EP3258008B1 - Procédé de fabrication d'une couche de renfort - Google Patents

Procédé de fabrication d'une couche de renfort Download PDF

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Publication number
EP3258008B1
EP3258008B1 EP17169841.8A EP17169841A EP3258008B1 EP 3258008 B1 EP3258008 B1 EP 3258008B1 EP 17169841 A EP17169841 A EP 17169841A EP 3258008 B1 EP3258008 B1 EP 3258008B1
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blocked
process according
strength members
nylon
group
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EP3258008A1 (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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    • 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
    • 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
    • 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.
  • a reinforcing layer produced by the method as well as a vehicle tire containing at least one reinforcing layer according to the invention is also disclosed.
  • 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 Gummi réellesmischung.
  • One problem is that the reinforcements and the surrounding rubber mixture have different strengths.
  • 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.
  • a further subject matter of the present description is a reinforcement layer comprising textile reinforcement which has been produced by the method according to the invention.
  • 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 produced 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 as well as 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 malein-functionalized polymer is available, for example, under the trade name Ricobond® 7004 from Cray Valley 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 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 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.
  • silane coupling agents can be used in rubber mixtures.
  • 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 known from the prior art coupling agents are bifunctional organosilanes having on the silicon atom at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group and have as other functionality a group which may optionally undergo a chemical reaction with the double bonds of the polymer after cleavage ,
  • a group which may optionally undergo a chemical reaction with the double bonds of the polymer after cleavage In the latter group may be z.
  • 3-mercaptopropyltriethoxysilane, 3-thiocyanato-propyltrimethoxysilane or 3,3'-bis (triethoxysilylpropyl) polysulfides having 2 to 8 sulfur atoms such as.
  • 3,3'-bis (triethoxysilylpropyl) tetrasulfide (TESPT) TESPT
  • TESPD disulfide
  • TESPT can also be added as a mixture with carbon black (trade name X50S® from Evonik).
  • 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.
  • 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.
  • silane coupling agent can be used as a silane coupling agent.
  • 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.
  • the gum 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 good property level with respect to the other properties.
  • 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.
  • 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 contains cords of 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.
  • Inventive Example 1 (El): Nylon cords as textile reinforcements, pre-dip containing DMP-blocked HDI trimer, dip containing maleic polymer
  • 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
  • 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
  • the cords according to Comparative Example 1 were prepared analogously to E1 with the exception that instead of Acrafix PCI (DMP-blocked HDI trimer) Grilbond® IL-6 (caprolactam blocked MDI) was used.
  • the pre-dip contained 93.5% by weight of water and 3.42% by weight of Grilbond® IL-6 and 3.08% by weight of Grilbond® G 1701.
  • the first drying step was carried out at 165 ° C. and the subsequent 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. 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 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 compound 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)

Claims (10)

  1. Procédé de fabrication d'une couche de renfort comprenant des renforts textiles pour des produits élastomères, le procédé comprenant au moins les étapes de procédé suivantes dans l'ordre suivant :
    a) l'immersion des renforts textiles dans au moins un premier bain, qui contient au moins un diisocyanate bloqué et qui est exempt de résorcine libre et de formaldéhyde libre, ainsi que leurs précondensats, les groupes protecteurs du ou des diisocyanates bloqués étant choisis dans le groupe constitué par les oximes, telles que de préférence les cétoximes telles que la méthyléthylcétoxime, et/ou les dérivés de pyrazole, tels que de préférence le 3,5-diméthylpyrazole, puis
    b) le séchage des renforts à une température de 120 à 140 °C, puis
    c) le chauffage des renforts à une température de 160 à 200 °C, et
    d) l'immersion des renforts textiles dans au moins un deuxième bain, qui contient au moins un polymère à fonctionnalisation maléine et qui est exempt de résorcine libre et de formaldéhyde libre, ainsi que leurs précondensats, puis
    e) le séchage des renforts à une température de 120 à 155 °C, puis
    f) le séchage des renforts à une température de 210 à 250 °C, et
    g) l'enrobage par un caoutchouc des renforts textiles prétraités selon a) à f) avec un mélange d'enrobage par un caoutchouc, qui contient au moins un caoutchouc diénique, qui est choisi dans le groupe constitué par le polyisoprène naturel et/ou le polyisoprène synthétique et/ou le caoutchouc de butadiène et/ou le caoutchouc de styrène-butadiène, et 20 à 90 pce d'au moins une charge choisie dans le groupe constitué par le noir de carbone et/ou la silice.
  2. Procédé selon la revendication 1, caractérisé en ce que le diisocyanate présente une fonctionnalité supérieure à 2, de préférence supérieure ou égale à 3.
  3. Procédé selon la revendication 2 caractérisé en ce que le diisocyanate est un polyisocyanate choisi dans le groupe constitué par le trimère de diisocyanate de 1,6-hexaméthylène bloqué et ses homologues supérieurs bloqués, ainsi que le trimère de diisocyanate de toluène bloqué et ses homologues supérieurs bloqués, ainsi que le trimère de diisocyanate d'isophorone bloqué et ses homologues supérieurs bloqués.
  4. Procédé selon la revendication 3, caractérisé en ce que le polyisocyanate est choisi dans le groupe constitué par le trimère de diisocyanate de 1,6-hexaméthylène bloqué par la méthyléthylcétoxime et le trimère de diisocyanate de 1,6-hexaméthylène bloqué par le 3,5-diméthylpyrazole.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le polymère de maléine présente un poids moléculaire de 5 000 à 20 000 g/mol.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le premier bain selon l'étape de procédé a) comprend au moins un composé époxy.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le polymère à l'étape d) est un polybutadiène à fonctionnalisation maléine.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les renforts textiles contiennent du polyéthylène téréphtalate (PET) et/ou du polyéthylène naphtalate (PEN) et/ou du polybutylène téréphtalate (PBT) et/ou du polycarbonate (PC) et/ou de la cellulose et/ou des esters de cellulose et/ou du m-aramide et/ou du p-aramide et/ou un mélange de m-aramide et de p-aramide et/ou un polyamide qui est choisi dans le groupe constitué par le polyamide 46 (PA 4.6) et/ou le polyamide 410 (PA 4.10) et/ou le polyamide 6 (PA 6) et/ou le polyamide 66 (PA 6.6 polyhexaméthylène-adipinamide) et/ou le polyamide 612 (PA 6.12) et/ou le polyamide 1010 (PA 10.10) et/ou le polyamide 1212 (PA 12.12).
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le mélange d'enrobage par un caoutchouc contient 50 à 100 pce d'au moins un polyisoprène naturel et/ou synthétique et 30 à 90 pce d'au moins un noir de carbone.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le noir de carbone du mélange d'enrobage par un caoutchouc présente un indice d'adsorption d'iode selon ASTM D 1510 de 40 à 110 g/kg et une surface STSA (selon ASTM D 6556) de 40 à 120 m2/g.
EP17169841.8A 2016-06-14 2017-05-08 Procédé de fabrication d'une couche de renfort Active EP3258008B1 (fr)

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PT3597816T (pt) 2018-07-19 2021-07-05 Ems Chemie Ag Composições de banho de imersão para o tratamento de insertos de reforço
PL3617285T3 (pl) * 2018-08-28 2022-02-21 Cordenka Gmbh & Co. Kg Sposób wyposażenia tekstylnych materiałów wzmacniających w mieszaninę klejącą
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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CN100523057C (zh) 2003-09-12 2009-08-05 帝人阿拉米德有限公司 用于浸渍合成纤维的两步法
JP4213026B2 (ja) * 2003-12-16 2009-01-21 帝人テクノプロダクツ株式会社 ゴム補強用繊維の製造方法
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US7968634B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing silated core polysulfides
US7968635B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing free-flowing filler compositions
US7968633B2 (en) 2006-12-28 2011-06-28 Continental Ag Tire compositions and components containing free-flowing filler compositions
DE102008037714A1 (de) 2008-07-31 2010-02-04 Continental Reifen Deutschland Gmbh Kautschukmischung mit umweltfreundlichem Weichmacher
JP2012012456A (ja) 2010-06-30 2012-01-19 Sumitomo Chemical Co Ltd Ｓ−（３−アミノプロピル）チオ硫酸および／またはその金属塩の使用方法
JP5584050B2 (ja) * 2010-08-17 2014-09-03 帝人株式会社 ゴム補強用ハイブリッドコードおよびその製造方法
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