EP3258008A1 - Procédé de fabrication d'une couche de renfort, couche de renfort et pneu de véhicule - Google Patents

Procédé de fabrication d'une couche de renfort, couche de renfort et pneu de véhicule Download PDF

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Publication number
EP3258008A1
EP3258008A1 EP17169841.8A EP17169841A EP3258008A1 EP 3258008 A1 EP3258008 A1 EP 3258008A1 EP 17169841 A EP17169841 A EP 17169841A EP 3258008 A1 EP3258008 A1 EP 3258008A1
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Prior art keywords
blocked
polyamide
free
group
reinforcement
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German (de)
English (en)
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EP3258008B1 (fr
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Nermeen Nabih
Thomas Kramer
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Continental Reifen Deutschland GmbH
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Continental Reifen Deutschland GmbH
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693Treating 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/73Treating 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
    • D06M11/74Treating 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/77Treating 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
    • D06M11/79Treating 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating 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
    • D06M13/395Isocyanates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • D06M2101/08Esters or ethers of cellulose
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • D06M2101/36Aromatic 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, in which an influence on the physical properties of the textile reinforcement is avoided, at the same time the prepared reinforcement layer have an equal or even improved adhesion between reinforcements and gum mixture and also to 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 a structural durability which is comparable to the state of the art, 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 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 diisocyanate and is free of free resorcinol and free formaldehyde and their precondensates, the protecting groups of the blocked diisocyanate (s ) are selected from the group consisting of oximes, such as preferably ketoximes such as methyl ethyl ketoxime, and / or pyrazole derivatives, such as preferably 3,5-dimethylpyrazole.
  • oximes such as preferably ketoximes such as methyl ethyl ketoxime
  • pyrazole derivatives such as preferably 3,5-dimethylpyrazole.
  • the first bath is preferably an aqueous dispersion which may contain, in addition to water and the blocked diisocyanate, at least one epoxy compound such as glycerol triglyceride ether and / or bisphenol A diglycidyl ether and / or 2,3-epoxybutyl azidoformate and / or sorbitol polyglycidyl ether.
  • 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.
  • 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 diisocyanates are understood to mean molecules which carry two blocked, ie protected, terminal isocyanate groups or formally arise by condensation of molecules with two isocyanate groups. These may be monomers, dimers, trimers or higher homologues of the diisocyanates.
  • diisocyanate monomers examples include methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate.
  • MDI methylenediphenyl diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • isophorone diisocyanate examples include methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate.
  • Diisocyanate trimers or higher homologs are grouped together as polyisocyanates and are compounds having three or more terminal isocyanate groups. They arise z. B. formally by condensation of three or more molecules, each with two isocyanate groups (diisocyanates). Formally, the condensation usually takes place via in each case one isocyanate group of each molecule, so that the polyisocyanates correspondingly have three or more 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 , Because z. B.
  • the 1,6-hexamethylene diisocyanate trimer formally formed by condensation of three 1,6-hexamethylene diisocyanate molecules on each one isocyanate group of the diisocyanates, the 1,6-hexamethylene diisocyanate trimer has three (leftover) terminal isocyanate groups on.
  • the higher homologues of the precondensed isocyanates give, depending on the degree of condensation, average functionalities of greater than three.
  • 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 diisocyanate has a functionality greater than 2.
  • the blocked diisocyanate is a blocked polyisocyanate having a functionality of greater than or equal to 3, particularly preferably 3 to 5, very particularly 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 and blocked toluene diisocyanate trimer and its blocked higher homologues as well as blocked isophorone diisocyanate trimer and its blocked higher homologs. More preferably, the blocked polyisocyanate is blocked 1,6-hexamethylene diisocyanate trimer or blocked toluene diisocyanate trimer, most preferably 1,6-hexamethylene diisocyanate trimer.
  • HDI blocked 1,6-hexamethylene diisocyanate trimer
  • the protecting groups of the blocked diisocyanate (s) are selected from the group consisting of oximes, such as preferably ketoximes such as methyl ethyl ketoxime, and / or pyrazole derivatives, such as preferably 3,5-dimethylpyrazole.
  • Oxime and pyrazoles require a comparatively low temperature for cleaving off the protective groups, so that in the process according to the invention in particular temperature-sensitive textile reinforcements are spared.
  • the protecting groups of the blocked diisocyanate (s) are selected from the group consisting of methyl ethyl ketoxime (MEKO), and / or 3,5-dimethylpyrazole (DMP).
  • 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 140 ° C.
  • the temperature must not be too high, so that there is no deprotection of the blocked isocyanates, to prevent an undesirable side reaction with the evaporating (residual) water.
  • the duration of the drying step b) is preferably 30 to 120 seconds.
  • the dried reinforcements in process step c) are heated to 160 to 200 ° C to deprotect the isocyanates. It is essential to the invention that the diisocyanates carry the protective groups mentioned in process step a), so that heating to more than 200 ° C. can be dispensed with. This protects the textile reinforcement and avoids an influence that adversely affects the subsequent adhesion to the rubber compound.
  • the method according to the invention is comparatively energy-saving, but nevertheless a very good adhesion is achieved, at the same time waiving environmental and harmful substances.
  • 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, the resulting maleimide polymer has both maleic groups 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 from 0 to 0.01% by weight, but preferably 0% by weight, of such substances.
  • the combination of the dipping containing the maleic polymer according to step d) with said pre-dip containing the selection of blocked diisocyanates according to step a) leads to very good adhesion results of reinforcing agents to the respective surrounding gum mixture, the advantages also and in particular by avoiding influencing the physical properties of the textile materials.
  • RFL pretreatments 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 means of process steps a) to f) are, according to the invention, in process step g) with at least one gumming mixture gummed, ie encased.
  • 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 wt .-% and a vinyl content (content of 1,2-bound butadiene, based on the total polymer) of 10 to 70 wt. %, 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 fully functionalized form.
  • 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.
  • the rubberizing mixture particularly in reinforcing layers of vehicle tires, very good physical properties of the rubberizing mixture are evident in terms of processability, durability and tear properties while achieving a satisfactory level of adhesion.
  • phr parts per hundred parts of rubber by weight
  • 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, particularly 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.
  • 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 having 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 having 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 done in Presence of very low amounts of sulfur in combination with sulfur-donating substances done.
  • 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. 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 ester 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 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
  • PC Poly
  • 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 preferably first twisted and then treated with process steps a) to g). 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 84.05 wt .-% water and 2.01 wt .-% Grilbond ® G 1701 and 13 , 94% 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 140 ° C and then heated to 200 ° C.
  • Acrafix PCI DMP-blocked HDI trimer, solids content about 31.5% by weight
  • cords were then dipped through another dip bath containing 54 wt% water and 42.4 wt% VP latex (40 wt% VP polymer in water, ie 17 wt% 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 data 25 to 35% by weight). It was then dried again for 30 to 120 seconds at 150 ° C and then heated to 235 ° C.
  • RICOBOND 7004 Cray Valley
  • Example 2 Nylon cords as textile reinforcements, pre-dip containing MEKO-blocked HDI trimer, dip containing maleic polymer
  • nylon cords made of two nylon yarns having a thickness of 940 dtex (940 x 2) were passed through a pre-dip containing 88.35 wt .-% water and 1.29 wt .-% Grilbond ® G 1701 and 10 wt .-% EDOLAN ® XCIB (MEKO blocked HDI-trimer) immersed 36th Subsequently, the cords were dried for 30 to 120 seconds at 140 ° C and then heated to 200 ° C.
  • cords were then dipped through another dip bath containing 54 wt% water and 42.4 wt% VP latex (40 wt% VP polymer in water, ie 17 wt% 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 data 25 to 35% by weight). It was then dried again for 30 to 120 seconds at 150 ° C and then heated to 235 ° C.
  • RICOBOND 7004 Cray Valley
  • Comparative Example 1 Nylon cords as textile reinforcement, Pre-dip containing caprolactam blocked MDI, dip containing maleic polymer
  • the cords of Comparative Example 1 (V1) was prepared analogously to E1, except that instead of Acrafix PCI (DMP blocked HDI-trimer) Crilbond ® IL-6 (caprolactam-blocked MDI) was used.
  • the pre-dip containing 93.5 wt .-% water and 3.42 wt .-% ® Grilbond IL-6 and 3.08 wt .-% Grilbond ® G 1701.
  • the first drying step was carried out at 165 ° C and then Heat to 225 ° C as caprolactam requires a higher temperature for deprotection over the DMP protecting group.
  • the process step of drying involving hot drawing was undisturbed, ie, as known to those skilled in the art. 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.
  • 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.
  • the reinforcement layer produced by means of the method according to the invention shows, as can be seen in Table 2, a comparable durability, since the adhesion of the reinforcements to the rubber mixture is comparable, the method according to the invention being more energy-saving and gentler for the textile reinforcements. Further, in the example of the invention, the disadvantages associated with free resorcinol and formaldehyde in the dip are avoided.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP17169841.8A 2016-06-14 2017-05-08 Procédé de fabrication d'une couche de renfort Active EP3258008B1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3597816A1 (fr) * 2018-07-19 2020-01-22 EMS-Patent AG Compositions de bain destinées au traitement des inserts de renfort
EP3617285A1 (fr) * 2018-08-28 2020-03-04 Cordenka GmbH & Co. KG Procédé d'équipement des supports de résistance textiles d'un mélange adhésif
EP3907257A1 (fr) * 2020-05-05 2021-11-10 Continental Reifen Deutschland GmbH Mélange d'engommage réticulable au soufre
WO2023224586A1 (fr) * 2022-05-16 2023-11-23 Kordsa Teknik Tekstil A.S. Matériaux textiles à haute valeur d'adhérence

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Publication number Priority date Publication date Assignee Title
EP3597816A1 (fr) * 2018-07-19 2020-01-22 EMS-Patent AG Compositions de bain destinées au traitement des inserts de renfort
US11254794B2 (en) 2018-07-19 2022-02-22 Ems-Patent Ag Dipping bath compositions for treating reinforcing inserts
EP3617285A1 (fr) * 2018-08-28 2020-03-04 Cordenka GmbH & Co. KG Procédé d'équipement des supports de résistance textiles d'un mélange adhésif
EP3907257A1 (fr) * 2020-05-05 2021-11-10 Continental Reifen Deutschland GmbH Mélange d'engommage réticulable au soufre
WO2023224586A1 (fr) * 2022-05-16 2023-11-23 Kordsa Teknik Tekstil A.S. Matériaux textiles à haute valeur d'adhérence

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