Method for manufacturing a vehicle tire, vehicle tire manufactured by the method, and use of the treated reinforcing support material

Abstract

The present invention relates to a method for producing a vehicle tire, comprising the following steps: a) providing a textile reinforcing support; b) at least the following steps: b1) adding at least one polycarboxylic acid to water; b2) adding at least one base; b3) adding at least one epoxy compound; b4) adding at least one polyisocyanate compound; b5) adding at least one VP latex; and b6) mixing the substances from b1) to b5) to provide a resorcinol- and formaldehyde-free bath; c) immersing the reinforcing support from step a) in the bath from step b); d) subsequently hot-stretching the immersed reinforcing support from step c); and e) further processing the reinforcing support from step d) to form a reinforcing support layer into a vehicle tire blank. The present invention further relates to the use of reinforcing supports treated in such a method in vehicle tires and technical rubber articles produced using the method according to the invention.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a vehicle tire and to a vehicle tire manufactured by said method.The present invention further relates to the use of treated reinforcing members. [Background technology]

[0002] Automobile tires are known to have reinforcing members in various components for reinforcement, and industrial rubber articles such as belts, power transmission belts and hoses also have reinforcing members.

[0003] The reinforcing elements are typically surrounded by at least one rubber mixture, also called a rubberizing mixture. One problem is that the reinforcing elements and the surrounding rubberizing mixture have different strengths. Therefore, sufficient bonding between the reinforcing elements and the surrounding rubberizing mixture is necessary, especially under ongoing mechanical and dynamic stresses such as those encountered in the operation of an automobile tire.

[0004] The prior art discloses activation of reinforcing members prior to rubberization for sufficient bonding (bonding activation), typically by using what is called an RFL (resorcinol-formaldehyde latex) dip, through which the reinforcing members are dipped. Additionally, blocked isocyanates and / or epoxy compounds, among others, are used in combination with the RFL dip to pre-activate or further activate the reinforcing members. WO 2005 / 026239 A1, for example, discloses the use of polyisocyanates and RFLs lacking epoxy compounds.

[0005] However, resorcinol and formaldehyde are classified as harmful to the environment and health, and therefore efforts are being made to provide alternatives to them. For example, German Patent Application No. 102014211365 A1 discloses the treatment of textile weaves or textile reinforcing members with maleic acid-functionalized polymers to achieve improved bonding to rubber mixtures in the reinforcing member plies of automobile tires.

[0006] However, in the prior art, the manufacture of automobile tires, especially when non-preactivated reinforcing members are used, typically requires two different dips in succession to activate the reinforcing members sufficiently for bonding to the respective rubber mixtures, including natural rubber (NR), synthetic polyisoprene (IR), butadiene rubber (BR) and / or styrene-butadiene rubber (SBR). Summary of the Invention [Problem to be solved by the invention]

[0007] It is therefore an object of the present invention to provide a method for manufacturing an automobile tire comprising at least one reinforcing member ply with textile reinforcing members, which method is free of substances harmful to health and the environment and is also relatively simple, while at the same time the bond between the reinforcing members and the rubberized mixture is not significantly adversely affected or should even be improved as well. [Means for solving the problem]

[0008] The object is to provide a method for manufacturing an automobile tire comprising at least one reinforcing member ply having a textile reinforcing member, the method comprising at least the following method steps: a) providing a textile reinforcement member; b) at least the following method steps: b1) a process step of adding at least one polycarboxylic acid to water; and b2) a process step of adding at least one base; and b3) the method step of adding at least one epoxy compound; and b4) a method step of adding at least one polyisocyanate compound; and b5) a process step of adding at least one VP latex; and b6) a method step of mixing the substances from b1) to b5) to provide a bath free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and free of free formaldehyde and formaldehyde-releasing substances; c) the method step of immersing the reinforcing member from step a) in the bath from step b); d) thereafter, the method step of hot stretching the immersed reinforcement member from step c); e) a method step of further processing the reinforcing member from step d) to provide a reinforcing member ply in a green automobile tire; f) Method step for vulcanizing raw automobile tires This is achieved according to the present invention by a method comprising: DETAILED DESCRIPTION OF THE INVENTION

[0009] Due to the bath from step b) comprising the polycarboxylic acid, the epoxy compound, the polyisocyanate compound and the VP latex material, it is also possible in the manufacture of automobile tires to immerse the non-preactivated reinforcing members in only this one bath.

[0010] The components, in combination, allow for numerous chemical reactions, whereby the reinforcing members immersed therein undergo good activation of the bonding properties, while at the same time making it possible, in particular in the production of automobile tires, to dispense with free resorcinol and resorcinol precondensates, especially resorcinol-formaldehyde precondensates, as well as free formaldehyde and formaldehyde-releasing substances, i.e., substances that were or are present in prior art baths / dip solutions of this type and that are classified as harmful to health and the environment.

[0011] The method according to the invention for the production of automobile tires is therefore relatively simple and health- and environmentally friendly, with the simultaneous achievement of a comparable service life for the automobile tires.

[0012] In step a), textile reinforcing elements are provided in the method according to the invention. These can in principle be any textile reinforcing element that ensures sufficient reinforcement in the automobile tire. Preferably, the textile reinforcing members in step a) are made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycarbonate (PC), cellulose, regenerated cellulose, cellulose esters, carbon fibers, polyketones, m-aramid, p-aramid, mixtures of m-aramid and p-aramid, and polyamides selected from the group consisting of nylon-4,6 (PA4.6), nylon-4,10 (PA4.10), nylon-6 (PA6), nylon-6,6 (PA6.6 polyhexamethylene adipamide), nylon-6,12 (PA6.12), nylon-10,10 (PA10.10) and nylon-12,12 (PA12.12), including combinations of two or more of all the textile reinforcing members mentioned.

[0013] It is therefore possible for reinforcing member plies to be manufactured for automobile tires and for example have hybrid cords made of different textile yarns, for example hybrid cords made of PET and nylon-6,6 (PA6.6 polyhexamethylene adipamide).

[0014] More preferably, the textile reinforcing members comprise polyethylene terephthalate (PET), and / or cellulose, and / or regenerated cellulose, and / or cellulose ester, and / or nylon-6,6 (PA6.6 polyhexamethylene adipamide).

[0015] A preferred regenerated cellulose is known by the name "rayon."

[0016] The textile reinforcing member is preferably a cord having at least one twisted yarn. In this connection, all sizes (titers in decitex) and methods of twisting cords and yarns known in the prior art are considered. It is appropriate for the titer of each and every yarn to be between 200 and 5000 decitex and for the twist of the yarns and cords to be between 100 and 800 t / m.

[0017] The textile reinforcing members preferably already have the stated properties before method step a), meaning that they are preferably first twisted and then treated by method step a) (see below).

[0018] If the textile reinforcing members are embedded in the rubberized mixture as a weave, as known to those skilled in the art, there is preferably a weaving step after twisting and before treatment in method steps a) to f).

[0019] In a further development of the invention, the reinforcing elements are each mono-yarn cords, which means that one twisted thread constitutes each cord.

[0020] In a further preferred development of the invention, the reinforcing member is a cord made of at least two, more preferably two, threads.

[0021] In a further preferred development of the invention, the reinforcing member ply produced in step e) or that of the motor vehicle tire produced according to the invention comprises cords made of different numbers of threads as reinforcing members.

[0022] In step b), a bath is provided that is free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and free of free formaldehyde and formaldehyde-releasing substances. The expression "free" here means that the bath contains 0% to 0.1% by weight, but preferably 0% by weight, of such substances, the maximum amount being in each case based on the individual substance.

[0023] In step b) according to steps b1) to b5) detailed above, the essential components are combined and mixed in b6) to give a composition, i.e. to give a bath. In this case, the listing of b1) to b5) is not intended to impose any order in time. It is also possible that there are additional mixing steps (analogous to b6) in between, or that the components are added in groups.

[0024] However, it is preferred that the VP latex and any optional additional latex are added at a pH of 5 to 11. At pH values ​​above 5, lump formation is avoided.

[0025] In step b1), at least one polycarboxylic acid is added to water or provided in water. Compared to prior art baths, the polycarboxylic acid allows additional chemical reactions, such as acid / epoxy, acid / isocyanate, alcohol / isocyanate reactions, in interaction with the other components mentioned. Alcohol groups are introduced into the reaction system by the reaction of the polycarboxylic acid with the epoxy compound.

[0026] Preferably, the polycarboxylic acid in step b1) is based in the range of 10 to 100 mol %, more preferably 30 to 100 mol %, even more preferably 50 to 100 mol %, preferably then 70 to 100 mol %, even more preferably then 90 to 100 mol % on monomers containing carboxylic acid groups. In a particularly advantageous embodiment of the present invention, the polycarboxylic acid in step b1) is based in the range of 100 mol % on monomers containing carboxylic acid groups, without excluding further functional groups.

[0027] As a result of this, activation of the bonding properties of the reinforcing members in automobile tires manufactured in accordance with the present invention is particularly effective, and more particularly the chemical reactions mentioned are highly likely to occur.

[0028] Preferably, the polycarboxylic acid in step b1) has a weight average molecular weight Mw according to GPC of 1000 to 500000 g / mol, preferably 3000 to 100000 g / mol.

[0029] Preferably, the polycarboxylic acid is based on acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid and / or maleic acid monomers.

[0030] In a preferred embodiment, the polycarboxylic acid (based on acrylic acid monomers) is an acrylic resin.

[0031] More preferably, the polycarboxylic acid comprises a polyalcohol as a cross-linking agent.

[0032] Particularly suitable polycarboxylic acids based on acrylic acid monomers (acrylic resins containing carboxylic acid groups) containing polyalcohols are available, for example, from BASF Corp. under the Acrodur 950 L and Acrodur DS 3530 trademarks.

[0033] In step b2) according to the invention, at least one base is added. More particularly, the base should be used to set a pH of 5 to 11, preferably 7 to 11.

[0034] The base is preferably a volatile base that evaporates or whose constituents evaporate during the process.

[0035] In a particularly advantageous embodiment of the invention, the base in step b2) is ammonium hydroxide, i.e. an aqueous solution of ammonia, which activates the polycarboxylic acid for the chemical reaction described above, and the ammonia evaporates during the process.

[0036] In step b3) according to the present invention, at least one epoxy compound is added. Epoxy compounds as components of baths / immersions for textile reinforcing members are known to those skilled in the art. In the context of the present invention, the epoxy compound in step b3) is preferably selected from the group consisting of glycidyl-based glycerol, sorbitol-based epoxy compounds, phenol-based novolac epoxy compounds and cresol-based novolac epoxy compounds.

[0037] These compounds are particularly suitable for taking part in complex chemical reactions, especially with polycarboxylic acids, and therefore contribute particularly effectively to the activation of the bonding properties of the reinforcing members of motor vehicle tires produced according to the invention.

[0038] Particularly suitable examples are glycerol-based polyglycidyl ethers, e.g., Denacol TM EX-313, which is described inter alia in German Patent Specification No. 69722388 T2.

[0039] In step b4) according to the present invention, at least one polyisocyanate compound is added. Polyisocyanate compounds as constituents of baths / dipping solutions for textile reinforcing members are known to those skilled in the art.

[0040] The polyisocyanate compounds may be in the blocked form or in the form of dimers or higher homologs, i.e., "self-blocked."

[0041] The blocked polyisocyanates are obtained, for example and preferably, by blocking free isocyanates with at least one substance selected from the group comprising phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, tert-butyl alcohol, diphenylamine, dimethylaniline, phthalimide, δ-valerolactam, ε-caprolactam, dialkyl malonate, acetylacetone, alkyl acetoacetate, acetoxime, methyl ethyl ketoxime, 3,5-dimethylpyrazole, cyclohexanone oxime, 3-hydroxypyridine and sodium sulfite.

[0042] In the context of the present invention, it is preferred that the polyisocyanate compound in step b4) comprises units selected from the group consisting of aromatic diisocyanates, including tetramethylene diisocyanate, hexamethylene diisocyanate, diphenylmethane 4,4'-diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, toluene 2,4- or 2,6-diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, phenyl 1,3- or 1,4-diisocyanate.

[0043] In step b5) according to the present invention, at least one VP latex is added. VP latex is known to those skilled in the art. "VP" stands for "vinylpyridine", and known VP latexes may also contain additional monomers. A preferred example of a VP latex is vinylpyridine latex, which typically contains 15% vinylpyridine, 15% styrene, and 70% butadiene monomers.

[0044] As well as the VP latex added according to the invention, it is also possible for one or more additional latexes, for example styrene-butadiene latexes, to be added to the bath in step b).

[0045] In particular, using styrene-butadiene latex as the additional latex, optimization of the composition is possible without loss of properties.

[0046] Preferably, the butadiene component is selected from the group consisting of 1,3-butadiene and 2-methyl-1,3-butadiene. The styrene component is preferably selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, and hydroxymethylstyrene. The vinylpyridine monomer is preferably selected from the group consisting of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, and 5-ethyl-2-vinylpyridine.

[0047] In addition, it is contemplated that carboxylated VP latex and / or carboxylated styrene-butadiene latex may be further added, where "carboxylated" means that the latex may have carboxylic acid groups as functional groups.

[0048] As a result of this, the reaction system as described above is further assisted to further optimize binding activation.

[0049] In step b6), the components are mixed with each other, although it is also possible to carry out intermediate mixing steps as indicated above.

[0050] These materials are mixed by methods known to those skilled in the art.

[0051] The amounts of the individual substances mentioned can vary depending on the amount and molecular weight. It is particularly preferred if the bath from step b6) contains polycarboxylic acid in an amount of 0.1% to 10% by weight, preferably 0.1% to 2% by weight, epoxy compound in an amount of 0.1% to 2% by weight, polyisocyanate compound in an amount of 0.7% to 3% by weight, and at least one VP latex in an amount of 6% to 25% by weight. The remainder may be, inter alia, water, or additional substances such as the mentioned styrene-butadiene latex, and / or tackifiers and / or antifoaming agents may be present. The use of the mentioned optional substances and their amounts are guided by the textile material of the reinforcing member and the desired properties in the production, i.e., during the process and subsequent use, especially in tires, etc.

[0052] In step c) according to the invention, the reinforcing members from step a) are immersed in the bath from step b), which activates the integrity of the textile reinforcing members for a good service life in the automobile tire.

[0053] Immersion is accomplished using known equipment and methods known to those skilled in the art.

[0054] The reinforcing members provided in step a) do not need to be pre-activated by an additional immersion step.

[0055] However, the reinforcing members can be pre-activated. In particular in the case of non-pre-activated textile materials, it can prove advantageous to immerse the reinforcing members in a bath containing one or more epoxy compounds and one or more polyisocyanate compounds before immersion in the bath from step b). This results in an additional immersion step, but at the same time further optimizes the activation of the bond for attachment to the rubber / rubberized mixture in the automobile tire.

[0056] In step d) according to the invention, the immersed reinforcing members from step c) are then hot-stretched. This is also achieved using known apparatus, in particular one- or two-zone ovens, through which the reinforcing members are preferably guided continuously, and in each case in a manner adapted to the textile material. The hot-stretching temperature is preferably between 100 and 260°C.

[0057] Here, it is also possible to carry out two or more heat treatments at different temperatures in succession.

[0058] Preferably and by way of example, the immersed reinforcing members made of nylon (PA6.6) as the textile material are treated at 180-210°C for 30-60 seconds and then at 220-260°C for 20-100 seconds.

[0059] A further advantage of the present invention is that the dipped reinforcing members, especially the cords, do not show any obvious discoloration, which allows the production of reinforcing members in various colors by addition of dyes, which can be utilized, for example, for better marketing of the product or to avoid, for example, inadvertent changeovers in the further processing of the dipped reinforcing members.

[0060] In step e) according to the invention, the reinforcing members from step d) are further processed to provide a reinforcing member ply in a raw automobile tire. In this connection, the method of further processing is guided in particular by the component of the automobile tire in which the reinforcing member ply is used. More particularly and in a preferred embodiment of the invention, the reinforcing members from step d) are sheathed with a rubberized mixture.

[0061] For this purpose, the rubberized mixture preferably comprises at least one diene rubber, more preferably chosen from the group consisting of natural polyisoprene (NR), and / or synthetic polyisoprene (IR), and / or butadiene rubber (BR), and / or styrene-butadiene rubber (SBR), and preferably between 20 and 90 phr of at least one filler, preferably chosen from the group consisting of carbon black and silica.

[0062] The diene rubber can be any diene rubber known to a person skilled in the art from the group mentioned above.

[0063] The rubberizing mixture may contain polyisoprene (IR, NR) as the diene rubber. This may be either cis-1,4-polyisoprene or 3,4-polyisoprene. However, it is preferable to use cis-1,4-polyisoprene with a cis-1,4 content of more than 90% by weight. First, such polyisoprene can be obtained by stereospecific polymerization in solution using Ziegler-Natta catalysts or with fractionated lithium alkyls. Second, natural rubber (NR) is one such cis-1,4-polyisoprene; the cis-1,4 content in natural rubber is more than 99% by weight.

[0064] When the rubberizing mixture contains polybutadiene (BR) as diene rubber, it can be either cis-1,4-polybutadiene or vinyl polybutadiene (vinyl content of about 10% to 90% by weight). It is preferred to use cis-1,4-polybutadiene with a cis-1,4 content of more than 90% by weight, which can be prepared, for example, by solution polymerization in the presence of a catalyst of the rare earth element type.

[0065] Another usable diene rubber is a styrene-butadiene copolymer. The styrene-butadiene copolymer may be a solution-polymerized styrene-butadiene copolymer (S-SBR) having a styrene content of about 10% to 45% by weight based on the polymer and a vinyl content (content of 1,2-bonded butadiene based on the total polymer) of 10% to 70% by weight, which can be prepared, for example, using a lithium alkyl in an organic solvent. S-SBR may also be coupled and end-group modified. Alternatively, emulsion-polymerized styrene-butadiene copolymer (E-SBR) and mixtures of E-SBR and S-SBR may be used. The styrene content of E-SBR is about 15% to 50% by weight, and products known from the prior art, obtained by copolymerization of styrene and 1,3-butadiene in aqueous emulsion, may be used.

[0066] The diene rubbers used in the mixture, especially styrene-butadiene copolymers, can also be partially or fully functionalized. Functionalization can be achieved with groups capable of interacting with the fillers used, especially fillers with OH groups. Functionalization can be, for example, with hydroxyl groups, and / or epoxy groups, and / or siloxane groups, and / or amino groups, and / or phthalocyanine groups, and / or carboxyl groups, and / or silane sulfide groups.

[0067] The rubberizing mixture preferably contains 25 to 100 phr, more preferably 50 to 100 phr, more preferably next to 70 to 100 phr of natural and / or synthetic polyisoprene, natural polyisoprene being preferred here.

[0068] In a preferred development of the invention, the rubberizing mixture contains 100 phr of at least one natural polyisoprene (NR) and / or synthetic polyisoprene (IR), which means that mixtures of NR and IR are also conceivable.

[0069] In a further preferred development of the invention, the rubberized 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. Particularly in these rubbers and especially in the reinforcing plies of automobile tires, very good physical properties of the rubberized mixture are found in terms of processability, service life and tear properties, while a sufficient level of bondability is achieved.

[0070] The expression phr (parts by weight per 100 parts by weight of rubber) used in this text is the standard unit of quantity for blend recipes in the rubber industry. The dosage in parts by weight of an individual substance here always refers to 100 parts by weight of the total mass of all rubbers present in the mixture, which masses add up to 100.

[0071] In an advantageous embodiment of the invention, the rubberized 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, which results in a particularly good structural life of the reinforcing member plies produced, especially for use in automobile tires.

[0072] Small amounts, from 0 to 10 phr, and in a preferred embodiment from 0.1 to 10 phr, of further fillers such as aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gel can also be present.

[0073] It is further contemplated that the rubber compound comprises carbon nanotubes (CNTs), such as discrete CNTs known as hollow carbon fibers (HCFs) and modified CNTs containing one or more functional groups, such as hydroxyl, carboxyl, and carbonyl groups.

[0074] Graphite and graphene and also "carbon-silica dual phase fillers" are contemplated as fillers.

[0075] Preferably, however, the rubberizing mixture is free of these further fillers, ie it preferably contains 0 to 0.001 phr of these further fillers.

[0076] In the context of the present invention, zinc oxide is not considered a filler.

[0077] When carbon black is used in the rubberizing mixture, it should be 30 m 2 / g or more, preferably 30 to 120m 2 / g (according to ASTM D6556). They can be mixed in a simple manner and ensure low heat build-up.

[0078] In a preferred development of the invention, the rubberized mixture has an iodine adsorption according to ASTM D1510 of 40 to 110 g / kg and an iodine content of 40 to 120 m 2 The rubber composition of the present invention comprises at least one carbon black having an STSA surface area (according to ASTM D 6556) of 82 g / kg and a strength of 76 m / g. With this type of carbon black, sufficient reinforcement and strength of the rubberized mixture is achieved, in particular due to the relatively high surface area, in order to compensate as much as possible for the difference in strength between the reinforcing members and the rubber of the rubberized mixture. Possible preferred carbon black types are, for example, carbon blacks having an iodine adsorption according to ASTM D 1510 of 82 g / kg and a strength of 76 m / g. 2 / g (according to ASTM D 6556). Further possible preferred carbon black types are, for example, carbon black N326 having an iodine adsorption capacity according to ASTM D 1510 of 36 g / kg and an iodine content of 34 m 2 The carbon black is carbon black N660 having an STSA surface area (according to ASTM D 6556) of 1.0g / g.

[0079] If silicas are present in the mixture, they may be those conventional for tire rubber mixtures. 2 / g, preferably 120 to 250m 2It is particularly preferred when finely divided precipitated silica having a CTAB surface area (according to ASTM D 3765) of 1000 / g is used. The silica used can be either a conventional silica, such as that of type VN3 (trademark) manufactured by Evonik, or a highly dispersible silica known as HD silica (e.g., Ultrasil 7000 manufactured by Evonik). Silica is preferably used in an amount of less than 15 phr.

[0080] In order to improve processability and to bond the silica and any other polar fillers present to diene rubber, silane coupling agents can be used in rubber mixtures.It is possible to use one or more different silane coupling agents in combination here.The rubberized mixture can therefore contain a mixture of various silanes.

[0081] Silane coupling agents react with the surface silanol groups or other polar groups of the silica during the (in situ) mixing of the rubber or rubber mixture, or even during pretreatment (premodification) before adding fillers to the rubber. All silane coupling agents known to those skilled in the art for use in rubber mixtures can be used as silane coupling agents. Such coupling agents known from the prior art are bifunctional organosilanes that have at least one alkoxy, cycloalkoxy or phenoxy group on the silicon atom as a leaving group, and optionally, as another functional group, a group that, after dissociation, can undergo a chemical reaction with the double bond of the polymer. The latter group can be, for example, one of the following chemical groups: -SCN, -SH, -NH or -S. x - (where x=2 to 8).

[0082] For example, the silane coupling agent used can be, for example, 3-mercaptopropyltriethoxysilane, 3-thiocyanatopropyltrimethoxysilane, or a 3,3'-bis(triethoxysilylpropyl) polysulfide having 2 to 8 sulfur atoms, such as 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT), the corresponding disulfide (TESPD), or a mixture of sulfides having 1 to 8 sulfur atoms with various sulfides having different sulfide contents. TESPT can also be added as a mixture with, for example, industrial carbon black (trademark X50S® from Evonik).

[0083] It is preferred to use silane mixtures containing 40% to 100% by weight of disulfides, more preferably 55% to 85% by weight of disulfides, most preferably 60% to 80% by weight of disulfides. Mixtures of this type are available, for example, from Evonik under the trademark Si 261® and are described, for example, in DE 10 2006 004 062 A1.

[0084] For example, blocked mercaptosilanes, such as those known from WO 99 / 09036, can also be used as silane coupling agents. Silanes such as those described in WO 2008 / 083241 A1, WO 2008 / 083242 A1, WO 2008 / 083243 A1, and WO 2008 / 083244 A1 can also be used. For example, the silane marketed by Momentive, USA under the name NXT in many variations or that marketed by Evonik Industries under the name VP Si 363 (registered trademark) can be used.

[0085] It is also contemplated that one of the above mercaptosilanes, particularly 3-mercaptopropyltriethoxysilane, may be used in combination with a processing aid (listed below), particularly a PEG carboxylate.

[0086] In a preferred embodiment of the present invention, the rubberizing mixture comprises a combination of 3-mercaptopropyltriethoxysilane and PEG carboxylate, which notably solves the technical problem to be solved, in particular good properties and an overall good level of properties with regard to other properties.

[0087] In addition, the rubberizing mixture may further comprise an activator and / or an agent for the incorporation of fillers, especially carbon black. The latter may be, for example, the compound S-(3-aminopropyl)thiosulfuric acid and / or its metal salts, as disclosed, for example, in EP 2 589 619 A1, which, in combination with at least one carbon black as filler, gives rise to very good physical properties of the rubberizing mixture.

[0088] It is also possible for 0 to 70 phr, preferably 0.1 to 60 phr, of at least one plasticizer to be present in the rubberizing mixture. Such plasticizers include all plasticizers known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (light extractive solvates) or TDAE (aromatic extracts of processed distillates), or rubber liquid (RTL) or biomass liquid (BTL; as disclosed in DE 10 2008 037714 A1) or oils based on renewable raw materials (for example rapeseed oil, terpene oils (for example orange oil)), or factices, or plasticizer resins, or liquid polymers (such as liquid BR) whose average molecular weight (determined by GPC = gel permeation chromatography using the method according to BS ISO 11344:2004) is in the range of 500 to 20,000 g / mol. When liquid polymers are used as plasticizers in rubberized mixtures, they are not counted as rubber in calculating the composition of the polymer matrix (phr calculation).

[0089] If a mineral oil is used, it is preferably selected from the group consisting of DAE (Distillate Aromatic Extract), and / or RAE (Residual Aromatic Extract), and / or TDAE (Treatment Distillate Aromatic Extract), and / or MES (Minor Extraction Solvates), and / or naphthenic oils.

[0090] Furthermore, the rubberized mixture may contain standard additives in customary proportions by weight. These additives include: A) aging stabilizers, such as 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), B) activators, such as zinc oxide and fatty acids (e.g., stearic acid); C) wax, D) resins, especially tackifying resins that are not plasticizer resins; E) Resorcinol substitutes such as resorcinol and resorcinol equivalents, methylene acceptors and / or methylene donors / formaldehyde donors, e.g., hexamethoxymethylmelamine (HMMM) and / or hexamethylenetetramine (HMT) or phenolic resins and modified phenolic resins; F) chewing aids, such as 2,2'-dibenzamidodiphenyl disulfide (DBD), and G) Processing aids, such as fatty acid salts, e.g. zinc soaps, and fatty acid esters and their derivatives, e.g. PEG carboxylates Includes:

[0091] Vulcanization is carried out in the presence of sulfur and / or sulfur donors, some of which may also serve as vulcanization accelerators. Sulfur or sulfur donors are added to the rubberized mixture in the final mixing stage in amounts commonly used by those skilled in the art (0.4 to 8 phr of sulfur, preferably 0.4 to 4 phr). Vulcanization can also be achieved in the presence of very small amounts of sulfur in combination with sulfur donor substances.

[0092] In addition, the rubberizing mixture may contain conventional amounts of vulcanization-influencing substances, such as vulcanization accelerators, vulcanization retarders and vulcanization activators, to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanizate. The vulcanization accelerators may be selected, for example, from the following group of vulcanization accelerators: thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole, sulfenamide vulcanization accelerators, such as benzothiazyl-2-cyclohexylsulfenamide (CBS), guanidine vulcanization accelerators, such as N,N'-diphenylguanidine (DPG), dithiocarbamate vulcanization accelerators, such as zinc dibenzyldithiocarbamate, disulfides, thiophosphates. The vulcanization accelerators may also be used in combination with one another, which may produce a synergistic effect.

[0093] Rubberized mixtures are generally prepared in a conventional manner by first preparing a base mixture containing all the constituents except for the vulcanization system (sulfur and vulcanization-affecting substances) in one or more mixing stages, and then preparing a finished mixture by adding the vulcanization system, after which the mixture is further processed.

[0094] The reinforcing members are also rubberized in a manner known to those skilled in the art.

[0095] Further processing to provide the reinforcing member plies in the green tire is also accomplished by methods known to those skilled in the art.

[0096] For example, the reinforcing members may be calendered with the rubberized mixture, cut to size, and the rubberized reinforcing member plies thus obtained may be placed at appropriate points on a tire building machine.

[0097] Preferably, the reinforcing elements in step f) are processed at least in the carcass ply, and / or the belt, and / or the bandage, and / or the bead reinforcement. It is conceivable that the reinforcing elements processed according to the invention as described herein may be used in all of the components mentioned, providing the above-mentioned advantages in terms of material, ease of manufacture and sufficient bonding. The bandage is in particular one or more belt bandages.

[0098] The invention further provides a vehicle tire manufactured by the method according to the invention. All the above details are applicable here.

[0099] The automobile tire of the present invention has a relatively simple manufacturing mode that dispenses with resorcinol and formaldehyde, substances that are harmful to health and the environment.

[0100] The present invention relates to a method for producing industrial rubber articles, such as in particular belts, in particular conveyor belts, power transmission belts, in particular drive belts, hoses, strip belts, in particular conveyor belts and air bellows, by at least the following method steps: a) providing a textile reinforcement member; b) at least the following method steps: b1) a process step of adding at least one polycarboxylic acid to water; and b2) a process step of adding at least one base; and b3) the method step of adding at least one epoxy compound; and b4) a method step of adding at least one polyisocyanate compound; and b5) a process step of adding at least one VP latex; and b6) a method step of mixing the substances from b1) to b5) to provide a bath free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and free of free formaldehyde and formaldehyde-releasing substances; c) the method step of immersing the reinforcing member from step a) in the bath from step b); d) thereafter, the method step of hot stretching the immersed reinforcement member from step c). There is further provided a use of a fabric reinforcement member produced by a method comprising:

[0101] All of the above details are applicable to the present method. The use of reinforcing members treated as described in industrial rubber articles allows them to have comparable service life and to dispense with resorcinol and formaldehyde (substances that are harmful to the environment and health) in the baths for the reinforcing members. Alternatively, industrial rubber articles can be manufactured using the treated reinforcing members by methods and with equipment known in the prior art. [Example]

[0102] The invention will now be elucidated in detail with reference to the following examples.

[0103] Nylon (PA6.6 a) ) was provided and immersed in a comparative bath (from the prior art based on resorcinol-formaldehyde Latex RFL) and also in an inventive bath (without resorcinol and formaldehyde RF) according to the details in Table 1.

[0104] In addition, polyester (PET b) ) were provided and immersed in the baths mentioned. In the case of the RFL bath (comparison bath from the prior art), the non-bond-activated PET cord (PET b) ) was a pre-soak solution (95.26 wt.% water and 0.90 wt.% Denacol EX313 h) , and 3.84 wt. % Grilbond IL6 i)Pre-treated by immersion in a pre-immersion bath containing k) In the case of the bath of the present invention, the non-bonding activated cord (PET b) ) is first pretreated with the pre-soaking solution mentioned above. k) and then pre-soaked b) Used without.

[0105] Raw materials used a) Nylon-6,6 (Nylon): Two-yarn cord: 940 decitex x 2; 80 epdm (ends per decimeter; a measure of cord density in the fabric ply) cord weave b) Polyethylene terephthalate (PET): Two-thread cord: 1440 dtex x 2; 121 epdm cord weave; bond-unactivated c) Aqueous solution; 25% by weight ammonium hydroxide d) Aqueous solution; 50% by weight sodium hydroxide e) Resorcinol-formaldehyde precondensate: solids content 75% by weight in aqueous solution f) Aqueous solution: 37% by weight of formaldehyde g) Acrylic resin (polycarboxylic acid): solid content 50% by weight in aqueous solution h) Epoxy compounds: glycerol-based polyglycidyl ethers i) Polyisocyanate compound: solid content 60% by weight in aqueous solution j) Vinylpyridine latex: 41% by weight of VP polymer in water k) 95.26% by weight of water and 0.90% by weight of Denacol EX313 h) , and 3.84 wt. % Grilbond IL6 i) Bond activation by pre-soak bath containing l) No binding activation by pre-soak bath.

[0106] [Table 1]

[0107] After immersion and subsequent hot stretching, the reinforcing members were each coated with a rubberized mixture according to Table 2. The coating was then coated with

[0108] [Table 2]

[0109] For all reinforcing members described, bond testing with the rubberized mixtures described above was performed according to ISO 36:2011. The vulcanized samples were heated to 120°C for 30 minutes, and bond testing was performed within 30 seconds after removal from the oven. Bond strength evaluation was performed according to DIN ISO 6133. In addition, the peel area was rated on a scale of 0 to 10 for coverage with the rubberized mixture. This evaluation was achieved by visual inspection according to ASTM D4393. For each example, the reported bond strength and reported coverage are the average values ​​from three measurements in each case.

[0110] The results are summarized in Table 3.

[0111] [Table 3]

[0112] As can be seen in Table 3, the strength members treated in accordance with the present invention have comparable or even improved bonding properties.

[0113] Non-bonding activated PET reinforcement material (PET b) ) could in particular be treated by the above-specified RF-free bath according to the invention in that bath alone without the need for a pre-immersion, as was the case with RFL baths from the prior art.

[0114] Automobile tires or industrial rubber articles manufactured according to the invention using reinforcing members treated according to the invention therefore have a comparable service life and can dispense with resorcinol and formaldehyde (substances that are harmful to the environment and health) in the baths for the reinforcing members.

Claims

1. 1. A method for manufacturing an automobile tire including at least one reinforcing member ply having a fabric reinforcing member, comprising at least the following steps: a) providing a fabric reinforcement member that is polyethylene terephthalate (PET); b) at least the following method steps: b1) adding at least one acrylic polycarboxylic acid to water; and b2) a process step of adding at least one base; and b3) the process step of adding at least one epoxy compound; and b4) the process step of adding at least one polyisocyanate compound; and b5) a process step of adding at least one VP latex; and b6) method step of mixing the substances from b1) to b5). providing a bath free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and free of free formaldehyde and formaldehyde-releasing substances, by c) immersing the reinforcement member from step a) in the bath from step b); d) thereafter hot stretching (heat treating) the immersed reinforcement member from step c); e) further processing the reinforcing member from step d) to provide a reinforcing member ply into a green automobile tire; wherein the reinforcing members from step d) are coated with a rubberized mixture, said rubberized mixture comprising at least one diene rubber selected from the group consisting of natural polyisoprene (NR), and / or synthetic polyisoprene (IR), and / or butadiene rubber (BR), and / or styrene-butadiene rubber (SBR), and at least one filler selected from the group consisting of carbon black and silica, f) vulcanizing the raw automobile tire A method comprising:

2. 2. The method according to claim 1, wherein the polycarboxylic acid in step b1) is based in the range of 10 to 100 mol % on monomers containing carboxylic acid groups.

3. The polycarboxylic acid in step b1) has a weight average molecular weight M according to GPC of 1,000 to 500,000 g / mol. ｗ 3. The method according to claim 1 or 2, characterized in that it comprises:

4. 4. The method according to claim 1, wherein the polycarboxylic acid comprises a polyalcohol as a cross-linking agent.

5. 5. The process according to claim 1, wherein the base used in step b2) is ammonium hydroxide.

6. 6. The method according to claim 1, wherein the epoxy compound in step b3) is selected from the group consisting of glycidyl-based glycerol, sorbitol-based epoxy compounds, phenol-based novolac epoxy compounds and cresol-based novolac epoxy compounds.

7. The method according to any one of claims 1 to 6, characterized in that the polyisocyanate compound in step b4) contains a unit selected from the group consisting of aromatic diisocyanates including tetramethylene diisocyanate, hexamethylene diisocyanate, diphenylmethane 4,4'-diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, toluene 2,4- or 2,6-diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, and phenyl 1,3- or 1,4-diisocyanate.

8. 8. The method according to any one of claims 1 to 7, characterized in that the bath from step b6) contains the polycarboxylic acid in an amount of 0.1% to 10% by weight, preferably 0.1% to 2% by weight, the epoxy compound in an amount of 0.1% to 2% by weight, the polyisocyanate compound in an amount of 0.7% to 3% by weight, and the at least one VP latex in an amount of 6% to 25% by weight.

9. 9. Method according to any one of claims 1 to 8, characterized in that the reinforcing members in step f) are processed at least in the carcass ply, and / or in the belt, and / or in the bandage, and / or in the bead reinforcement.

10. The temperature of the heat stretching (heat treatment) is 100 to 260°C; The method according to any one of claims 1 to 9, characterized in that the hot stretching (heat treatment) is performed at 180 to 210°C for 30 to 60 seconds, and then at 220 to 260°C for 20 to 100 seconds.

11. 11. The method according to any one of claims 1 to 10, characterized in that the rubberized mixture comprises from 20 to 90 phr of at least one filler selected from the group consisting of carbon black and silica.

12. 12. The method according to claim 1, wherein the rubberized mixture contains from 25 to 85 phr of at least one natural and / or synthetic polyisoprene, and from 15 to 50 phr of at least one butadiene rubber and / or from 15 to 50 phr of at least one styrene-butadiene rubber.

13. 12. The method according to claim 1, wherein the rubberizing mixture contains from 50 to 100 phr of at least one natural and / or synthetic polyisoprene and from 30 to 90 phr of at least one carbon black.

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