therefore, sufficient adhesion between the strength carrier and the surrounding gum mixture is necessary.
In the prior art it is known to activate the strength members before the rubber coating for sufficient adhesion (adhesion activation), whereby usually so-called RFL dips (resorcinol-formaldehyde latex) are used, through which the strength members are immersed.
Furthermore, inter alia, blocked isocyanate and / or epoxy compounds in combination with RFL dips are used to further activate the strength carriers. The WO 2005/026239 A1 for example, discloses the use of polyisocyanates and RFL without epoxy compounds.

Allerdings sind Resorcin und Formaldehyde als umwelt- und gesundheitsschädlich eingestuft, sodass man bestrebt ist hierfür Alternativen bereitzustellen. So offenbaren die EP 1745079 B1 sowie die DE 102014211365 A1 die Behandlung von textilem Gewebe bzw. textilen Festigkeitsträgern mit einem Malein-funktionalisiertem Polymer, um eine verbesserte Haftung an Kautschukmischungen zu erzielen.However, resorcinol and formaldehyde are classified as harmful to the environment and to health, so that one endeavors to provide alternatives for this purpose. This is what the EP 1745079 B1 as well as the DE 102014211365 A1 the treatment of textile fabric or textile reinforcements with a maleic-functionalized polymer to achieve improved adhesion to rubber compounds.

Der vorliegenden Erfindung liegt nun die Aufgabe zu Grunde, ein Verfahren zur Herstellung einer Festigkeitsträgerlage umfassend textile Festigkeitsträger bereitzustellen, wodurch die hergestellte Festigkeitsträgerlage eine gleiche oder sogar verbesserte Haftung zwischen Festigkeitsträgern und Gummierungsmischung aufweisen und zudem auf umwelt- und gesundheitsschädliche Substanzen verzichtet werden soll.The present invention is based on the object to provide a method for producing a reinforcement layer comprising textile reinforcement, whereby the reinforcement layer produced have the same or even improved adhesion between reinforcements and rubberizing mixture and also should be dispensed with environmentally and harmful substances.

Gelöst wird diese Aufgabe erfindungsgemäß durch ein Verfahren zur Herstellung einer Festigkeitsträgerlage umfassend textile Festigkeitsträger für elastomere Erzeugnisse, wobei das Verfahren wenigstens die Verfahrensschritte in folgender Reihenfolge umfasst:

  1. a) Tauchen der textilen Festigkeitsträger in wenigstens einem ersten Bad, welches wenigstens ein geblocktes Polyisocyanat enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, und
  2. b) Anschließendes Trocknen der Festigkeitsträger bei 120 bis 180 °C, und
  3. c) Anschließendes Erhitzen der Festigkeitsträger auf 160 bis 230 °C, und
  4. d) Tauchen der textilen Festigkeitsträger in wenigstens einem zweiten Bad, welches wenigstens ein Malein-funktionalisertes Polymer enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, und
  5. e) Anschließendes Trocknen der Festigkeitsträger bei 120 bis 155 °C, und
  6. f) Anschließendes Erhitzen der Festigkeitsträger auf 210 bis 250 °C, und
  7. g) Gummierung der mittels a) bis f) vorbehandelten textilen Festigkeitsträger mit einer Gummierungsmischung, die wenigstens einen Dienkautschuk, der ausgewählt ist aus der Gruppe bestehend aus natürlichem Polyisopren und/oder synthetischem Polyisopren und/oder Butadien-Kautschuk und/oder Styrol-Butadien-Kautschuk, und 20 bis 90 phr wenigstens eines Füllstoffes ausgewählt aus der Gruppe bestehend aus Ruß und/oder Kieselsäure enthält.
This object is achieved according to the invention by a process for producing a reinforcement layer comprising textile reinforcement for elastomeric products, the method comprising at least the method steps in the following sequence:
  1. a) immersing the textile reinforcement in at least one first bath containing at least one blocked polyisocyanate and is free of free resorcinol and free formaldehyde and their precondensates, and
  2. b) Subsequent drying of the reinforcements at 120 to 180 ° C, and
  3. c) then heating the reinforcements to 160 to 230 ° C, and
  4. d) immersing the textile reinforcement in at least one second bath, which contains at least one malein-functionalized polymer and is free of free resorcinol and free formaldehyde and their precondensates, and
  5. e) then drying the strength members at 120 to 155 ° C, and
  6. f) then heating the reinforcements to 210 to 250 ° C, and
  7. g) gumming of the textile reinforcements pretreated by means of a) to f) with a gumming composition comprising at least one diene rubber selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or butadiene rubber and / or styrene-butadiene rubber. Rubber, and 20 to 90 phr of at least one filler selected from the group consisting of carbon black and / or silica.

Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Festigkeitsträgerlage umfassend textile Festigkeitsträger, die durch das erfindungsgemäße Verfahren hergestellt wurde.
Eine weitere Aufgabe, die der Erfindung zu Grunde liegt, besteht darin, einen Fahrzeugreifen bereitzustellen, der eine verbesserte oder zumindest gleiche strukturelle Haltbarkeit aufweist wobei in wenigstens einer Festigkeitsträgerlage auf umwelt- und gesundheitsschädliche Substanzen verzichtet werden soll. Es soll somit zumindest eine umweltfreundliche Alternative geschaffen werden.Another object of the present invention is a reinforcement layer comprising textile reinforcement, which was prepared by the inventive method.
A further object on which the invention is based is to provide a vehicle tire which has improved or at least the same structural durability, wherein environmentally and harmful substances are to be dispensed with in at least one reinforcement layer. It should thus be created at least one environmentally friendly alternative.

Gelöst wird diese Aufgabe erfindungsgemäß durch einen Fahrzeugreifen, enthaltend in wenigstens einem Bauteil wenigstens eine erfindungsgemäße Festigkeitsträgerlage, die durch das erfindungsgemäße Verfahren hergestellt wurde.This object is achieved according to the invention by a vehicle tire, comprising in at least one component at least one reinforcement layer according to the invention, which was prepared by the method according to the invention.

Es wurde gefunden, dass die erfindungsgemäße Festigkeitsträgerlage bzw. die Festigkeitsträgerlage des erfindungsgemäßen Fahrzeugreifens eine verbesserte Haftung zwischen den Festigkeitsträgern und der umgebenden Gummierungsmischung aufweist, wobei das Haftungsniveau vergleichbar ist mit dem mit Standard-RFL-Dip behandelten Festigkeitsträgern.
Bevorzugt handelt es sich bei dem Fahrzeugreifen um einen Fahrzeugluftreifen.It has been found that the reinforcement layer according to the invention or the reinforcement layer of the vehicle tire according to the invention has improved adhesion between the reinforcements and the surrounding rubber mixture, the adhesion level being comparable to the standard RFL dip treated reinforcements.
The vehicle tire is preferably a pneumatic vehicle tire.

Erfindungsgemäß werden die textilen Festigkeitsträger in Verfahrensschritt a) durch Tauchen in wenigstens einem ersten Bad vorbehandelt, wobei das erste Bad wenigstens ein geblocktes Polyisocyanat enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten. Die textilen Festigkeitsträger sind vor und nach diesem Verfahrensschritt noch ungummiert. Das erste Bad ist bevorzugt eine wässrige Dispersion, die neben Wasser und dem geblockten Polyisocyanat wenigstens eine Epoxy-Verbindung, wie z.B. Glycerintriglyceridether und/oder Bisphenol-A-diglycidylether und/oder 2,3-Epoxybutylazidoformat und/oder Sorbitolpolyglycidylether, enthalten kann, enthalten kann.
Gemäß einer bevorzugten Ausführungsform der Erfindung enthält das erste Bad wenigstens eine Epoxy-Verbindung, bevorzugt Glycerintriglyceridether, welches z.B. unter dem Handelsnamen Grilbond® G 1701 bekannt ist. Das Tauchen in der Festigkeitsträger in diesem ersten Bad erfolgt auf dem Fachmann bekannte Art und Weise. Ein derartiger Behandlungsschritt wird auch als Pre-Dip bezeichnet.
Das erste Bad ist frei von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, d.h. es enthält 0 bis 0,01 Gew.-%, bevorzugt jedoch 0 Gew.-%, derartiger Substanzen.According to the invention, the textile reinforcements in step a) are pretreated by immersion in at least one first bath, wherein the first bath contains at least one blocked polyisocyanate and is free of free resorcinol and free formaldehyde and their precondensates. The textile reinforcements are still ungummed before and after this process step. The first bath is preferably an aqueous dispersion containing, in addition to water and the blocked polyisocyanate, at least one epoxy compound such as glycerol triglyceride ether and / or bisphenol A diglycidyl ether and / or 2,3-epoxybutyl azide formate and / or sorbitol polyglycidyl ether, may contain.
According to a preferred embodiment of the invention, the first bath contains at least one epoxy compound, preferably glycerol triglyceride ether, which is known, for example, under the trade name Grilbond® G 1701. Dipping in the reinforcement in this first bath is carried out in a manner known to those skilled in the art. Such a treatment step is also referred to as pre-dip.
The first bath is free of free resorcinol and free formaldehyde and their precondensates, ie it contains 0 to 0.01 wt .-%, but preferably 0 wt .-%, of such substances.

Unter geblockten Polyisocyanaten werden im Rahmen der vorliegenden Erfindung Substanzen verstanden, die drei oder mehr terminale Isocyanat-Gruppen aufweisen, die lediglich durch eine Schutzgruppe geblockt sind und nach/bei Abspaltung der Schutzgruppe für weitere chemische Reaktionen zur Verfügung stehen.In the context of the present invention, blocked polyisocyanates are understood as meaning substances which have three or more terminal isocyanate groups which are blocked only by a protective group and are available for further chemical reactions after / during the removal of the protective group.

Die Isocyanate können dann als Gemisch aus verschiedenen Molekülen mit unterschiedlichen Funktionalitäten vorliegen, wobei die mittlere Zahl der terminalen Isocyanat-Gruppen der mittleren Funktionalität entspricht.
Diese sogenannte Isocyanatzahl wird, wie dem Fachmann bekannt, über Titration bestimmt (ISO 14896/3, s. Metrohm, Application Bulletin 200/3 e; http://www.***.de/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&ved=0ahUKEwib np6n1KTNAhXoD8AKHQY4ApQQFggfMAA&url=http%3A%2F%2Fpartners.metrohm. com%2FGetDocument%3Faction%3Dget_dms_document%26docid%3D1662929&usg=A FQjCNEOo_1vxWxdWsscUzU830rsT6JbxQ).The isocyanates can then be present as a mixture of different molecules with different functionalities, wherein the average number of terminal isocyanate groups corresponds to the average functionality.
As known to the person skilled in the art, this so-called isocyanate number is determined by titration (ISO 14896/3, see Metrohm, Application Bulletin 200/3 e; http://www.***.de/url?sa=t&rct=j&q=&esrc= s & source = web & cd = 1 & ved = 0ahUKEwib np6n1KTNAhXoD8AKHQY4ApQQFggfMAA & url = http% 3A% 2F% 2Fpartners.metrohm. com% 2FGetDocument% 3Faction% 3Dget_dms_document% 26docid% 3D1662929 & usg = A FQjCNEOo_1vxWxdWsscUzU830rsT6JbxQ).

Gemäß einer vorteilhaften Ausführungsform der Erfindung weist das geblockte Polyisocyanat eine Funktionalität von größer oder gleich 3, besonders bevorzugt 3 bis 5, ganz besonders bevorzugt 3 bis 4, auf, beispielsweise insbesondere 3,3.
Hierbei ist das geblockte Polyisocyanat bevorzugt ausgewählt aus der Gruppe bestehend aus geblocktem 1,6-Hexamethylendiisocyanat-Trimer (HDI) und dessen geblockten höheren Homologen sowie geblocktem Toluoldiisocyanat-Trimer und dessen geblockten höheren Homologen sowie geblocktem Isophorondiisocyanat-Trimer und dessen geblockten höheren Homologen.
Bevorzugt ist das geblockte Polyisocyanat geblocktes 1,6-Hexamethylendiisocyanat-Trimer oder geblocktes Toluoldiisocyanat-Trimer, besonders bevorzugt 1,6-Hexamethylendiisocyanat-Trimer.
Da das 1,6-Hexamethylendiisocyanat-Trimer formal durch Kondensation von drei 1,6-Hexamethylendiisocyanat-Molekülen an jeweils einer Isocyanat-Gruppe der Diisocyanate entsteht, weist das 1,6-Hexamethylendiisocyanat-Trimer drei (übrig gebliebene) terminale Isocyanat-Gruppen auf.According to an advantageous embodiment of the invention, the blocked polyisocyanate has a functionality of greater than or equal to 3, more preferably 3 to 5, most preferably 3 to 4, for example, in particular 3.3.
Here, the blocked polyisocyanate is preferably selected from the group consisting of blocked 1,6-hexamethylene diisocyanate trimer (HDI) and its blocked higher homologues as well as blocked toluene diisocyanate trimer and its blocked higher homologues as well as blocked isophorone diisocyanate trimer and its blocked higher homologs.
Preferably, the blocked polyisocyanate is blocked 1,6-hexamethylene diisocyanate trimer or blocked toluene diisocyanate trimer, more preferably 1,6-hexamethylene diisocyanate trimer.
Since the 1,6-hexamethylene diisocyanate trimer is formed formally by condensation of three 1,6-hexamethylene diisocyanate molecules on one isocyanate group of the diisocyanates, the 1,6-hexamethylene diisocyanate trimer has three (remaining) terminal isocyanate groups ,

Bei den Schutzgruppen des oder der geblockten Polyisocyanate kann es sich um alle dem Fachmann bekannten Schutzgruppen handeln. Bevorzugt sind die Schutzgruppen des oder der geblockten Polyisocyanat(e) ausgewählt aus der Gruppe bestehend aus Ketoximen, wie bevorzugt Methylethylketoxim (MEKO), und/oder Pyrazol-Derivaten, wie bevorzugt 3,5-Dimethylpyrazol (DMP), und/oder Estern, wie bevorzugt Malonsäureester oder Caprolactam oder alkylierte Phenole. Bevorzugt handelt es sich bei der Schutzgruppe um Methylethylketoxim und/oder 3,5-Dimethylpyrazol.The protecting groups of the blocked polyisocyanate (s) may be any protecting group known to those skilled in the art. The protective groups of the blocked polyisocyanate (s) are preferably selected from the group consisting of ketoximes, such as preferably methyl ethyl ketoxime (MEKO), and / or pyrazole derivatives, such as preferably 3,5-dimethylpyrazole (DMP), and / or esters, as preferred malonic acid ester or caprolactam or alkylated phenols. The protective group is preferably methyl ethyl ketoxime and / or 3,5-dimethylpyrazole.

Gemäß einer besonders vorteilhaften Weiterbildung der Erfindung ist das geblockte Polyisocyanat in Verfahrensschritt a)
Methylethylketoxim geblocktes 1,6-Hexamethylendiisocyanat-Trimer oder 3,5-Dimethylpyrazol geblocktes 1,6-Hexamethylendiisocyanat-Trimer.
Hierdurch ergeben sich in Kombination mit dem Malein-Polymer aus Schritt b) besonders gute Hafteigenschaften, wobei zudem auf umwelt- und gesundheitsschädliche Substanzen verzichtet werden kann.According to a particularly advantageous embodiment of the invention, the blocked polyisocyanate in process step a)
Methyl ethyl ketoxime blocked 1,6-hexamethylene diisocyanate trimer or 3,5-dimethylpyrazole blocked 1,6-hexamethylene diisocyanate trimer.
This results in combination with the maleic polymer from step b) particularly good adhesive properties, in addition to environmental and harmful substances can be dispensed with.

Im Anschluss an den Verfahrensschritt a) werden die Festigkeitsträger in Verfahrensschritt b) bei 120 bis 180 °C getrocknet. Hierbei darf die Temperatur nicht zu hoch sein, sodass noch keine Entschützung der geblockten Isocyanate erfolgt, um eine unerwünschte Nebenreaktion mit dem verdampfenden (Rest-)Wasser zu verhindern. Die Dauer des Trocknungsschrittes b) beträgt bevorzugt 30 bis 120 Sekunden.Subsequent to process step a), the reinforcements in process step b) are dried at 120 to 180 ° C. In this case, the temperature must not be too high, so that there is no deprotection of the blocked isocyanates, to an undesirable To prevent side reaction with the evaporating (residual) water. The duration of the drying step b) is preferably 30 to 120 seconds.

Im Anschluss an die Trocknung werden die getrockneten Festigkeitsträger in Verfahrensschritt c) auf 160 bis 230 °C erhitzt, um die Isocyanate zu entschützen.After drying, the dried reinforcements are heated in process step c) to 160 to 230 ° C to deprotect the isocyanates.

Die Dauer des Erhitzens in Schritt c) beträgt bevorzugt 30 bis 120 Sekunden. Erfindungsgemäß werden die Festigkeitsträger in Verfahrensschritt d) durch Tauchen in wenigstens einem zweiten Bad behandelt, wobei das zweite Bad wenigstens ein Malein-funktionalisertes Polymer enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten.
Ein Malein-funktionalisertes Polymer ist ein Polymer, welches durch Reaktion mit Maleinsäure und/oder Maleinsäureanhydrid Malein-Gruppen als funktionelle Gruppen trägt. Ein Malein-funktionalisiertes Polymer ist beispielsweise unter dem Handelsnamen Ricobond® 7004 der Firma Cray Valley als wässrige Dispersion erhältlich.
Das zweite Bad ist bevorzugt eine wässrige Dispersion, welche neben Wasser und dem Malein-funktionaliserten Polymer bevorzugt wenigstens ein VP-Latex (Vinyl-Pyridin-Latex, typischerweise 15 % Vinyl-Pyridin, 15 % Styrol und 70 % Butadien) enthält. Gemäß einer bevorzugten Ausführungsform der Erfindung besteht die wässrige Dispersion zu 90 bis 99,9 Gew.-% aus Wasser, VP-Latex und dem genannten Malein-Polymer. Bevorzugt enthält die wässrige Dispersion hierbei 40 bis 90 Gew.-% Wasser und 5 bis 40 Gew.-% VP-Latex und 1 bis 10 Gew.-% des genannten Malein-Polymers. Der VP-Latex wird ebenfalls bevorzugt als wässrige Dispersion eingesetzt, wobei die obigen Mengenangaben sich auf wasserfreien VP-Latex beziehen, bzw. der in der VP-Latex-Dispersion enthaltene Wasseranteil bereits der Gesamtmenge an Wasser der wässrigen Dispersion zugerechnet wurde.The heating time in step c) is preferably 30 to 120 seconds. According to the invention, the reinforcements in process step d) are treated by being dipped in at least one second bath, the second bath containing at least one malein-functionalized polymer and being free of free resorcinol and free formaldehyde and their precondensates.
A maleic-functionalized polymer is a polymer which carries maleic groups as functional groups by reaction with maleic acid and / or maleic anhydride. A maleic-functionalized polymer is, for example, under the trade name Ricobond ® 7004 Cray Valley available as an aqueous dispersion.
The second bath is preferably an aqueous dispersion which preferably contains at least one VP latex (vinyl pyridine latex, typically 15% vinyl pyridine, 15% styrene and 70% butadiene) in addition to water and the malein functionalized polymer. According to a preferred embodiment of the invention, the aqueous dispersion consists of 90 to 99.9 wt .-% of water, VP latex and said maleic polymer. The aqueous dispersion here preferably comprises 40 to 90% by weight of water and 5 to 40% by weight of VP latex and 1 to 10% by weight of the said maleic polymer. The VP latex is likewise preferably used as aqueous dispersion, the above quantities being based on anhydrous VP latex, or the water content contained in the VP latex dispersion already having been added to the total amount of water of the aqueous dispersion.

Wie in der EP 1745079 B1 offenbart, entstehen aus mit Malein-funktionalisierten Polymeren durch Reaktion mit Aminen Imid-Funktionalitäten und somit Maleinimid-Polymere. Da hierbei nicht alle Malein-Gruppen zu Imid-Gruppen umgesetzt sein müssen, weist das resultierende Maleinimid-Polymer sowohl Malein-Gruppen als auch Imid-Gruppen auf.Like in the EP 1745079 B1 discloses arise from malein-functionalized polymers by reaction with amines imide functionalities and thus maleimide polymers. Since not all malein groups have to be converted into imide groups, For example, the resulting maleimide polymer has both maleic and imide groups.

Die Begriffe "Gruppe" und "Funktionalisierung" werden in dem Zusammenhang mit den chemischen Merkmalen der eingesetzten Polymere synonym verwendet.The terms "group" and "functionalization" are used synonymously in the context of the chemical characteristics of the polymers used.

Bevorzugt weist das eingesetzte Malein-Polymer ein Molekulargewicht von 5000 bis 20000 g/mol, besonders bevorzugt 5000 bis 15000 g/mol, ganz besonders bevorzugt 7000 bis 13000 g/mol, wiederum ganz besonders bevorzugt 10500 bis 13000 g/mol.
Mit einem derartigen Molekulargewicht des Malein-Polymers ergibt sich eine ausreichende Haftung an den Festigkeitsträger, wobei die Verarbeitbarkeit der Dispersion gut ist.The maleic polymer used preferably has a molecular weight of 5,000 to 20,000 g / mol, particularly preferably 5,000 to 15,000 g / mol, very particularly preferably 7,000 to 13,000 g / mol, again very particularly preferably 10,500 to 13,000 g / mol.
With such a molecular weight of the maleic polymer, sufficient adhesion to the strength member results, and the workability of the dispersion is good.

Das oben beschriebene mit Malein-Gruppen funktionalisierte Polymer ist gemäß einer bevorzugten Weiterbildung der Erfindung ein Polybutadien.The maleic-functionalized polymer described above, according to a preferred embodiment of the invention, is a polybutadiene.

Das zweite Bad gemäß Schritt d) ist frei von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, d.h. es enthält 0 bis 0,01 Gew.-%, bevorzugt jedoch 0 Gew.-%, derartiger Substanzen.The second bath according to step d) is free of free resorcinol and free formaldehyde and their precondensates, i. it contains 0 to 0.01 wt .-%, but preferably 0 wt .-%, of such substances.

Insbesondere die Kombination des Dips enthaltend das Malein-Polymer gemäß Schritt d) mit dem genannten Pre-Dip enthaltend Polyisocyanate gemäß Schritt a) führt zu verbesserten Haftungsergebnissen von Festigkeitsträgern an die jeweilige umgebende Gummierungsmischung, wobei sich die Vorteile insbesondere bei einem Polyamid, bevorzugt Nylon, und einem Polyester, bevorzugt PET, als textile Festigkeitsträgermaterialien gegenüber einer aus dem Stand der Technik bekannten Vorbehandlung mit geblockten Diisocyanaten zeigen. Im Vergleich zu im Stand der Technik bekannten RFL-Vorbehandlungen wird ein ausreichendes Haftungsniveau erzielt, wobei auf umwelt- und gesundheitsschädliche Substanzen verzichtet wird.In particular, the combination of the dipping containing the maleic polymer according to step d) with said pre-dip containing polyisocyanates according to step a) leads to improved adhesion results of reinforcing agents to the respective surrounding rubberizing mixture, wherein the advantages in particular in a polyamide, preferably nylon, and a polyester, preferably PET, as textile reinforcing materials in comparison to a pretreatment with blocked diisocyanates known from the prior art. Compared to known in the art RFL pretreatments a sufficient level of adhesion is achieved, which is dispensed with environmentally and harmful substances.

Im Anschluss an den Verfahrensschritt d) werden die Festigkeitsträger in Verfahrensschritt e) bei 120 bis 155 °C getrocknet. Auch hier dient dieser Schritt dazu, zunächst Wasser zu entfernen, damit es in anschließenden Reaktionen nicht zu Nebenreaktionen führt. Die Dauer des Trocknungsschrittes e) beträgt bevorzugt 30 bis 120 Sekunden.Subsequent to process step d), the reinforcements in process step e) are dried at 120 to 155 ° C. Again, this step is to first remove water so that it does not lead to side reactions in subsequent reactions. The duration of the drying step e) is preferably 30 to 120 seconds.

Im Anschluss an die Trocknung in Schritt e) werden die getrockneten Festigkeitsträger in Verfahrensschritt f) auf 210 bis 250 °C erhitzt. Dies dient der Reaktion der entschützten Substanzen aus dem ersten Bad in Schritt a) mit den Substanzen aus dem zweiten Bad in Schritt d). Bevorzugt beträgt die Zeit des Erhitzens in Verfahrensschritt f) 30 bis 120 Sekunden.Following the drying in step e), the dried reinforcements are heated to 210 to 250 ° C. in process step f). This serves to react the deprotected substances from the first bath in step a) with the substances from the second bath in step d). Preferably, the heating time in process step f) is 30 to 120 seconds.

Sämtliche beschriebenen Trocknungsschritte und Schritte zum Erhitzen der Festigkeitsträger erfolgen in dem Fachmann bekannten dafür geeigneten Vorrichtungen, wie insbesondere 1- oder 2-Zonen-Öfen, durch welche die Festigkeitsträger bevorzugt kontinuierlich hindurch geführt werden.All of the described drying steps and steps for heating the reinforcements are carried out in devices known to those skilled in the art, such as in particular 1- or 2-zone furnaces, through which the reinforcements are preferably passed continuously.

Die mittels Verfahrensschritten a) bis f) behandelten Festigkeitsträger werden erfindungsgemäß in Verfahrensschritt g) mit wenigstens einer Gummierungsmischung gummiert, d.h. ummantelt. Die Gummierungsmischung enthält hierzu wenigstens einen Dienkautschuk, der ausgewählt ist aus der Gruppe bestehend aus natürlichem Polyisopren und/oder synthetischem Polyisopren und/oder Butadien-Kautschuk und/oder Styrol-Butadien-Kautschuk, und 20 bis 90 phr wenigstens eines Füllstoffes ausgewählt aus der Gruppe bestehend aus Ruß und/oder Kieselsäure.The strength carriers treated by method steps a) to f) are gummed according to the invention in step g) with at least one gumming mixture, i. jacketed. The gum mixture for this purpose contains at least one diene rubber selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or butadiene rubber and / or styrene-butadiene rubber, and 20 to 90 phr of at least one filler selected from the group consisting of carbon black and / or silica.

Im Folgenden werden die Bestandteile der Gummierungsmischung näher erläutert. Sämtliche Ausführungsformen gelten auch für die erfindungsgemäße Festigkeitsträgerlage, die durch das erfindungsgemäße Verfahren hergestellt wurde sowie den Fahrzeugreifen, der die erfindungsgemäße Festigkeitsträgerlage in wenigstens einem Bauteil aufweist. Dem Fachmann ist klar, dass die Bestandteile, insbesondere die Kautschuke, im vulkanisierten Reifen chemisch verändert vorliegen.In the following, the ingredients of the gum mixture are explained in more detail. All embodiments also apply to the reinforcement layer according to the invention, which was produced by the method according to the invention and the vehicle tire having the reinforcement layer according to the invention in at least one component. It is clear to the person skilled in the art that the constituents, in particular the rubbers, are chemically modified in the vulcanized tire.

Es kann sich um alle dem Fachmann bekannten Dienkautschuke der oben genannten Gruppe handeln.
Die Gummierungsmischung kann als Dienkautschuk Polyisopren (IR, NR) enthalten. Dabei kann es sich sowohl um cis-1,4-Polyisopren als auch um 3,4-Polyisopren handeln. Bevorzugt ist allerdings die Verwendung von cis-1,4-Polyisoprenen mit einem cis-1,4-Anteil > 90 Gew.-%. Zum einen kann solch ein Polyisopren durch stereospezifische Polymerisation in Lösung mit Ziegler-Natta-Katalysatoren oder unter Verwendung von fein verteilten Lithiumalkylen erhalten werden. Zum anderen handelt es sich bei Naturkautschuk (NR) um ein solches cis-1,4 Polyisopren, der cis-1,4-Anteil im Naturkautschuk ist größer 99 Gew.-%.
Enthält die Gummierungsmischung als Dienkautschuk Polybutadien (BR), kann es sich dabei sowohl um cis-1,4- als auch um Vinyl-Polybutadien (ca 10-90 Gew.-% Vinyl-Anteil) handeln. Bevorzugt ist die Verwendung von cis-1,4-Polybutadien mit einem cis-1,4-Anteil größer 90 Gew.-%, welches z. B. durch Lösungspolymerisation in Anwesenheit von Katalysatoren vom Typ der seltenen Erden hergestellt werden kann.These may be all diene rubbers of the abovementioned group known to the person skilled in the art.
The gum mixture may contain polyisoprene (IR, NR) as the diene rubber. These may be both cis-1,4-polyisoprene and 3,4-polyisoprene. However, preference is given to the use of cis-1,4-polyisoprenes having a cis-1,4 content of> 90% by weight. First, such a polyisoprene can be obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls. On the other hand, natural rubber (NR) is such a cis-1,4-polyisoprene, the cis-1,4-content in natural rubber is greater than 99% by weight.
If the rubber mixture contains polybutadiene (BR) as the diene rubber, these may be either cis-1,4- or vinyl-polybutadiene (about 10-90% by weight vinyl content). Preference is given to the use of cis-1,4-polybutadiene with a cis-1,4 content greater than 90 wt .-%, which z. By solution polymerization in the presence of rare earth type catalysts.

Als weitere Dienkautschuke sind Styrol-Butadien-Copolymere einsetzbar. Bei den Styrol-Butadien-Copolymeren kann es sich um lösungspolymerisierte Styrol-Butadien-Copolymere (S-SBR) mit einem Styrolgehalt, bezogen auf das Polymer, von ca. 10 bis 45 Gew.-% und einem Vinylgehalt (Gehalt an 1,2-gebundenem Butadien, bezogen auf das gesamte Polymer) von 10 bis 70 Gew.-% handeln, welches zum Beispiel unter Verwendung von Lithiumalkylen in organischem Lösungsmittel hergestellt werden können. Die S-SBR können auch gekoppelt und endgruppenmodifiziert sein. Es können aber auch emulsionspolymerisierte Styrol-Butadien-Copolymere (E-SBR) sowie Mischungen aus E-SBR und S-SBR eingesetzt werden. Der Styrolgehalt des E-SBR beträgt ca. 15 bis 50 Gew.-% und es können die aus dem Stand der Technik bekannten Typen, die durch Copolymerisation von Styrol und 1,3-Butadien in wässriger Emulsion erhalten wurden, verwendet werden.As further diene rubbers styrene-butadiene copolymers can be used. The styrene-butadiene copolymers may be solution-polymerized styrene-butadiene copolymers (S-SBR) having a styrene content, based on the polymer, of about 10 to 45% by weight and a vinyl content (content of 1.2 bound butadiene, based on the total polymer) of from 10 to 70% by weight, which can be prepared using, for example, lithium alkyls in organic solvent. The S-SBR can also be coupled and end-group modified. However, it is also possible to use emulsion-polymerized styrene-butadiene copolymers (E-SBR) and mixtures of E-SBR and S-SBR. The styrene content of the E-SBR is about 15 to 50% by weight, and the types known in the art obtained by copolymerization of styrene and 1,3-butadiene in aqueous emulsion can be used.

Die in der Mischung eingesetzten Dienkautschuke, insbesondere die Styrol-Butadien-Copolymere, können auch in teilweiser oder vollständig funktionalisierter Form eingesetzt werden. Die Funktionalisierung kann dabei mit Gruppen erfolgen, die mit den verwendeten Füllstoffen, insbesondere mit OH-Gruppen tragenden Füllstoffen, wechselwirken können. Es kann sich dabei z. B. um Funktionalisierungen mit Hydroxylgruppen und/oder Epoxygruppen und/oder Siloxangruppen und/oder Aminogruppen und/oder Phthalocyaningruppen und/oder Carboxygruppen und/oder Silan-Sulfid-Gruppen handeln.The diene rubbers used in the mixture, in particular the styrene-butadiene copolymers, can also be used in a partially or completely functionalized form become. The functionalization can be carried out with groups that can interact with the fillers used, in particular with OH-bearing fillers. It may be z. B. functionalizations with hydroxyl groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or phthalocyanine groups and / or carboxy groups and / or silane-sulfide groups act.

Die Gummierungsmischung enthält bevorzugt 25 bis 100 phr, besonders bevorzugt 50 bis 100 phr, wiederum besonders bevorzugt 70 bis 100 phr natürliches Polyisopren und/oder synthetisches Polyisopren, bevorzugt hierbei natürliches Polyisopren.The gum mixture preferably contains from 25 to 100 phr, particularly preferably from 50 to 100 phr, again particularly preferably from 70 to 100 phr of natural polyisoprene and / or synthetic polyisoprene, in which case natural polyisoprene is preferred.

Gemäß einer bevorzugten Weiterbildung der Erfindung enthält die Gummierungsmischung 100 phr wenigstens eines natürlichen Polyisoprens (NR) und/oder synthetischen Polyisoprens (IR), womit auch ein Gemisch aus NR und IR denkbar ist.According to a preferred embodiment of the invention, the gumming mixture contains 100 phr of at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR), whereby a mixture of NR and IR is conceivable.

Gemäß einer weiteren bevorzugten Weiterbildung der Erfindung enthält die Gummierungsmischung 25 bis 85 phr wenigstens eines natürlichen und/oder synthetischen Polyisoprens und 15 bis 50 phr wenigstens eines Butadien-Kautschuks und/oder 15 bis 50 phr wenigstens eines Styrol-Butadien-Kautschuks. Insbesondere mit diesen Kautschuken zeigen sich, insbesondere in Festigkeitsträgerlagen von Fahrzeugreifen, sehr gute physikalische Eigenschaften der Gummierungsmischung hinsichtlich der Verarbeitbarkeit, der Haltbarkeit und der Reißeigenschaften, während ein ausreichendes Haftungsniveau erzielt wird.According to a further preferred development of the invention, the gumming mixture contains 25 to 85 phr of at least one natural and / or synthetic polyisoprene and 15 to 50 phr of at least one butadiene rubber and / or 15 to 50 phr of at least one styrene-butadiene rubber. In particular, with these rubbers, particularly in reinforcing layers of vehicle tires, very good physical properties of the rubberizing mixture are manifested in terms of processability, durability and tear properties while achieving a sufficient level of adhesion.

Die in dieser Schrift verwendete Angabe phr (parts per hundred parts of rubber by weight) ist dabei die in der Kautschukindustrie übliche Mengenangabe für Mischungsrezepturen. Die Dosierung der Gewichtsteile der einzelnen Substanzen wird dabei stets auf 100 Gewichtsteile der gesamten Masse aller in der Mischung vorhandenen Kautschuke bezogen. Die Masse aller in der Mischung vorhandenen Kautschuke addiert sich zu 100. Die Gummierungsmischung kann als Füllstoffe Ruße und/oder Kieselsäuren enthalten, wobei die Füllstoffe in Kombination eingesetzt werden können und die Gesamtmenge aus Ruß und Kieselsäure 20 bis 90 phr beträgt. Bevorzugt werden 30 bis 90 phr, besonders bevorzugt 50 bis 70 phr wenigstens eines Rußes eingesetzt.The term phr (parts per hundred parts of rubber by weight) used in this document is the quantity used in the rubber industry for mixture formulations. The dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture. The mass of all rubbers present in the mixture adds up to 100. The gum mixture may contain as fillers carbon blacks and / or silicic acids, the fillers may be used in combination and the total amount of carbon black and silica is 20 to 90 phr. Preferably 30 to 90 phr, more preferably 50 to 70 phr of at least one carbon black are used.

Gemäß einer vorteilhaften Ausführungsform der Erfindung enthält die Gummierungsmischung 50 bis 100 phr wenigstens eines natürlichen und/oder synthetischen Polyisoprens und 30 bis 90 phr wenigstens eines Rußes. Hierdurch ergibt sich eine besonders gute strukturelle Haltbarkeit der hergestellten Festigkeitsträgerlage, insbesondere bei der Verwendung in Fahrzeugreifen.According to an advantageous embodiment of the invention, the gumming mixture contains 50 to 100 phr of at least one natural and / or synthetic polyisoprene and 30 to 90 phr of at least one carbon black. This results in a particularly good structural durability of the reinforcement layer produced, especially when used in vehicle tires.

Ferner können in geringen Mengen, 0 bis 10 phr, gemäß einer bevorzugten Ausführungsform von 0,1 bis 10 phr, weitere Füllstoffe wie Alumosilicate, Kreide, Stärke, Magnesiumoxid, Titandioxid oder Kautschukgele enthalten sein.
Weiterhin ist es denkbar, dass die Kautschukmischung Kohlenstoffnanoröhrchen (carbon nanotubes (CNT) inklusive diskreter CNTs, sogenannten hollow carbon fibers (HCF) und modifizierter CNT enthaltend eine oder mehrere funktionelle Gruppen, wie Hydroxy-, Carboxy und Carbonyl-Gruppen) enthält.
Auch Graphit und Graphene sowie sogenannte "carbon-silica dual-phase filler" sind als Füllstoff denkbar.
Bevorzugt ist die Gummierungsmischung jedoch frei von diesen weiteren Füllstoffen, d.h sie enthält bevorzugt 0 bis 0,001 phr dieser weiteren Füllstoffe.
Zinkoxid wird im Rahmen der vorliegenden Erfindung nicht als Füllstoff betrachtet.Furthermore, in small amounts, 0 to 10 phr, according to a preferred embodiment of 0.1 to 10 phr, further fillers such as aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gels may be included.
Furthermore, it is conceivable that the rubber mixture carbon nanotubes (CNT) including discrete CNTs, so-called hollow carbon fibers (HCF) and modified CNT containing one or more functional groups, such as hydroxyl, carboxyl and carbonyl groups).
Graphite and graphene as well as so-called "carbon-silica dual-phase filler" are conceivable as filler.
However, the gum mixture is preferably free of these further fillers, ie it preferably contains 0 to 0.001 phr of these further fillers.
Zinc oxide is not considered a filler in the present invention.

Wird Ruß in der Gummierungsmischung eingesetzt, handelt es sich bevorzugt um solche Typen, die eine STSA-Oberfläche (gemäß ASTM D 6556) von mehr als 30 m2/g, bevorzugt 30 bis 120 m2/g, aufweisen. Diese lassen sich einfach einmischen und gewährleisten einen geringen Wärmeaufbau.When carbon black is used in the gum mixture, it is preferably those types having an STSA surface area (in accordance with ASTM D 6556) of more than 30 m 2 / g, preferably 30 to 120 m 2 / g. These can be easily incorporated and ensure low heat build-up.

Gemäß einer bevorzugten Weiterbildung der Erfindung enthält die Gummierungsmischung wenigstens einen Ruß, der eine Jodadsorptionszahl gemäß ASTM D 1510 von 40 bis 110 g/kg und eine STSA-Oberfläche (gemäß ASTM D 6556) von 40 bis 120 m2/g aufweist. Mit einem derartigen Ruß wird insbesondere aufgrund der vergleichsweise hohen Oberfläche eine ausreichende Verstärkung und Festigkeit der Gummierungsmischung erreicht, um die Festigkeitsunterschiede zwischen Festigkeitsträgern und Kautschuk der Gummierungsmischung möglichst gut auszugleichen. Ein möglicher bevorzugter Rußtyp ist z.B. der Ruß N326 mit einer Jodadsorptionszahl gemäß ASTM D 1510 von 82 g/kg und einer STSA-Oberfläche (gemäß ASTM D 6556) von 76 m2/g. Ein weiterer möglicher bevorzugter Rußtyp ist z.B. der Ruß N660 mit einer Jodadsorptionszahl gemäß ASTM D 1510 von 36 g/kg und einer STSA-Oberfläche (gemäß ASTM D 6556) von 34 m2/g.According to a preferred development of the invention, the gumming mixture contains at least one carbon black which has an iodine adsorption number according to ASTM D 1510 of 40 to 110 g / kg and an STSA surface (according to ASTM D 6556) of 40 to 120 m 2 / g. With such a carbon black, in particular due to the comparatively high surface area, a sufficient reinforcement and strength of the rubberizing mixture is achieved in order to balance the differences in strength between reinforcements and rubber of the rubbering mixture as well as possible. A possible preferred type of carbon black is, for example, carbon black N326 having an iodine adsorption number according to ASTM D 1510 of 82 g / kg and an STSA surface (according to ASTM D 6556) of 76 m 2 / g. Another possible preferred type of carbon black is, for example, carbon black N660 having an iodine adsorption number according to ASTM D 1510 of 36 g / kg and an STSA surface (according to ASTM D 6556) of 34 m 2 / g.

Sind Kieselsäuren in der Mischung enthalten, kann es sich um die für Reifenkautschukmischungen üblichen Kieselsäuren handeln. Besonders bevorzugt ist es, wenn eine fein verteilte, gefällte Kieselsäure verwendet wird, die eine CTAB-Oberfläche (gemäß ASTM D 3765) von 30 bis 350 m2/g, vorzugsweise von 120 bis 250 m2/g, aufweist. Als Kieselsäuren können sowohl konventionelle Kieselsäure wie die des Typs VN3 (Handelsname) der Firma Evonik als auch hoch dispergierbare Kieselsäuren, so genannte HD-Kieselsäuren (z. B. Ultrasil 7000 der Firma Evonik), zum Einsatz kommen. Kieselsäuren werden bevorzugt in Mengen von weniger als 15 phr eingesetzt.If silicas are present in the mixture, these may be the silicas customary for tire rubber mixtures. It is particularly preferred when a finely divided, precipitated silica is used which has a CTAB surface area (according to ASTM D 3765) of 30 to 350 m 2 / g, preferably from 120 to 250 m 2 / g. As silicic acids it is possible to use both conventional silica such as VN3 (trade name) from Evonik and highly dispersible silicas, so-called HD silicas (eg Ultrasil 7000 from Evonik). Silicas are preferably used in amounts of less than 15 phr.

Zur Verbesserung der Verarbeitbarkeit und zur Anbindung der Kieselsäure und anderer ggf. vorhandener polarer Füllstoffe an den Dienkautschuk können Silan-Kupplungsagenzien in Kautschukmischungen eingesetzt werden. Hierbei können ein oder mehrere verschiedene Silan-Kupplungsagenzien in Kombination miteinander eingesetzt werden. Die Gummierungsmischung kann somit ein Gemisch verschiedener Silane enthalten.
Die Silan-Kupplungsagenzien reagieren mit den oberflächlichen Silanolgruppen der Kieselsäure oder anderen polaren Gruppen während des Mischens des Kautschuks bzw. der Kautschukmischung (in situ) oder bereits vor der Zugabe des Füllstoffes zum Kautschuk im Sinne einer Vorbehandlung (Vormodifizierung). Als Silan-Kupplungsagenzien können dabei alle dem Fachmann für die Verwendung in Kautschukmischungen bekannten Silan-Kupplungsagenzien verwendet werden. Solche aus dem Stand der Technik bekannten Kupplungsagenzien sind bifunktionelle Organosilane, die am Siliciumatom mindestens eine Alkoxy-, Cycloalkoxy- oder Phenoxygruppe als Abgangsgruppe besitzen und die als andere Funktionalität eine Gruppe aufweisen, die gegebenenfalls nach Spaltung eine chemische Reaktion mit den Doppelbindungen des Polymers eingehen kann. Bei der letztgenannten Gruppe kann es sich z. B. um die folgenden chemischen Gruppen handeln:

  • -SCN, -SH, -NH2 oder -Sx- (mit x = 2 bis 8).
So können als Silan-Kupplungsagenzien z. B. 3-Mercaptopropyltriethoxysilan, 3-Thiocyanato-propyltrimethoxysilan oder 3,3'-Bis(triethoxysilylpropyl)polysulfide mit 2 bis 8 Schwefelatomen, wie z. B. 3,3'-Bis(triethoxysilylpropyl)tetrasulfid (TESPT), das entsprechende Disulfid (TESPD) oder auch Gemische aus den Sulfiden mit 1 bis 8 Schwefelatomen mit unterschiedlichen Gehalten an den verschiedenen Sulfiden, verwendet werden. TESPT kann dabei beispielsweise auch als Gemisch mit Industrieruß (Handelsname X50S® der Firma Evonik) zugesetzt werden.
Bevorzugt wird ein Silan-Gemisch eingesetzt, welches zu 40 bis 100 Gew.-% Disulfide, besonders bevorzugt 55 bis 85 Gew.-% Disulfide und ganz besonders bevorzugt 60 bis 80 Gew.-% Disulfide enthält. Ein solches Gemisch ist z.B. unter dem Handelsnamen Si 261® der Firma Evonik erhältlich, welches z.B. in der DE 102006004062 A1 beschrieben ist. Auch geblockte Mercaptosilane, wie sie z. B. aus der WO 99/09036 bekannt sind, können als Silan-Kupplungsagens eingesetzt werden. Auch Silane, wie sie in der WO 2008/083241 A1 , der WO 2008/083242 A1 , der WO 2008/083243 A1 und der WO 2008/083244 A1 beschrieben sind, können eingesetzt werden. Verwendbar sind z. B. Silane, die unter dem Namen NXT in verschiedenen Varianten von der Firma Momentive, USA, oder solche, die unter dem Namen VP Si 363® von der Firma Evonik Industries vertrieben werden. Ferner ist es denkbar, dass eines der oben genannten Mercaptosilane, insbesondere 3-Mercaptopropyltriethoxysilan, in Kombination mit Verarbeitungshilfsmitteln (die unten aufgeführt sind), insbesondere PEG-Carbonsäureester, eingesetzt werden.
Gemäß einer bevorzugten Ausführungsform der Erfindung enthält die Gummierungsmischung eine Kombination aus 3-Mercaptopropyltriethoxysilan und PEG-Carbonsäureester, wodurch besonders gute Eigenschaften ergeben, und zwar insbesondere im Hinblick auf die zu lösende technische Aufgabe sowie insgesamt ein gutes Eigenschaftsniveau hinsichtlich der sonstigen Eigenschaften.
Weiterhin kann die Gummierungsmischung weitere Aktivatoren und/oder Agenzien für die Anbindung von Füllstoffen, insbesondere Ruß, enthalten. Hierbei kann es sich beispielsweise um die z.B. in der EP 2589619 A1 offenbarte Verbindung S-(3-Aminopropyl)Thioschwefelsäure und/oder deren Metallsalze handeln, wodurch sich insbesondere bei der Kombination mit wenigstens einem Ruß als Füllstoff sehr gute physikalische Eigenschaften der Gummierungsmischung ergeben.To improve the processability and to attach the silica and other optional polar fillers to the diene rubber silane coupling agents can be used in rubber mixtures. Here, one or more different silane coupling agents can be used in combination with each other. The gum mixture may thus contain a mixture of different silanes.
The silane coupling agents react with the superficial silanol groups of the silica or other polar groups during the mixing of the rubber or the rubber mixture (in situ) or even before the addition of the filler to the rubber in the sense of a pretreatment (pre-modification). All silane coupling agents known to the person skilled in the art for use in rubber mixtures can be used as silane coupling agents. Such out The coupling agents known in the prior art are bifunctional organosilanes which have at least one alkoxy, cycloalkoxy or phenoxy group as leaving group on the silicon atom and which, as other functionality, have a group which, if desired, can undergo a chemical reaction with the double bonds of the polymer after cleavage. In the latter group may be z. For example, they may be the following chemical groups:
  • -SCN, -SH, -NH 2 or -S x - (where x = 2 to 8).
Thus, as silane coupling agents z. For example, 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms, such as. For example, 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT), the corresponding disulfide (TESPD) or mixtures of the sulfides having 1 to 8 sulfur atoms with different contents of the various sulfides, are used. For example, TESPT can also be added as a mixture with carbon black (trade name X50S® from Evonik).
Preference is given to using a silane mixture which comprises 40 to 100% by weight of disulfides, particularly preferably 55 to 85% by weight of disulfides and very particularly preferably 60 to 80% by weight of disulfides. Such a mixture is available, for example, under the trade name Si 261® Evonik, which, for example, in the DE 102006004062 A1 is described. Also blocked mercaptosilanes, as z. B. from the WO 99/09036 are known, can be used as a silane coupling agent. Also silanes, as in the WO 2008/083241 A1 , of the WO 2008/083242 A1 , of the WO 2008/083243 A1 and the WO 2008/083244 A1 can be used, can be used. Suitable for. B. silanes, which are sold under the name NXT in different variants by the company Momentive, USA, or those sold under the name VP Si 363® by Evonik Industries. Furthermore, it is conceivable that one of the abovementioned mercaptosilanes, in particular 3-mercaptopropyltriethoxysilane, can be used in combination with processing aids (which are listed below), in particular PEG-carboxylic acid esters.
According to a preferred embodiment of the invention, the gumming mixture contains a combination of 3-mercaptopropyltriethoxysilane and PEG-carboxylic acid ester, which gives particularly good properties, in particular with regard to the technical problem to be solved and overall a good level of properties with regard to the other properties.
Furthermore, the gumming mixture can contain further activators and / or agents for the binding of fillers, in particular carbon black. This may be, for example, the example in the EP 2589619 A1 disclosed compound S- (3-aminopropyl) thiosulfuric acid and / or their metal salts, resulting in very good physical properties of the gumming especially when combined with at least one carbon black as a filler.

Es können in der Gummierungsmischung noch 0 bis 70 phr, bevorzugt 0,1 bis 60 phr, zumindest eines Weichmachers vorhanden sein. Hierzu gehören alle dem Fachmann bekannten Weichmacher wie aromatische, naphthenische oder paraffinische Mineralölweichmacher, wie z.B. MES (mild extraction solvate) oder TDAE (treated distillate aromatic extract), oder Rubber-to-Liquid-Öle (RTL) oder Biomass-to-Liquid-Öle (BTL; wie sie in der DE 10 2008 037714 A1 offenbart sind)) oder Öle auf Basis nachwachsender Rohstoffe (wie z. B. Rapsöl, Terpenöle (z. B. Orangenöle) oder Faktisse oder Weichmacherharze oder Flüssig-Polymere (wie Flüssig-BR), deren mittleres Molekulargewicht (Bestimmung per GPC = gel permeation chromatography, in Anlehnung an BS ISO 11344:2004) zwischen 500 und 20000 g/mol liegt. Werden in der Gummierungsmischung Flüssig-Polymere als Weichmacher eingesetzt, so gehen diese nicht als Kautschuk in die Berechnung der Zusammensetzung der Polymermatrix (phr-Berechnung) ein.
Bei der Verwendung von Mineralöl ist dieses bevorzugt ausgewählt aus der Gruppe, bestehend aus DAE (Destillated Aromatic Extracts) und/oder RAE (Residual Aromatic Extract) und/oder TDAE (Treated Destillated Aromatic Extracts) und/oder MES (Mild Extracted Solvents) und/oder naphthenische Öle.From 0 to 70 phr, preferably from 0.1 to 60 phr, of at least one plasticizer may be present in the gum mixture. These include all plasticizers known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as, for example, MES (mild extraction solvate) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid. Oils (BTL, as used in the DE 10 2008 037714 A1 disclosed)) or oils based on renewable raw materials (such as rapeseed oil, terpene oils (eg orange oils) or Faktisse or plasticizer resins or liquid polymers (such as liquid BR) whose average molecular weight (determination by GPC = gel permeation chromatography, based on BS ISO 11344: 2004) is between 500 and 20000 g / mol If liquid polymers are used as plasticizers in the gumming mixture, they are not used as rubber in the calculation of the composition of the polymer matrix (phr calculation). one.
When using mineral oil, this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.

Des Weiteren kann die Gummierungsmischung übliche Zusatzstoffe in üblichen Gewichtsteilen enthalten. Zu diesen Zusatzstoffen zählen

  1. A) Alterungsschutzmittel, wie z. B. N-Phenyl-N'-(1,3-dimethylbutyl)-p-phenylendiamin (6PPD), N,N'-Diphenyl-p-phenylendiamin (DPPD), N,N'-Ditolyl-p-phenylendiamin (DTPD), N-Isopropyl-N'-phenyl-p-phenylendiamin (IPPD), 2,2,4-Trimethyl-1,2-dihydrochinolin (TMQ) und andere Substanzen, wie sie beispielsweise aus J. Schnetger, Lexikon der Kautschuktechnik, 2. Auflage, Hüthig Buch Verlag, Heidelberg, 1991, S. 42-48 bekannt sind,
  2. B) Aktivatoren, wie z. B. Zinkoxid und Fettsäuren (z. B. Stearinsäure),
  3. C) Wachse,
  4. D) Harze, insbesondere Klebharze, die keine Weichmacherharze sind,
  5. E) Methylenakzeptoren, wie Resorcin und Resorcinäquivalente, und/oder Methylendonor/Formaldehydspender, wie z. B. Hexamethoxymethylmelamin (HMMM) und/oder Hexamethylentetramin (HMT)
  6. F) Mastikationshilfsmittel, wie z. B. 2,2'-Dibenzamidodiphenyldisulfid (DBD) und
  7. G) Verarbeitungshilfsmittel, wie z.B. Fettsäuresalze, wie z.B. Zinkseifen, und Fettsäureester und deren Derivate, wie z.B. PEG-Carbonsäureester.
Furthermore, the gum mixture may contain conventional additives in conventional parts by weight. These additives include
  1. A) anti-aging agents, such. N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine (6PPD), N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) and other substances such as J. Schnetger, Encyclopedia of Rubber Technology, 2nd edition, Hüthig Book Verlag, Heidelberg, 1991, pp. 42-48 are known,
  2. B) activators, such. Zinc oxide and fatty acids (eg stearic acid),
  3. C) waxes,
  4. D) Resins, in particular tackifier resins which are not plasticizer resins,
  5. E) methylene acceptors, such as resorcinol and resorcinol equivalents, and / or methylene donor / formaldehyde donors, such as. Hexamethoxymethylmelamine (HMMM) and / or hexamethylenetetramine (HMT)
  6. F) Mastikationshilfsmittel such. B. 2,2'-Dibenzamidodiphenyldisulfid (DBD) and
  7. G) processing aids, such as fatty acid salts, such as zinc soaps, and fatty acid esters and their derivatives, such as PEG carboxylic acid ester.

Die Vulkanisation wird in Anwesenheit von Schwefel und/oder Schwefelspendern durchgeführt, wobei einige Schwefelspender zugleich als Vulkanisationsbeschleuniger wirken können. Schwefel oder Schwefelspender werden im letzten Mischungsschritt in den vom Fachmann gebräuchlichen Mengen (0,4 bis 8 phr, Schwefel bevorzugt in Mengen von 0,4 bis 4 phr) der Gummierungsmischung zugesetzt. Die Vulkanisation kann auch in Anwesenheit von sehr geringen Schwefelmengen in Kombination mit schwefelspendenden Substanzen erfolgen.The vulcanization is carried out in the presence of sulfur and / or sulfur donors, with some sulfur donors can also act as a vulcanization accelerator. Sulfur or sulfur donors are added in the last mixing step in the amounts customary by the skilled person (0.4 to 8 phr, sulfur, preferably in amounts of 0.4 to 4 phr) of the gum mixture. The vulcanization can also be carried out in the presence of very small amounts of sulfur in combination with sulfur-donating substances.

Des Weiteren kann die Gummierungsmischung vulkanisationsbeeinflussende Substanzen wie Vulkanisationsbeschleuniger, Vulkanisationsverzögerer und Vulkanisationsaktivatoren in üblichen Mengen enthalten, um die erforderliche Zeit und/oder die erforderliche Temperatur der Vulkanisation zu kontrollieren und die Vulkanisateigenschaften zu verbessern. Die Vulkanisationsbeschleuniger können dabei zum Beispiel ausgewählt sein aus folgenden Beschleunigergruppen: Thiazolbeschleuniger wie z. B. 2-Mercaptobenzothiazol, Sulfenamidbeschleuniger wie z. B. Benzothiazyl-2-cyclohexylsulfenamid (CBS), Guanidinbeschleuniger wie z. B. N,N'-Diphenylguanidin (DPG), Dithiocarbamatbeschleuniger wie z. B. Zinkdibenzyldithiocarbamat, Disulfide, Thiophosphate. Die Beschleuniger können auch in Kombination miteinander eingesetzt werden, wobei sich synergistische Effekte ergeben können.Furthermore, the gum mixture may contain vulcanization-affecting substances such as vulcanization accelerators, vulcanization retarders and vulcanization activators in conventional amounts in order to control the time and / or temperature of vulcanization required and to improve the vulcanizate properties. The vulcanization accelerators may be selected, for example, from the following groups of accelerators: thiazole accelerators such as. B. 2-mercaptobenzothiazole, sulfenamide accelerators such as. B. benzothiazyl-2-cyclohexylsulfenamid (CBS), guanidine accelerators such as. N, N'-diphenylguanidine (DPG), dithiocarbamate accelerators such as. Zinc dibenzyldithiocarbamate, disulfides, Thiophosphates. The accelerators can also be used in combination with each other, which can result in synergistic effects.

Die Herstellung der Gummierungsmischung erfolgt auf herkömmliche Art und Weise, wobei zunächst in der Regel eine Grundmischung, die sämtliche Bestandteile mit Ausnahme des Vulkanisationssystems (Schwefel und vulkanisationsbeeinflussende Stoffe) enthält, in ein oder mehreren Mischstufen hergestellt wird und im Anschluss durch Zugabe des Vulkanisationssystems die Fertigmischung erzeugt wird. Anschließend wird die Mischung weiterverarbeitet.The preparation of the gum mixture is carried out in a conventional manner, wherein first of all a masterbatch containing all constituents except for the vulcanization system (sulfur and vulcanization-affecting substances) is prepared in one or more mixing stages followed by the addition of the curing system is produced. Subsequently, the mixture is processed further.

Die Gummierung der Festigkeitsträger in Schritt g) erfolgt ebenfalls auf dem Fachmann bekannte Weise.The gumming of the reinforcement in step g) also takes place in a manner known to those skilled in the art.

Im Folgenden werden die Eigenschaften der textilen Festigkeitsträger näher erläutert. Sämtliche Ausführungsformen gelten für das erfindungsgemäße Verfahren, die erfindungsgemäße Festigkeitsträgerlage sowie den erfindungsgemäßen Fahrzeugreifen.In the following, the properties of the textile reinforcement are explained in more detail. All embodiments are valid for the inventive method, the reinforcement layer according to the invention and the vehicle tire according to the invention.

Bevorzugt enthalten die textilen Festigkeitsträger Polyethylenterephthalat (PET) und/oder Polyethylennaphthalat (PEN) und/oder Polybutylenterephthalat (PBT) und/oder Polycarbonat (PC) und/oder Cellulose und/oder Celluloseester und/oder m-Aramid und/oder p-Aramid und/oder ein Gemisch aus m-Aramid und p-Aramid und/oder ein Polyamid, welches ausgewählt ist aus der Gruppe bestehend aus Polyamid 46 (PA 4.6) und/oder Polyamid 410 (PA 4.10) und/oder Polyamid 6 (PA 6) und/oder Polyamid 66 (PA 6.6 Polyhexamethylenadipinamid) und/oder Polyamid 612 (PA 6.12) und/oder Polyamid 1010 (PA 10.10) und/oder Polyamid 1212 (PA 12.12).The textile reinforcements preferably comprise polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN) and / or polybutylene terephthalate (PBT) and / or polycarbonate (PC) and / or cellulose and / or cellulose esters and / or m-aramid and / or p-aramid and / or a mixture of m-aramid and p-aramid and / or a polyamide which is selected from the group consisting of polyamide 46 (PA 4.6) and / or polyamide 410 (PA 4.10) and / or polyamide 6 (PA 6 ) and / or polyamide 66 (PA 6.6 polyhexamethylene adipamide) and / or polyamide 612 (PA 6.12) and / or polyamide 1010 (PA 10.10) and / or polyamide 1212 (PA 12.12).

Besonders bevorzugt enthalten die textilen Festigkeitsträger Polyethylenterephthalat (PET) und/oder Cellulose und/oder Celluloseester und/oder Polyamid 66 (PA 6.6 Polyhexamethylenadipinamid).The textile reinforcements particularly preferably comprise polyethylene terephthalate (PET) and / or cellulose and / or cellulose esters and / or polyamide 66 (PA 6.6 polyhexamethylene adipamide).

Die textilen Festigkeitsträger sind bevorzugt Corde, die wenigstens ein verdrehtes Garn aufweisen.
Hierbei sind alle im Stand der Technik bekannten Feinheiten (Titer in der Einheit dtex) und Verdrehungen der Corde und Garne denkbar. Zweckmäßig ist es, wenn der Titer eines jeden Garnes zwischen 200 und 5000 dtex beträgt und wenn die Verdrehung der Garne und Corde zwischen 100 und 800 t/m beträgt.
Die textilen Festigkeitsträger weisen die genannten Eigenschaften bevorzugt bereits vor dem Verfahrensschritt a) auf, d.h. sie werden erst verdreht und anschließend mit den Verfahrensschritten a) bis f) behandelt.
Für den Fall, dass die textilen Festigkeitsträger als Gewebe in die Gummierungsmischung eingebettet werden, erfolgt bevorzugt nach dem Verdrehen und vor der Behandlung gemäß der Verfahrensschritte a) bis f) wie dem Fachmann bekannt ein Webschritt.The textile reinforcement are preferably cords having at least one twisted yarn.
In this case, all known in the prior art subtleties (titer in the unit dtex) and twisting of the cords and yarns are conceivable. It is expedient if the denier of each yarn is between 200 and 5000 dtex and if the twist of the yarns and cords is between 100 and 800 t / m.
The textile reinforcing materials preferably have the stated properties already before process step a), ie they are first twisted and then treated with process steps a) to f).
In the event that the textile reinforcing elements are embedded as a tissue in the rubberizing mixture, preferably after twisting and before the treatment according to the process steps a) to f), as known to those skilled in a weaving step.

Gemäß einer bevorzugten Weiterbildung der Erfindung sind die Festigkeitsträger Corde aus jeweils einem Garn, womit ein verdrehtes Garn jeweils einen Cord darstellt.According to a preferred development of the invention, the reinforcing members are cords of a respective yarn, with which a twisted yarn represents a cord in each case.

Gemäß einer weiteren bevorzugten Weiterbildung der Erfindung sind die Festigkeitsträger Corde aus wenigstens zwei, besonders bevorzugt zwei, Garnen.According to a further preferred development of the invention, the strength carriers are cords of at least two, more preferably two, yarns.

Gemäß einer weiteren bevorzugten Weiterbildung der Erfindung enthält die erfindungsgemäße Festigkeitsträgerlage bzw. die des erfindungsgemäßen Fahrzeugreifens Corde aus unterschiedlich vielen Garnen als Festigkeitsträger.According to a further preferred embodiment of the invention, the reinforcement layer according to the invention or that of the vehicle tire according to the invention cords from different numbers of yarns as reinforcement.

Die erfindungsgemäße Festigkeitsträgerlage kann in allen Bauteilen eines Fahrzeugreifens eingesetzt werden, welche Festigkeitsträger enthalten, wobei sich die oben genannten Vorteile hinsichtlich der Substanzen und der Herstellung sowie der ausreichenden Haftung ergeben. Bei diesen Bauteilen handelt es sich insbesondere um die Karkasslage und/oder den Gürtel (in der oder den Gürtellagen) und/oder die Gürtelbandage und/oder den Wulstverstärker.The reinforcement layer according to the invention can be used in all components of a vehicle tire, which contain reinforcements, resulting in the above-mentioned advantages in terms of substances and the production and sufficient adhesion. These components are, in particular, the carcass ply and / or the belt (in the belt layer or layers) and / or the belt bandage and / or the bead reinforcement.

Die oben beschriebenen Vorteile werden auch bei der Verwendung der vorbeschriebenen Festigkeitsträgerlage zur Herstellung von weiteren elastomeren Erzeugnissen, wie Fördergurte, Antriebsriemen, Schläuche und Luftfederbälge erzielt.The advantages described above are also achieved in the use of the above-described reinforcement layer for the production of other elastomeric products, such as conveyor belts, drive belts, hoses and bellows.

Die Erfindung soll nun anhand der nachstehenden Beispiele näher erläutert werden.The invention will now be explained in more detail with reference to the following examples.

Erfindungsgemäßes Beispiel 1 (E1): Nylon-Corde als textile Festigkeitsträger, Pre-Dip enthaltend DMP-geblocktes HDI-Trimer, Dip enthaltend Malein-PolymerInventive Example 1 (E1): Nylon cords as textile reinforcements, pre-dip containing DMP-blocked HDI trimer, dip containing maleic polymer

Corde aus Nylon hergestellt aus jeweils zwei Nylon-Garnen mit einer Stärke von 940 dtex (940 x 2) wurden durch ein Pre-Dip enthaltend 95,54 Gew.-% Wasser und 0,75 Gew.-% Grilbond® G 1701 und 3,71 Gew.-% Acrafix PCI (DMP-geblocktes HDI-Trimer; Feststoffgehalt ca. 31,5 Gew.-%) getaucht. Anschließend wurden die Corde für 30 bis 120 Sekunden bei 165 °C getrocknet und anschließend auf 225 °C erhitzt.
Diese Corde wurden durch ein weiteres Dip-Bad getaucht, wobei dieses 54 Gew.-% Wasser und 42,4 Gew.-% VP-Latex (40 Gew.-% VP-Polymer in Wasser, d.h. 17 Gew.-% VP-Latex in dem Dip) und 3,6 Gew.-% RICOBOND 7004, Fa. Cray Valley (30 Gew.-% Malein-Polymer in Wasser: Mittelwert aus Herstellerangabe 25 bis 35 Gew.-%) enthielt. Anschließend wurde erneut für 30 bis 120 Sekunden bei 140 °C getrocknet und anschließend auf 235 °C erhitzt.Of nylon cords made of two nylon yarns having a thickness of 940 dtex (940 x 2) were passed through a pre-dip containing 95.54 wt .-% water and 0.75 wt .-% Grilbond ® G 1701 and 3 , 71% by weight of Acrafix PCI (DMP-blocked HDI trimer, solids content about 31.5% by weight). Subsequently, the cords were dried for 30 to 120 seconds at 165 ° C and then heated to 225 ° C.
These cords were dipped through another dip bath containing 54% by weight of water and 42.4% by weight of VP latex (40% by weight of VP polymer in water, ie 17% by weight of VP). Latex in the dip) and 3.6% by weight of RICOBOND 7004, Cray Valley (30% by weight of maleic polymer in water: mean value from manufacturer's information 25 to 35% by weight). It was then dried again at 140 ° C. for 30 to 120 seconds and then heated to 235 ° C.

Vergleichsbeispiel 1 (V1): Nylon-Corde als textile Festigkeitsträger, Pre-Dip enthaltend Caprolactam geblocktes MDI, Dip enthaltend Malein-PolymerComparative Example 1 (V1): Nylon cords as textile reinforcement, Pre-dip containing caprolactam blocked MDI, dip containing maleic polymer

Die Corde gemäß Vergleichsbeispiel 1 (V1) wurden analog E1 hergestellt mit der Ausnahme, dass anstelle von Acrafix PCI (DMP-geblocktes HDI-Trimer) Crrilbond® IL-6 (Caprolactam geblocktes MDI) verwendet wurde. Der Pre-Dip enthielt 96,71 Gew.-% Wasser und 2,54 Gew.-% Grilbond® IL-6 und 0,75 Gew.-% Grilbond® G 1701.
Bei sämtlichen Corden wurde der Verfahrensschritt der Trocknung, der eine Heißverstreckung beinhaltet, unbeeinträchtigt, d.h. wie der fachkundigen Person bekannt, ausgeführt. Dies dient dazu, die Eigenschaften, wie beispielsweise Reißdehnung, Bruchdehnung und Heißschrumpf des Cords durch gezielte Verstreckung auf das gewünschte Niveau einzustellen. wobei die auf den Cord angelegte Spannung zwischen Zug und Relaxation variiert wird.The cords of Comparative Example 1 (V1) was prepared analogously to E1, except that instead of Acrafix PCI (DMP blocked HDI-trimer) Crrilbond ® IL-6 (caprolactam-blocked MDI) was used. The pre-dip containing 96.71 wt .-% water and 2.54 wt .-% ® Grilbond IL-6 and 0.75 wt .-% Grilbond ® G 1,701th
For all the cords, the process step of drying involving hot drawing was undisturbed, ie, as known to those skilled in the art. This serves to improve the properties, such as elongation at break, elongation at break and heat shrinkage of the cord by targeted stretching on the to set the desired level. wherein the tension applied to the cord is varied between tension and relaxation.

Vergleich der Haftung Beispiel 1 (E1) vs. Vergleichsbeispiel 1 (V1)Comparison of liability Example 1 (E1) vs. Comparative Example 1 (V1)

Mit den unterschiedlich behandelten Corden wurden Haftversuche, so genannte Peel-Tests, gemäß ISO 36:2011 (E) mit Auswertung gemäß DIN ISO 6133 ohne Alterung vorgenommen. Dazu wurden die Festigkeitsträgercorde mit einer unvulkanisierten Gummierungsmischung mit der Zusammensetzung gemäß Tabelle 1 gummiert (gemäß Verfahrensschritt g)) und anschließend vulkanisiert. Die Gummierung erfolgt, in dem die Corde auf bzw. zwischen kalandrierte dünne Gummiplatten der Gummierungsmischung gelegt und anschließend der gesamte Probekörper in der Heizpresse zusammengedrückt wird.
Anschließend wurde die Kraft zum Abschälen der Mischung von den Corden ermittelt (Haftung) und die Bedeckung der Corde mit Mischung nach dem Abziehen optisch ermittelt. 5 bedeutet vollständige Bedeckung, 0 bedeutet, dass keine Gummireste mehr auf dem Cord verblieben sind. Ferner wurden die Bruchkraft, die Dehnung bei 45 N, die Schrumpfung bei 180 °C sowie die Rest-Schrumpfung in Anlehnung an ASTM D 855 ermittelt.Adhesive tests, so-called peel tests, according to ISO 36: 2011 (E) with evaluation in accordance with DIN ISO 6133 without aging were carried out with the differently treated cords. For this purpose, the strength carrier cords were rubberized with an uncured gum mixture having the composition according to Table 1 (according to process step g)) and then vulcanized. The gumming takes place by placing the cords on or between calendered thin rubber sheets of the gumming compound and then compressing the entire specimen in the heating press.
Then, the force for peeling off the mixture from the cords was determined (adhesion), and the coverage of the cords with mixture after peeling was optically determined. 5 means complete coverage, 0 means no rubber remains on the cord. Furthermore, the breaking force, the elongation at 45 N, the shrinkage at 180 ° C and the residual shrinkage based on ASTM D 855 were determined.

Die Ergebnisse der Haftversuche sind in Tabelle 2 dargestellt. Tabelle 1: Bestandteile der Gummierungsmischung Bestandteile Menge (phr) NR/IR 70 BR/SBR 30 Ruß N660 50 Weichmacheröl/Klebharz 5 Sonstige Zusatzstoffe a) 8 Harz aus Resorcin und Formaldehydspender 5 Schwefel und Beschleuniger 3,3 a) Alterungsschutzmittel, ZnO, Stearinsäure The results of the adhesion tests are shown in Table 2. Table 1: Components of the gum mixture ingredients Quantity (phr) NR / IR 70 BR / SBR 30 Soot N660 50 Processing oil / adhesive resin 5 Other additives a) 8th Resin from resorcinol and formaldehyde donor 5 Sulfur and accelerator 3.3 a) anti-aging agent, ZnO, stearic acid

Die mittels dem erfindungsgemäßen Verfahren hergestellte Festigkeitsträgerlage zeigt wie in Tabelle 2 erkennbar eine vergleichbare oder sogar verbesserte Haltbarkeit, da die Haftung der Festigkeitsträger an die Gummierungsmischung verbessert ist. Ferner werden im erfindungsgemäßen Beispiel die Nachteile, die mit Resorcin und Formaldehyd verbunden sind, vermieden. Tabelle 2 Eigenschaft Einheit V1 E1 Haftung N/25mm 190,7 195,4 Bedeckung (1 bis 5) 3,5 4,5 Bruchkraft N 150 152 Dehnung bei 45 N % 5,4 5,2 Schrumpfung bei 180 °C % 6,1 6,0 Rest-Schrumpfung % 3,7 3,6 The reinforcement layer produced by means of the method according to the invention shows, as can be seen in Table 2, a comparable or even improved durability, since the adhesion of the reinforcements to the rubber coating mixture is improved. Furthermore, in the example of the invention, the disadvantages associated with resorcinol and formaldehyde are avoided. Table 2 property unit V1 E1 liability N / 25mm 190.7 195.4 covering (1 to 5) 3.5 4.5 breaking force N 150 152 Elongation at 45 N % 5.4 5.2 Shrinkage at 180 ° C % 6.1 6.0 Residual shrinkage % 3.7 3.6

Erfindungsgemäßes Beispiel 2 (E2): Polyester-Corde als textile Festigkeitsträger, Pre-Dip enthaltend MEKO geblocktes HDI-Trimer, Dip enthaltend Malein-PolymerInventive Example 2 (E2): polyester cords as textile reinforcements, pre-dip containing MEKO blocked HDI trimer, dip containing maleic polymer

Corde aus Polyester hergestellt aus jeweils zwei Polyester-Garnen (Polyethylenterephthalat PET) mit einer Stärke von 1440 dtex (1440 x 2) wurden durch ein Pre-Dip enthaltend 96,71 Gew.-% Wasser und 0,75 Gew.-% Crrilbond® G 1701 und 2,54 Gew.-% Edolan® XCIB (MEKO-geblocktes HDI-Trimer) getaucht. Anschließend wurden die Corde für 30 bis 120 Sekunden bei 160 °C getrocknet und anschließend auf 235 °C erhitzt.
Diese getrockneten Corde wurden durch ein weiteres Dip-Bad getaucht, wobei dieses 54 Gew.-% Wasser und 42,4 Gew.-% VP-Latex (40 Gew.-% VP-Polymer in Wasser) und 3,6 Gew.-% RICOBOND 7004, Fa. Cray Valley (30 Gew.-% Malein-Polymer in Wasser: Mittelwert aus Herstellerangabe 25 bis 35 Gew.-%) enthielt. Anschließend wurde erneut für 30 bis 120 Sekunden bei 165 °C getrocknet und anschließend auf 235 °C erhitzt.Cords made of polyester, each made of two polyester yarns (polyethylene terephthalate PET) with a thickness of 1440 dtex (1440 x 2) were obtained by a pre-dip containing 96.71% by weight of water and 0.75% by weight of Crrilbond® G wt .-% EDOLAN ® XCIB (MEKO blocked HDI-trimer) immersed 1701 and 2.54. Subsequently, the cords were dried for 30 to 120 seconds at 160 ° C and then heated to 235 ° C.
These dried cords were dipped through another dip bath containing 54% by weight of water and 42.4% by weight of VP latex (40% by weight VP polymer in water) and 3.6% by weight. % RICOBOND 7004, Cray Valley (30 wt .-% maleic polymer in water: average from manufacturer 25 to 35 wt .-%) contained. It was then dried again at 165 ° C. for 30 to 120 seconds and then heated to 235 ° C.

Erfindungsgemäßes Beispiel 3 (E3): Polyester-Corde als textile Festigkeitsträger, Pre-Dip enthaltend MEKO geblocktes TDI-Trimer, Dip enthaltend Malein-PolymerInventive Example 3 (E3): polyester cords as textile reinforcement, pre-dip containing MEKO blocked TDI trimer, dip containing maleic polymer

Die Corde gemäß erfindungsgemäßem Beispiel 3 (E3) wurden analog E2 hergestellt mit der Ausnahme, dass anstelle von Edolan® XCIB (MEKO-geblocktem HDI-Trimer) 2,54 Gew.-% Baygard® EDW (MEKO geblocktes TDI) verwendet wurde.The cords according to Inventive Example 3 (E3) were prepared analogously E2 prepared with the exception that instead of EDOLAN ® XCIB (MEKO a blocked HDI-trimer) (MEKO blocked TDI) 2.54 wt .-% Baygard EDW ® was used.

Vergleichsbeispiel 2 (V2): Polyester-Corde als textile Festigkeitsträger, Pre-Dip enthaltend Caprolactam geblocktes MDI, Dip enthaltend Malein-PolymerComparative Example 2 (V2): polyester cords as textile reinforcements, pre-dip containing caprolactam blocked MDI, dip containing maleic polymer

Die Corde gemäß Vergleichsbeispiel 2 (V2) wurden analog E2 hergestellt mit der Ausnahme, dass anstelle von von Edolan® XCIB (MEKO-geblocktem HDI-Trimer) 2,54 Gew.-% Grilbond IL-6 (Caprolactam geblocktes MDI) verwendet wurde.The cords according to Comparative Example 2 (C2) were prepared analogously to E2 with the exception that was used instead of of EDOLAN ® XCIB (MEKO a blocked HDI-trimer) 2.54 wt .-% Grilbond IL-6 (caprolactam-blocked MDI).

Bei sämtlichen Corden wurde der Verfahrensschritt der Trocknung, der eine Heißverstreckung beinhaltet, unbeeinträchtigt durch das Maleinimid-Polymer, d.h. wie der fachkundigen Person bekannt, ausgeführt. Dies dient dazu, die Eigenschaften, wie beispielsweise Reißdehnung, Bruchdehnung und Heißschrumpf des Cords durch gezielte Verstreckung auf das gewünschte Niveau einzustellen. wobei die auf den Cord angelegte Spannung zwischen Zug und Relaxation variiert wird.In all the cords, the drying step, which involves hot drawing, was unaffected by the maleimide polymer, i. as known to the skilled person. This serves to adjust the properties, such as elongation at break, elongation at break and heat shrinkage of the cord by targeted stretching to the desired level. wherein the tension applied to the cord is varied between tension and relaxation.

Die Corde der Beispiele E2 sowie E3 und V2 wurden analog zu den Beispielen E1 und V1 mit einer Gummierungsmischung gemäß Tabelle 2 gummiert und anschließend die Haftung und Bedeckung sowie die Steifigkeit wie oben beschrieben getestet.
Ferner wurden die Bruchkraft, die Dehnung bei 45 N, die Schrumpfung bei 180 °C sowie die Rest-Schrumpfung in Anlehnung an ASTM D 855 ermittelt.The cords of Examples E2 and E3 and V2 were gummed analogously to Examples E1 and V1 with a gumming mixture according to Table 2 and then the adhesion and coverage as well as the rigidity were tested as described above.
Furthermore, the breaking force, the elongation at 45 N, the shrinkage at 180 ° C and the residual shrinkage based on ASTM D 855 were determined.

Die Ergebnisse sind in Tabelle 3 zusammengefasst. Tabelle 3 Eigenschaft Einheit V2 E2 E3 Haftung N/25mm 108 125 125 Bedeckung (1 bis 5) 4 5 4,7 Bruchkraft N 201 198 198 Dehnung bei 45 N % 2,9 2,9 2,9 Schrumpfung bei 180 °C % 5,1 4,8 4,9 Rest-Schrumpfung % 4,9 4,6 4,7 The results are summarized in Table 3. Table 3 property unit V2 E2 E3 liability N / 25mm 108 125 125 covering (1 to 5) 4 5 4.7 breaking force N 201 198 198 Elongation at 45 N % 2.9 2.9 2.9 Shrinkage at 180 ° C % 5.1 4.8 4.9 Residual shrinkage % 4.9 4.6 4.7

Ein erfindungsgemäßer Fahrzeugreifen, bevorzugt Fahrzeugluftreifen, der in wenigstens einem Bauteil wenigstens eine erfindungsgemäß hergestellte Festigkeitsträgerlage enthält, zeichnet sich durch eine zum Stand der Technik vergleichbare Haltbarkeit aus, wobei bei der Haftungsaktivierung in den Dips auf den Einsatz von freiem Resorcin und Formaldehyd sowie Resorcin-Formaldehyd-Vorkondensaten verzichtet werden kann.A vehicle tire according to the invention, preferably a pneumatic vehicle tire, which contains at least one reinforcement layer produced according to the invention in at least one component, is distinguished by a durability comparable to the prior art, with the activation of adhesion in the dips being based on the use of free resorcinol and formaldehyde as well as resorcinol-formaldehyde Pre-condensates can be dispensed with.

Claims (12)

Verfahren zur Herstellung einer Festigkeitsträgerlage umfassend textile Festigkeitsträger für elastomere Erzeugnisse, wobei das Verfahren wenigstens die Verfahrensschritte in folgender Reihenfolge umfasst: a) Tauchen der textilen Festigkeitsträger in wenigstens einem ersten Bad, welches wenigstens ein geblocktes Polyisocyanat enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, und b) Anschließendes Trocknen der Festigkeitsträger bei 120 bis 180 °C, und c) Anschließendes Erhitzen der Festigkeitsträger auf 160 bis 230 °C, und d) Tauchen der textilen Festigkeitsträger in wenigstens einem zweiten Bad, welches wenigstens ein Malein-funktionalisertes Polymer enthält und frei ist von freiem Resorcin und freiem Formaldehyd sowie deren Vorkondensaten, und e) Anschließendes Trocknen der Festigkeitsträger bei 120 bis 155 °C, und f) Anschließendes Erhitzen der Festigkeitsträger auf 210 bis 250 °C, und g) Gummierung der mittels a) bis f) vorbehandelten textilen Festigkeitsträger mit einer Gummierungsmischung, die wenigstens einen Dienkautschuk, der ausgewählt ist aus der Gruppe bestehend aus natürlichem Polyisopren und/oder synthetischem Polyisopren und/oder Butadien-Kautschuk und/oder Styrol-Butadien-Kautschuk, und
20 bis 90 phr wenigstens eines Füllstoffes ausgewählt aus der Gruppe bestehend aus Ruß und/oder Kieselsäure enthält. Process for producing a reinforcement layer comprising textile reinforcement for elastomeric products, the method comprising at least the steps in the following order: a) immersing the textile reinforcement in at least one first bath containing at least one blocked polyisocyanate and is free of free resorcinol and free formaldehyde and their precondensates, and b) Subsequent drying of the reinforcements at 120 to 180 ° C, and c) then heating the reinforcements to 160 to 230 ° C, and d) immersing the textile reinforcement in at least one second bath, which contains at least one malein-functionalized polymer and is free of free resorcinol and free formaldehyde and their precondensates, and e) then drying the strength members at 120 to 155 ° C, and f) then heating the reinforcements to 210 to 250 ° C, and g) gumming of the textile reinforcements pretreated by means of a) to f) with a gumming composition comprising at least one diene rubber selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or butadiene rubber and / or styrene-butadiene rubber. Rubber, and
20 to 90 phr at least one filler selected from the group consisting of carbon black and / or silica. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Polyisocyanat eine Funktionalität von größer oder gleich 3 aufweist.A method according to claim 1, characterized in that the polyisocyanate has a functionality of greater than or equal to 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das Polyisocyanat ausgewählt ist aus der Gruppe bestehend aus geblocktem 1,6-Hexamethylendiisocyanat-Trimer und dessen geblockten höheren Homologen sowie geblocktem Toluoldiisocyanat-Trimer und dessen geblockten höheren Homologen sowie geblocktem Isophorondiisocyanat-Trimer und dessen geblockten höheren Homologen.A method according to claim 2, characterized in that the polyisocyanate is selected from the group consisting of blocked 1,6-hexamethylene diisocyanate trimer and its blocked higher homologs and blocked toluene diisocyanate trimer and its blocked higher homologs, as well as blocked isophorone diisocyanate trimer and its blocked higher homologs. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Schutzgruppen des oder der geblockten Polyisocyanat(e) ausgewählt sind aus der Gruppe bestehend aus Ketoximen, wie bevorzugt Methylethylketoxim, und/oder Pyrazol-Derivaten, wie bevorzugt 3,5-Dimethylpyrazol, und/oder Estern, wie bevorzugt Malonsäureester oder Caprolactam oder alkylierte Phenole.Method according to one of the preceding claims, characterized in that the protecting groups of the blocked polyisocyanate (s) are selected from the group consisting of ketoximes, such as preferably methyl ethyl ketoxime, and / or pyrazole derivatives, such as preferably 3,5-dimethylpyrazole, and or esters, such as preferably malonic acid esters or caprolactam or alkylated phenols. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das Malein-Polymer ein Molekulargewicht von 5000 bis 20000 g/mol aufweist.Method according to one of the preceding claims, characterized in that the maleic polymer has a molecular weight of 5000 to 20,000 g / mol. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das Polymer in Schritt d) ein Malein-funktionalisiertes Polybutadien ist.Method according to one of the preceding claims, characterized in that the polymer in step d) is a maleic-functionalized polybutadiene. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die textilen Festigkeitsträger Polyethylenterephthalat (PET) und/oder Polyethylennaphthalat (PEN) und/oder Polybutylenterephthalat (PBT) und/oder Polycarbonat (PC) und/oder Cellulose und/oder Celluloseester und/oder m-Aramid und/oder p-Aramid und/oder ein Gemisch aus m-Aramid und p-Aramid und/oder ein Polyamid, welches ausgewählt ist aus der Gruppe bestehend aus Polyamid 46 (PA 4.6) und/oder Polyamid 410 (PA 4.10) und/oder Polyamid 6 (PA 6) und/oder Polyamid 66 (PA 6.6 Polyhexamethylenadipinamid) und/oder Polyamid 612 (PA 6.12) und/oder Polyamid 1010 (PA 10.10) und/oder Polyamid 1212 (PA 12.12), enthalten.Method according to one of the preceding claims, characterized in that the textile reinforcement polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN) and / or polybutylene terephthalate (PBT) and / or polycarbonate (PC) and / or cellulose and / or cellulose esters and / or m-aramid and / or p-aramid and / or a mixture of m-aramid and p-aramid and / or a polyamide which is selected from the group consisting of polyamide 46 (PA 4.6) and / or polyamide 410 (PA 4.10 ) and / or polyamide 6 (PA 6) and / or polyamide 66 (PA 6.6 polyhexamethylene adipamide) and / or polyamide 612 (PA 6.12) and / or polyamide 1010 (PA 10.10) and / or polyamide 1212 (PA 12.12). Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Gummierungsmischung 50 bis 100 phr wenigstens eines natürlichen und/oder synthetischen Polyisoprens und 30 bis 90 phr wenigstens eines Rußes enthält.Method according to one of the preceding claims, characterized in that the gumming mixture contains 50 to 100 phr of at least one natural and / or synthetic polyisoprene and 30 to 90 phr of at least one carbon black. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Ruß der Gummierungsmischung eine Jodadsorptionszahl gemäß ASTM D 1510 von 40 bis 110 g/kg und eine STSA-Oberfläche (gemäß ASTM D 6556) von 40 bis 120 m2/g aufweist.Method according to one of the preceding claims, characterized in that the carbon black of the gumming mixture has an iodine adsorption number according to ASTM D 1510 of 40 to 110 g / kg and an STSA surface (according to ASTM D 6556) of 40 to 120 m 2 / g. Festigkeitsträgerlage für elastomere Erzeugnisse, wobei sie durch wenigstens ein Verfahren nach einem der Ansprüche 1 bis 9 hergestellt ist.Reinforcing layer for elastomeric products, wherein it is produced by at least one method according to one of claims 1 to 9. Fahrzeugreifen, enthaltend in wenigstens einem Bauteil wenigstens eine Festigkeitsträgerlage nach Anspruch 10.Vehicle tire comprising at least one reinforcement layer according to claim 10 in at least one component. Fahrzeugreifen nach Anspruch 11, dadurch gekennzeichnet, dass er die Festigkeitsträgerlage wenigstens in der Karkasslage und/oder der Gürtelbandage und/oder dem Gürtel und/oder dem Wulstverstärker aufweist.A vehicle tire according to claim 11, characterized in that it comprises the reinforcement layer at least in the carcass ply and / or the belt bandage and / or the belt and / or the bead reinforcement.
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