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

[Technology Field]

[0001] This invention relates to a method for manufacturing automobile tires and automobile tires manufactured by this method. The invention further relates to the use of treated reinforcing members. [Background technology]

[0002] It is well known that automobile tires have reinforcing members in various components for strengthening purposes. Industrial rubber articles such as belts, transmission belts, and hoses also have reinforcing members.

[0003] The reinforcing member is typically surrounded by at least one rubberized mixture, also known as a rubberizing mixture. One problem is that the reinforcing member and the surrounding rubberized mixture have different strengths. In particular, under ongoing mechanical and dynamic stresses such as those encountered during the operation of an automobile tire, sufficient bonding between the reinforcing member and the surrounding rubberized mixture is therefore required.

[0004] Prior art discloses the activation of pre-rubberized reinforcing materials for sufficient bonding (bonding activation) by using what is typically called RFL (resorcinol-formaldehyde dipping), through which the reinforcing material is immersed. In addition, blocked isocyanates and / or epoxy compounds, in particular, are used in combination with RFL dipping to pre-activate or further activate the reinforcing material. International Publication No. 2005 / 026239 A1 discloses, for example, the use of polyisocyanates and RFL 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. For example, German Patent Application Publication No. 102014211365 A1 discloses the treatment of a woven weave or woven reinforcing member with a malein-functionalized polymer to achieve improved bonding to the rubber mixture in the reinforcing member ply of an automobile tire.

[0006] However, in the prior art, the manufacture of automobile tires typically requires two consecutive immersions to sufficiently activate the reinforcing material for bonding to the respective rubber mixtures, including natural rubber (NR), synthetic polyisoprene (IR), butadiene rubber (BR), and / or styrene-butadiene rubber (SBR), especially when non-pre-activated reinforcing material is used. [Overview of the project] [Problems that the invention aims to solve]

[0007] Therefore, the object of the present invention is to provide a method for manufacturing an automobile tire comprising at least one reinforcing ply having a woven reinforcing member, which is free of substances harmful to health and the environment and is also relatively simple. At the same time, the bonding between the reinforcing member and the rubberized mixture should not be significantly adversely affected, or should be further improved. [Means for solving the problem]

[0008] The objective is a method for manufacturing an automobile tire comprising at least one reinforcing member ply having a woven reinforcing member, comprising at least the following method steps: a) A method and process for providing a textile reinforcing member; b) At least the following method steps: b1) A step of adding at least one polycarboxylic acid to water; and b2) A method step of adding at least one type of base; and b3) A method step of adding at least one epoxy compound; and b4) A method step of adding at least one polyisocyanate compound; and b5) A method for adding at least one type of VP latex; and b6) A method of mixing substances from b1) to b5) A method and process for providing a bath that does not contain free resorcinol and resorcinol precondensates, particularly resorcinol-formaldehyde precondensates, and does not contain free formaldehyde or formaldehyde-releasing substances; c) A method of immersing the reinforcing member from step a) in the bath from step b); d) A method step of heat stretching the reinforced member that has been immersed in step c); e) A method for further processing the reinforcing member from step d) in order to provide the reinforcing member ply into the raw automobile tire; f) Process for vulcanizing raw automobile tires This is achieved according to the present invention by a method including the following. [Modes for carrying out the invention]

[0009] Because the bath from step b) contains polycarboxylic acid, epoxy compounds, polyisocyanate compounds, and VP latex material, it is also possible to immerse the non-pre-activated reinforcing material in only this one bath in the manufacture of automobile tires.

[0010] The aforementioned components, in their combination, enable numerous chemical reactions, thereby allowing the reinforcing material immersed therein to undergo good bonding activation. At the same time, it is particularly possible in the manufacture of automobile tires to do so without free resorcinol and resorcinol precondensates, especially resorcinol-formaldehyde precondensates, and free formaldehyde and formaldehyde-releasing substances, i.e., without substances that were present or are present in this type of prior art bath / immersion solution and are classified as harmful to health and the environment.

[0011] The method according to the present invention for the manufacture of automobile tires is therefore relatively simple and is also health and environmentally friendly, while simultaneously achieving a comparable service life for automobile tires.

[0012] In step a), the woven reinforcing member is provided by the method according to the present invention. These can, in principle, be any woven reinforcing member that ensures sufficient reinforcement in an automobile tire. The fabric reinforcing member in step a) is preferably made of a polyamide selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycarbonate (PC), cellulose, regenerated cellulose, cellulose ester, carbon fiber, polyketone, m-aramid, p-aramid, mixtures of m-aramid and p-aramid, and 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), and is preferably selected from the group which also includes combinations of two or more of all the fabric reinforcing members described.

[0013] Therefore, it is possible for reinforcing plies to be manufactured for automobile tires, and for example, to have hybrid cords made of different woven yarns, such as hybrid cords made of PET and nylon-6,6 (PA6.6 polyhexamethylene adipamide).

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

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

[0016] The fabric reinforcement member is preferably a cord having at least one twisted yarn. In this connection, the total fineness (titer in unit decitex) and the twisting method of the cords and yarns known in the prior art can be considered. It is appropriate when the titer of each and every yarn is 200 to 5000 decitex and when the twist of the yarn and cord is 100 to 800 t / m.

[0017] The fabric reinforcement member preferably already has the described properties before method step a), which means that they are preferably first twisted and then processed by method step a) (see below).

[0018] When the fabric reinforcement member is embedded as a weave in the rubberized mixture as known to those skilled in the art, a weaving step is preferably present after twisting and before the treatment in method steps a) to f).

[0019] In a further development of the invention, the reinforcement member is a cord made of one yarn each, which means that one twisted yarn constitutes each cord.

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

[0021] In a further preferred development of the invention, the reinforcement member ply produced in step e) or that of the automotive tire produced according to the invention contains cords made of different numbers of yarns as reinforcement members.

[0022] In step b), a bath is provided that does not contain free resorcinol and resorcinol precondensates, especially resorcinol-formaldehyde precondensates, and does not contain free formaldehyde and formaldehyde-releasing substances. The expression "does not contain" here means that the bath contains 0 wt% to 0.1 wt%, but preferably 0 wt% of this type of substance, where the maximum amount is based on each individual substance in each case.

[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., a bath. In this case, the listing of b1) to b5) is not intended to enforce any particular order in time. It is also possible that there are additional mixing steps (similar to b6) in between, or that components are added in groups.

[0024] However, it is preferable that VP latex and any optional additional latex be added at a pH of 5 to 11. Clumping is avoided at pH values ​​greater than 5.

[0025] In step b1), at least one polycarboxylic acid is added to water, or at least one polycarboxylic acid is provided in water. Compared to baths from the prior art, the polycarboxylic acid enables additional chemical reactions, such as acid / epoxy, acid / isocyanate, and alcohol / isocyanate reactions, in interaction with other components as described. The alcohol group is 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 on a monomer containing a carboxylic acid group 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%, and even more preferably then 90 to 100 mol%. In a particularly advantageous embodiment of the present invention, the polycarboxylic acid in step b1) is based on a monomer containing a carboxylic acid group in the range of 100 mol%, without excluding further functional groups.

[0027] As a result, the activation of the bonding properties of the reinforcing members in automobile tires manufactured according to the present invention is particularly effective, and the chemical reactions described in particular can occur to a high degree.

[0028] Preferably, the polycarboxylic acid in step b1) has a weight-average molecular weight Mw determined by GPC of 1,000 to 500,000 g / mol, preferably 3,000 to 100,000 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 an acrylic acid monomer) is an acrylic resin.

[0031] More preferably, the polycarboxylic acid includes a polyalcohol as a crosslinking agent.

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

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

[0034] The base is preferably a volatile base that evaporates during this method or whose constituent components evaporate.

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

[0036] In step b3) of the present invention, at least one epoxy compound is added. Epoxy compounds as components of the bath / immersion solution for the textile reinforcing member are known to those skilled in the art. In relation to 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 participating in complex chemical reactions with polycarboxylic acids, and therefore contribute particularly effectively to activating the bonding properties of reinforcing members of automobile tires manufactured according to the present invention.

[0038] Particularly preferred examples include glycerol-based polyglycidyl ethers, such as Denacol. TM This is EX-313, which is described in particular in German Patent No. 69722388 T2.

[0039] In step b4) of the present invention, at least one polyisocyanate compound is added. Polyisocyanate compounds as components of the bath / immersion solution for the textile reinforcing member are known to those skilled in the art.

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

[0041] Blocked polyisocyanates are obtained by blocking free isocyanates with at least one substance selected from the group including, for example and preferably, 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, dialkylmalonate, acetylacetone, alkylacetoacetate, acetoxime, methylethylketoxime, 3,5-dimethylpyrazole, cyclohexanone oxime, 3-hydroxypyridine, and acidic sodium sulfite.

[0042] In relation to the present invention, the polyisocyanate compound in step b4) preferably 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.

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

[0044] Similar to the VP latex added according to the present invention, one or more additional latexes, such as styrene-butadiene latex, may also be added to the bath in step b).

[0045] In particular, by using styrene-butadiene latex as an additional latex, the composition can be optimized 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, carboxylated VP latex and / or carboxylated styrene-butadiene latex may be further added, and "carboxylated" means that the latex may have a carboxylic acid group as a functional group.

[0048] As a result, the reaction systems described above are further supported in optimizing the activation of bonding.

[0049] In step b6), it is also possible to perform an intermediate mixing step as described above, but the constituent components are mixed with each other.

[0050] These substances are mixed in a manner known to those skilled in the art.

[0051] The amounts of the individual substances described can vary depending on the amount and molecular weight. It is particularly preferable that the bath from step b6) contains 0.1% to 10% by weight, preferably 0.1% to 2% by weight, of a polycarboxylic acid, 0.1% to 2% by weight, of an epoxy compound, 0.7% to 3% by weight, of a polyisocyanate compound, and 6% to 25% by weight, of at least one VP latex. The remainder may be, in particular, water, or additional substances such as the styrene-butadiene latex and / or tackifiers and / or anti-foaming agents. The use of the optional substances described and their amounts are guided by the desired properties of the woven material of the reinforcing member and in its manufacture, i.e., in this method and in subsequent use, particularly in tires, etc.

[0052] In step c) according to the present invention, the reinforcing member from step a) is immersed in the bath from step b). This activates the bonding properties of the woven reinforcing member for a good service life in the automobile tire.

[0053] Immersion is achieved using known apparatus and in a manner known to those skilled in the art.

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

[0055] However, the reinforcing material can be pre-activated. Particularly in the case of non-pre-activated textile materials, it may be advantageous to immerse the reinforcing material 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, the activation of the bonding for attachment to the rubber mixture / rubberized mixture in the automobile tire is further optimized.

[0056] In step d) according to the present invention, the immersed reinforcing member from step c) is then heat-stretched. This is also achieved using known apparatus, such as a one- or two-zone oven, through which the reinforcing member is preferably guided continuously, and in each case in a manner suitable for the textile material. The heat-stretching temperature is preferably 100 to 260°C.

[0057] Here, it is also possible to perform two or more heat treatments at different temperatures consecutively.

[0058] Preferably, and as an example, a dipped reinforcing member made of nylon (PA6.6) as a woven material is 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 immersed reinforcing material, in particular the cord, does not exhibit any obvious discoloration, which allows for the production of reinforcing material in various colors by adding dyes. This can be used, for example, for better marketing of the product, or to avoid accidental switching, for example, during further processing of the immersed reinforcing material.

[0060] In step e) according to the present invention, the reinforcing member from step d) is further processed to impart a reinforcing member ply to the raw automobile tire. In this regard, the method of further processing is guided in particular by the components of the automobile tire in which the reinforcing member ply is used. In a more particular and preferred embodiment of the present invention, the reinforcing member from step d) is housed in a sheath with a rubberized mixture.

[0061] For this purpose, the rubberized mixture preferably comprises at least one diene rubber more preferably 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 preferably selected from the group consisting of carbon black and silica, preferably in an amount of 20 to 90 phr.

[0062] The diene rubber can be any diene rubber known to those skilled in the art from the group described above.

[0063] The rubberized mixture may contain polyisoprene (IR, NR) as a 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. Firstly, such polyisoprene can be obtained by stereospecific polymerization in solution using a Ziegler-Natta catalyst or a subdivided lithium alkyl. Secondly, 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 rubberized mixture contains polybutadiene (BR) as the diene rubber, this may be either cis-1,4-polybutadiene or vinylpolybutadiene (with a vinyl content of about 10% to 90% by weight). For example, the use of cis-1,4-polybutadiene with a cis-1,4 content of more than 90% by weight, which can be prepared by solution polymerization in the presence of a rare-earth element type catalyst, is preferred.

[0065] A further usable diene rubber is styrene-butadiene copolymer. Styrene-butadiene copolymers can be solution-polymerized styrene-butadiene copolymers (S-SBRs) having a styrene content of about 10% to 45% by weight and a vinyl content of 10% to 70% by weight (1,2-butadiene content relative to the total polymer), which can be prepared, for example, using lithium alkyl in an organic solvent. S-SBRs can also be coupling and end-group modified. Alternatively, emulsion-polymerized styrene-butadiene copolymers (E-SBRs) and mixtures of E-SBRs and S-SBRs can be used. The styrene content of E-SBRs 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 emulsions, can be used.

[0066] The diene rubber used in the mixture, particularly the styrene-butadiene copolymer, can also be used in a partially or fully functionalized form. Functionalization can be achieved with groups that can interact with the fillers used, particularly those having OH groups. Functionalization may be, for example, by 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 rubberized mixture preferably contains 25 to 100 phr, more preferably 50 to 100 phr, and second most preferably 70 to 100 phr of natural polyisoprene and / or synthetic polyisoprene, with natural polyisoprene being preferred here.

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

[0069] In a more preferred development of the present invention, the rubberized mixture contains at least one natural and / or synthetic polyisoprene in a quantity of 25 to 85 phr and at least one butadiene rubber in a quantity of 15 to 50 phr and / or at least one styrene-butadiene rubber in a quantity of 15 to 50 phr. In particular, in these rubbers and especially in reinforcing plies of automobile tires, the very good physical properties of the rubberized mixture are found in terms of processability, service life and tear properties, while a sufficient level of bonding is achieved.

[0070] The expression phr (parts by weight per 100 parts by weight of rubber) used in this text is a standard unit of quantity for blend recipes in the rubber industry. The part-by-weight dosage of individual substances is always based on 100 parts by weight of the total mass of all rubber present in the mixture. The total mass of all rubber present in the mixture is 100.

[0071] In an advantageous embodiment of the present invention, the rubberized mixture contains at least one natural polyisoprene and / or synthetic polyisoprene in a quantity of 50 to 100 phr and at least one carbon black in a quantity of 30 to 90 phr. This results in a particularly good structural lifespan for the manufactured reinforced ply, especially when used in automobile tires.

[0072] Further fillers such as aluminosilicate, chalk, starch, magnesium oxide, titanium dioxide, or rubber gel may be present in small amounts, 0 to 10 phr, and preferably 0.1 to 10 phr.

[0073] It is also conceivable that the rubber mixture contains 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, as well as "carbon-silica biphase fillers," can also be considered as fillers.

[0075] However, preferably, the rubberized mixture does not contain these additional fillers, i.e., preferably contains 0 to 0.001 phr of these additional fillers.

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

[0077] When carbon black is used in a rubberized mixture, it is 30m 2 More than / g, preferably 30-120m 2 These are types with an STSA surface area of ​​1 / g (according to ASTM D6556). They can be mixed in a simple manner, ensuring low heat accumulation.

[0078] In a preferred advanced form of the present invention, the rubberized mixture has an iodine adsorption capacity of 40-110 g / kg according to ASTM D1510 and 40-120 m 2 It contains at least one type of carbon black having an STSA surface area (according to ASTM D 6556) of 82 g / kg. Using this type of carbon black, sufficient reinforcement and strength of the rubberized mixture are achieved, particularly due to its relatively high surface area, in order to offset as much as possible the difference in strength between the reinforcing member and the rubber of the rubberized mixture. Possible preferred carbon black types include, for example, those with an iodine adsorption capacity of 82 g / kg and 76 m² according to ASTM D 1510. 2 Carbon black N326 having an STSA surface area of ​​36 g / kg (according to ASTM D 6556). Further possible preferred carbon black types include, for example, iodine adsorption of 36 g / kg and 34 m² according to ASTM D 1510. 2 This is carbon black N660 with an STSA surface area of ​​1 / g (according to ASTM D 6556).

[0079] If silica is present in the mixture, it may be the silica that is conventional for tire rubber mixtures. 30–350m 2 / g, preferably 120-250m 2It is particularly preferred to use micronized precipitated silica having a CTAB surface area of / g (according to ASTM D 3765). The silica used can be either a conventional silica such as VN3 type (trademark) from Evonik or a highly disperse silica known as HD silica (for example, Ultrasil 7000 from Evonik). The silica is preferably used in an amount less than 15 phr.

[0080] In order to improve processability and for the binding of the existing silica and any other polar fillers to the diene rubber, it is possible to use a silane coupling agent in the rubber mixture. It is possible here to use one or more different silane coupling agents in combination with each other. The rubber blend can thus contain a mixture of various silanes.

[0081] The silane coupling agent reacts with the surface silanol groups or other polar groups of the silica during the in-situ mixing of the rubber or rubber mixture or in a pretreatment (pre-modification) before the addition of the filler to the rubber. As the silane coupling agent, it is possible to use all silane coupling agents known to those skilled in the art for use in rubber mixtures. Such coupling agents known from the prior art are bifunctional organosilanes having at least one alkoxy, cycloalkoxy or phenoxy group on the silicon atom as a leaving group and, as another functional group, a group capable of undergoing a chemical reaction with the double bond of the polymer, optionally after dissociation. The latter group can be, for example, one of the following chemical groups: -SCN, -SH, -NH2 or -S x -(where x = 2 to 8).

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

[0083] It is preferable to use a silane mixture containing 40% to 100% by weight of disulfide, more preferably 55% to 85% by weight of disulfide, and most preferably 60% to 80% by weight of disulfide. Such mixtures are available, for example, from Evonik under the trademark Si 261 (registered trademark), and are described, for example, in German Patent Application Publication No. 102006004062 A1.

[0084] For example, blocked mercaptosilanes, such as those publicly known from International Publication No. 99 / 09036, can also be used as silane coupling agents. Silanes described in International Publication Nos. 2008 / 083241 A1, 2008 / 083242 A1, 2008 / 083243 A1, and 2008 / 083244 A1 can also be used. For example, silanes marketed by Momentive, USA in numerous variations under the name NXT, or those marketed by Evonik Industries under the name VP Si 363 (registered trademark), can be used.

[0085] One of the mercaptosilanes mentioned above, in particular 3-mercaptopropyltriethoxysilane, may also be used in combination with processing aids (listed below), especially PEG carboxylate.

[0086] In a preferred embodiment of the present invention, the rubberized mixture comprises a combination of 3-mercaptopropyltriethoxysilane and PEG carboxylate, which yields an overall good level of properties with respect to technical issues to be addressed, particularly good properties and other properties.

[0087] In addition, the rubberized mixture may further contain activators and / or fillers, in particular reagents for incorporating carbon black. The latter may be, for example, the compound S-(3-aminopropyl)thiosulfate and / or its metal salt, as disclosed in, for example, European Patent Application Publication No. 2589619 A1, which, in combination with at least one type of carbon black as a filler, produces very good physical properties of the rubberized mixture.

[0088] It is also possible that at least one plasticizer in a concentration of 0 to 70 phr, preferably 0.1 to 60 phr, may be present in the rubberized mixture. Such plasticizers include all plasticizers known to those skilled in the art, such as aromatic, naphthenic, or paraffinic mineral oil plasticizers, e.g., MES (Mild Extract Solvate) or TDAE (Aromatic Extract of Treatment Distillate), or rubber liquefaction oil (RTL) or biomass liquefaction oil (BTL; as disclosed in German Patent Application Publication No. 10 2008 037714 A1), or oils based on renewable raw materials (e.g., rapeseed oil, terpene oil (e.g., orange oil)), or Factis, or plasticizer resins, or liquid polymers (such as liquid BR) having an average molecular weight (measured by GPC = gel permeation chromatography using the method according to BS ISO 11344:2004) in the range of 500 to 20000 g / mol. When liquid polymers are used as plasticizers in rubberized mixtures, they are not counted as rubber in the calculation of the polymer matrix composition (PHR calculation).

[0089] When mineral oil is used, it is preferably selected from the group consisting of DAE (distilled aromatic extract), and / or RAE (residual aromatic extract), and / or TDAE (treated distillate aromatic extract), and / or MES (mildly extracted solvate), and / or naphthenic oil.

[0090] Furthermore, the rubberized mixture may contain standard additives in conventional weight proportions. These additives include: A) Anti-aging stabilizers, such as N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditrilyl-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, particularly tackifying resins that are not plasticizer resins, E) Resorcinol and resorcinol equivalents, methylene acceptors and / or methylene donors / formaldehyde donors, such as hexamethoxymethylmelamine (HMMM) and / or hexamethylenetetramine (HMT), or resorcinol substitutes such as phenolic resins and modified phenolic resins. F) Chewing aids, such as 2,2'-dibenzamide diphenyl disulfide (DBD), and G) Processing aids, such as fatty acid salts, such as zinc soap, and fatty acid esters and their derivatives, such as PEG carboxylates. It includes.

[0091] Vulcanization is carried out in the presence of sulfur and / or a sulfur donor, some of which can simultaneously act as vulcanization accelerators. Sulfur or a sulfur donor is 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 combined with a sulfur donor substance.

[0092] In addition, the rubberized 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 vulcanized material. Vulcanization accelerators may be selected from, for example, the following group: thiazole vulcanization accelerators, e.g., 2-mercaptobenzothiazole; sulfenamide vulcanization accelerators, e.g., benzothiadyl-2-cyclohexylsulfenamide (CBS); guanidine vulcanization accelerators, e.g., N,N'-diphenylguanidine (DPG); and dithiocarbamate vulcanization accelerators, e.g., zinc dibenzyl dithiocarbamate, disulfides, and thiophosphates. Vulcanization accelerators may also be used in combination with each other to produce synergistic effects.

[0093] Rubberized mixtures are generally produced by conventional methods, which involve first preparing a base mixture containing all constituent components except for the vulcanizing agent (sulfur and vulcanization-inducing substances) in one or more mixing steps, and then producing a finish mixture by adding the vulcanizing agent. The mixture is then further processed.

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

[0095] Further processing to impart reinforcing plies to the green tire can also be achieved by methods known to those skilled in the art.

[0096] For example, the reinforcing material is calendered together with the rubberized mixture, cut to size, and the resulting rubberized reinforcing material plies are placed at the appropriate points on the tire assembly machine.

[0097] Preferably, the reinforcing member in step f) is processed in at least carcass plies and / or belts and / or straps and / or bead reinforcements. Herein, the reinforcing member processed according to the present invention as described can be used in all the components described and may also provide the above-mentioned advantages with respect to the material, as well as ease of manufacture and good bonding. The straps are, in particular, one or more belt straps.

[0098] The present invention further provides an automobile tire manufactured by the method according to the present invention. All of the above details are applicable herein.

[0099] The automobile tire of the present invention has a relatively simple manufacturing mode that does not require resorcinol and formaldehyde (substances harmful to health and the environment).

[0100] The present invention relates to industrial rubber articles, particularly belts, particularly conveyor belts, transmission belts, particularly drive belts, hoses, strip belts, particularly transport belts, and air bellows, and at least the following method steps: a) A method and process for providing a textile reinforcing member; b) At least the following method steps: b1) A step of adding at least one polycarboxylic acid to water; and b2) A method step of adding at least one type of base; and b3) A method step of adding at least one epoxy compound; and b4) A method step of adding at least one polyisocyanate compound; and b5) A method for adding at least one type of VP latex; and b6) A method of mixing substances from b1) to b5) A method and process for providing a bath that does not contain free resorcinol and resorcinol precondensates, particularly resorcinol-formaldehyde precondensates, and does not contain free formaldehyde or formaldehyde-releasing substances; c) A method of immersing the reinforcing member from step a) in the bath from step b); d) A method of heat stretching the reinforced member that has been immersed in step c) Further, the use of textile reinforcing members manufactured by a method including the present invention is provided.

[0101] All of the above details are applicable to this method. By using reinforced materials treated as described in the industrial rubber articles, they can have a comparable service life and can be processed without resorcinol and formaldehyde (substances harmful to the environment and health) in the bath for the reinforced materials. In addition, industrial rubber articles are manufactured using the treated reinforced materials by methods and apparatus known in the prior art. [Examples]

[0102] The present invention will be described in detail here in relation to the following embodiments.

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

[0104] In addition, polyester (PET b) ) provides an unbound-activated code made of PET and immersed in the bath described. In the case of the RFL bath (comparative bath from the prior art), the unbound-activated PET code (PET b) ) is a pre-immersion solution (95.26% by weight of water and 0.90% by weight of Denacol EX313 h) , and 3.84 wt% Grillbond IL6 i) Pretreatment by immersion in a pre-immersion bath containing [a specific substance].k) It had to be done. In the case of the bath of the present invention, the non-binding-activating code (PET b) ) is first pre-treated with the pre-immersion solution described above. k) And secondly, pre-immersion b) Used without any issues.

[0105] Raw materials used a) Nylon-6,6 (Nylon): Cord made of two threads: 940 dsitex x 2; weave made of cord at 80 epdm (ends per 1 decimeter; a measure of cord density in a fabric ply) b) Polyethylene terephthalate (PET): Cord made of two threads: 1440 dsitex x 2; Weave made of cord at 121 epdm; Unactivated binding c) Aqueous solution; 25% by weight of ammonium hydroxide d) Aqueous solution; 50% by weight of sodium hydroxide e) Resorcinol-formaldehyde pre-condensate: Solid content 75% by weight in aqueous solution f) Aqueous solution: 37% by weight of formaldehyde g) Acrylic resin (polycarboxylic acid): Solids content 50% by weight in aqueous solution h) Epoxy compounds: Glycerol-based polyglycidyl ethers i) Polyisocyanate compound: Solids 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% Grillbond IL6 i) Activation of bonding by pre-immersion bath containing l) No binding activation by pre-immersion bath.

[0106] [Table 1]

[0107] After immersion and subsequent heat stretching, the reinforcing members were each placed in sheaths with the rubberized mixture shown in Table 2.

[0108] [Table 2]

[0109] For all reinforced materials described, bonding tests with the aforementioned rubberized mixture were performed in accordance with ISO 36:2011. The vulcanized samples were heated at 120°C for 30 minutes, and the bonding test was performed within 30 seconds of removal from the oven. Bonding strength was evaluated in accordance with DIN ISO 6133. In addition, the delamination area was evaluated on a scale of 0 to 10 in relation to the coverage with the rubberized mixture. This evaluation was achieved by visual inspection in accordance with ASTM D4393. For each example, the reported bonding 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 is clear from Table 3, the reinforcing members treated according to the present invention have comparable or even improved bonding properties.

[0113] Non-binding-activated PET reinforced material (PET) b) In particular, the RF-free bath specified above in accordance with the present invention could be used for treatment with the bath alone without the need for pre-immersion, as in the case of RFL baths from the prior art.

[0114] Automobile tires or industrial rubber articles manufactured according to the present invention using reinforcing members treated according to the present invention therefore have a comparable service life and can be prepared without resorcinol and formaldehyde (substances harmful to the environment and health) in the bath for the reinforcing members.

Claims

1. 1. A method of manufacturing an automobile tire including at least one reinforcing member ply having a fabric reinforcing member, the method comprising at least the following 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) 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; c) immersing the reinforcement member from step a) in the bath from step b); d) thereafter hot stretching the immersed reinforcement member from step c); e) further processing the reinforcing member from step d) to provide a reinforcing member ply in a green automotive tire; f) vulcanizing the raw automobile tire A method comprising:

2. 2. The method of claim 1, wherein the woven reinforcing members in step a) are made of a polyamide selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycarbonate (PC), cellulose, regenerated cellulose, cellulose esters, carbon fibers, polyketones, m-aramid, p-aramid, a mixture of m-aramid and p-aramid, and 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 mentioned woven reinforcing members.

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

4. The polycarboxylic acid in step b1) has a weight average molecular weight M according to GPC of 1000 to 500000 g / mol. w 4. The method according to claim 1, wherein the method comprises:

5. 5. The method according to claim 1, wherein the carboxylic acid in step b1) is an acrylic resin.

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

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

8. 8. 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.

9. 9. The method according to claim 1, wherein the polyisocyanate compound in step b4) comprises 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, phenyl 1,3- or 1,4-diisocyanate.

10. 10. The method according to claim 1, wherein 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 blocked 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.

11. 11. The method according to any one of claims 1 to 10, 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.

12. 12. A vehicle tire manufactured as claimed in any one of claims 1 to 11.

13. In particular in industrial rubber articles such as belts, especially conveyor belts, transmission belts, especially drive belts, hoses, strip belts, especially conveyor belts and air bellows, 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) 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 said reinforcement member from step a) into said bath from step b); d) thereafter, the method step of hot stretching said immersed reinforcement member from step c).

12. Use of a textile reinforcing member manufactured by a method comprising: