Composite material for elastomeric products, in particular vehicle tyres, and method for manufacturing same

Abstract

The invention relates to a method for producing a vulcanisable composite material, said method comprising the steps of: a) producing or providing a textile reinforcement; b) treating the textile reinforcement with an aqueous dispersion in order to activate the adhesion of the textile reinforcement and to obtain an adhesion-activated textile reinforcement; and c) introducing the adhesion-activated textile reinforcement into a cross-linkable rubber-coating mixture in order to obtain the vulcanisable composite material, wherein the aqueous dispersion is substantially free from free resorcinol and from resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and is free from free formaldehyde and from formaldehyde-releasing substances, wherein the textile reinforcement in step a) comprises filaments, wherein the filaments contain one or more materials which are selected from the group consisting of a1) recycled polymers and a2) bio-based polymers, wherein the recycled and bio-based polymers are preferably selected from the group consisting of polyesters, such as in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and aramids, such as in particular m-aramid and p-aramid.

Description

[0001] Composite material for elastomeric products, in particular vehicle tires, and process for producing

[0002] Description

[0003] The invention relates to a method for producing a vulcanizable composite material and a method based thereon for producing a vulcanized composite material or an elastomeric product, as well as a corresponding vulcanizable composite material and a vulcanized composite material or a corresponding elastomeric product that can be produced therefrom.

[0004] It is well known that vehicle tires incorporate textile reinforcements in various components. Other technical rubber products, such as belts, straps, and hoses, also often incorporate reinforcements. These reinforcements are typically surrounded by at least one rubber compound, which is also referred to as a rubber compound or, in the vulcanized state, as a rubber lining.

[0005] One common problem is that the reinforcements and the surrounding rubber coating usually have different mechanical properties, particularly different strengths. Especially under continuous mechanical and dynamic stress, such as that encountered during vehicle tire operation, sufficient adhesion between the reinforcements and the surrounding rubber coating is necessary to ensure adequate bond strength.

[0006] In the prior art, it is known to activate the reinforcements before rubberizing to ensure sufficient adhesion (so-called adhesion activation or adhesion activation), whereby so-called RFL dips (short for resorcinol formaldehyde latex) are usually used, which can be applied, for example, by means of an immersion bath.

[0007] Furthermore, the prior art proposes aqueous dispersions for adhesion activation that are essentially free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and free of free formaldehyde and formaldehyde-releasing substances. Such dispersions are disclosed, for example, in WO 2019 / 015792 A1, EP 3702521 A1, EP 3702522 A1, and EP 3702523 A1. With the described dispersions, the production of elastomeric products comprising reinforcements, in particular vehicle tires, is made more environmentally friendly and less harmful to health than with dispersions containing free resorcinol, etc.

[0008] At the same time, compared to the use of dispersions as described in WO 2015 / 188939 A1, WO 2014 / 175844 A2 and WO 2014 / 091376 A1, an improved bond between the reinforcement and the rubber coating as well as improved processability, in particular storage stability of the treated reinforcements, is achieved.

[0009] In addition to the health, environmental and durability-related aspects described above, there is also a steadily increasing need in the area of ​​vehicle tire production to make the manufacturing process more sustainable and environmentally friendly with regard to the selection of materials.

[0010] The materials used in the strength members are usually selected according to their physical and chemical properties and in light of the respective requirement profile.

[0011] In order to increase the sustainability of the production of corresponding composite materials—comprising adhesion-activated reinforcements and surrounding rubber coatings—and to reduce dependence on fossil raw materials, attempts have been made in the prior art to replace the petrochemically produced reinforcements with natural fibers. However, this is often considered disadvantageous with regard to the quality and reproducibility of the composite materials produced with them, particularly because natural fibers often lack the necessary physicochemical properties, for example, with regard to shrinkage behavior. In addition, some natural fibers exhibit other properties that make them less suitable for use in composite materials in pneumatic vehicle tires, for example, the well-known moisture sensitivity of the material rayon.In addition, natural fibers are usually only available as staple fibers and not as continuous fibers.

[0012] The present invention is based on the object of providing a process for producing a composite material that can be operated in a more sustainable manner and reduces dependence on fossil raw materials. At the same time, the process should be as health- and environmentally-friendly as possible. The composite materials produced using the process should also exhibit optimized durability, so that they meet the high mechanical demands of their typical use. Thus, despite their high sustainability, the composite materials should possess excellent properties, allowing them to be used to manufacture high-performance vulcanized elastomer products, particularly vehicle tires.

[0013] Furthermore, it is an object of the present invention to provide a method for producing an elastomeric product, in particular a vehicle tire, and a corresponding elastomeric product, in particular a vehicle tire. It is an object of the present invention that the corresponding vehicle tires should have a more sustainable composition and contribute to driving safety.

[0014] The above-mentioned objects are achieved by the subject matter of the invention as defined in the claims. Preferred embodiments of the invention emerge from the further claims and the following statements.

[0015] Such embodiments, which are designated as preferred below, are combined in particularly preferred embodiments with features of other embodiments designated as preferred. Combinations of two or more of the embodiments designated as particularly preferred below are thus very particularly preferred. Likewise preferred are embodiments in which a feature of an embodiment designated as preferred to any extent is combined with one or more further features of other embodiments designated as preferred to any extent. Features of preferred vulcanizable composite materials, vulcanized composite materials, elastomeric products, and vehicle tires also emerge from the features of preferred processes.

[0016] The invention relates to a method for producing a vulcanizable composite material, comprising the steps: a) producing or providing a textile reinforcement, b) treating the textile reinforcement with an aqueous dispersion to activate the adhesion of the textile reinforcement and to obtain an adhesion-activated textile reinforcement, and c) introducing the adhesion-activated textile reinforcement into a crosslinkable rubberizing mixture to obtain the vulcanizable composite material, wherein the aqueous dispersion is substantially free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and is free of free formaldehyde and formaldehyde-releasing substances, wherein the textile reinforcement in step a) comprises filaments, wherein the filaments contain one or more materials,which are selected from the group consisting of a1) recycled polymers and a2) bio-based polymers, wherein the recycled and bio-based polymers are preferably selected from the group consisting of,

[0017] Polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0018] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0019] Aramids, especially m-aramid and p-aramid. Surprisingly, it has been found that the process according to the invention can be operated more sustainably by combining the selection of the aqueous dispersion for adhesion activation with the aforementioned materials, thereby reducing dependence on fossil raw materials. At the same time, the process is both health- and environmentally friendly. Furthermore, the produced composite materials surprisingly exhibit optimized durability despite their high level of sustainability.

[0020] By selecting the materials of the filaments of the reinforcement, it is possible to significantly reduce the dependence on fossil raw materials, especially petroleum, and to produce a particularly important component for the manufacture of vehicle tires using a sustainable process that results in particularly environmentally friendly products.

[0021] Due to the high demands placed on the physico-chemical properties of materials used in reinforcements, this finding is surprising, as it was not foreseeable that composite materials produced using corresponding processes could actually be suitable for use in modern vehicle tires and at the same time possess excellent properties comparable to those of composite materials equipped with petrochemically produced reinforcements.

[0022] The term "essentially free of" is to be understood, in accordance with the expert understanding, within the scope of the present invention to mean that the corresponding substances may only be present in amounts that do not significantly affect the essential properties of the claimed composition. For example, the amount of these substances must not exceed trace amounts resulting from contamination. Typically, the aqueous dispersion to be used according to the invention should contain no more than 0.1 wt.% (dry weight), based on the total weight of the aqueous dispersion, of each of the specified components, such as resorcinol, resorcinol precondensates, formaldehyde, and formaldehyde-releasing substances; i.e., 0.1% by weight is the maximum amount for each of the above components. Preferably, the content of all of these components in the aqueous dispersion is 0 wt.%.

[0023] Particularly suitable as aqueous dispersions for adhesion activation are those systems which are disclosed, for example, in WO 2019 / 015792 A1 as well as EP 3702521 A1, EP 3702522 A1 and EP 3702523 A1.

[0024] In principle, a process according to the invention is preferred in which the aqueous dispersion comprises:

[0025] (w1 ) at least one rubber latex, provided that this rubber latex is not a polyisoprene rubber latex (including synthetic and natural polyisoprene rubber latex), and

[0026] (w2) at least one protected isocyanate, and

[0027] (w3) at least one filler and / or at least one polymer having carboxylic acid functional groups and / or at least one polyisoprene rubber (including synthetic and natural polyisoprene rubber latex) and / or at least one wax.

[0028] A suitable rubber latex is VP latex, for example. VP latex is known to those skilled in the art. "VP" stands for "vinyl pyridine," whereby known VP latexes can also comprise additional monomers. A preferred example of a VP latex is a vinyl pyridine latex, which typically comprises 15% vinyl pyridine, 15% styrene, and 70% butadiene monomers. In addition to the VP latex, the aqueous dispersion can comprise one or more additional latexes, such as a styrene-butadiene latex (SBR) and natural rubber latex (NR).

[0029] For isoprene rubber, the use of natural latex with a high ammonia content, which comes from the “Hevea Brasiliensis” tree, is preferred.

[0030] Suitable polyisocyanate compounds as components of baths / dips for textile reinforcements are generally known to those skilled in the art. The polyisocyanate compound can be blocked with another compound or present as a dimer or higher homolog, i.e., "self-blocked." Blocked polyisocyanates are obtained, for example and preferably, by blocking free isocyanates with at least one substance selected from the group consisting of 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, malonic acid dialkyl esters, acetylacetone, acetoacetate alkyl esters, acetoxime, methyl ethyl ketoxime, 3,5-dimethylpyrazole, cyclohexanone oxime, 3-hydroxypyridine and acidic sodium sulfite.It is preferred in the context of the present invention that the polyisocyanate compound comprises building blocks which are selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic diisocyanates comprising 2,4- or 2,6-toluene diisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,3- or 1,4-phenyl diisocyanate.

[0031] The polycarboxylic acid is based, for example, to an extent of 10 to 100 mol%, preferably 30 to 100 mol%, particularly preferably 50 to 100 mol%, very particularly preferably 70 to 100 mol%, and especially preferably 90 to 100 mol% on monomers containing carboxylic acid groups. According to a particularly advantageous embodiment of the invention, the polycarboxylic acid is based to an extent of 100 mol% on monomers containing carboxylic acid groups, although further functional groups are not excluded. The polycarboxylic acid preferably has a weight-average molecular weight Mw according to GPC of 1,000 to 500,000 g / mol, preferably 3,000 to 100,000 g / mol. The polycarboxylic acid is preferably based on acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, and / or maleic acid monomers. According to a preferred embodiment, the polycarboxylic acid (based on acrylic acid monomers) is an acrylic resin.

[0032] Suitable epoxy compounds as components of corresponding aqueous dispersions are generally known to those skilled in the art. Within the scope of the present invention, it is preferred that the epoxy compound be selected from the group consisting of glycidyl-based glycerol, sorbitol-based epoxy compounds, phenol-based novolak epoxy compounds, and cresol-based novolak epoxy compounds. A particularly suitable epoxy compound is, for example, a glycerol-based polyglycidyl ether, such as Denacol™ EX-313, which is described, inter alia, in DE 69722388 T2.

[0033] Possible waxes as components of corresponding aqueous dispersions are generally known to the person skilled in the art. Preferred examples are paraffinic waxes, microcrystalline waxes, synthetic waxes, and waxes from natural sources such as beeswax, which also include combinations of two or more waxes.

[0034] Water-dispersible inorganic fillers are particularly suitable for the aqueous dispersion. Amorphous silicon dioxide (especially precipitated silica) and silicates with a BET surface area (according to ISO 9277:2010) of 30 to 450 m² are particularly preferred. 2 / g, preferably from 120 to 410 m 2 / G.

[0035] The aqueous dispersion preferably has a pH of 5 to 11, preferably 7 to 11, which can be conveniently adjusted with a base. The base is preferably a volatile base, which or its constituents evaporate during the process. According to a particularly advantageous embodiment of the invention, the base is ammonium hydroxide, i.e., an aqueous solution of ammonia.

[0036] In light of the above, a process according to the invention is preferred, wherein the aqueous dispersion comprises:

[0037] (x1) at least one rubber latex, preferably in a mass fraction of 4 to 60% based on the dry weight of the aqueous dispersion, and (x2) at least one protected isocyanate, preferably in a mass fraction of 0.1 to 10% based on the dry weight of the aqueous dispersion.

[0038] Also preferred is a process according to the invention, wherein the aqueous dispersion comprises:

[0039] (y1) at least one compound containing an epoxy group, preferably in a mass fraction of up to 6% based on the dry weight of the aqueous dispersion, and / or

[0040] (y2) at least one polymer having carboxylic acid functional groups, preferably in a mass fraction of up to 15% based on the dry weight of the aqueous dispersion.

[0041] Particularly preferred is a process according to the invention wherein the aqueous dispersion comprises one of the following components:

[0042] (z1) at least one filler, preferably in a mass fraction of 0.02 to 20% based on the dry weight of the aqueous dispersion, preferably with the proviso that the aqueous dispersion does not comprise a polymer having carboxylic acid functional groups, or

[0043] (z2) at least one polyisoprene rubber latex, preferably in a mass fraction of 1 to 20% based on the dry weight of the aqueous dispersion, preferably with the proviso that the aqueous dispersion comprises at least one rubber latex which is not a polyisoprene rubber latex, or

[0044] (z3) at least one wax, preferably in a mass fraction of 0.3 to 30% based on the dry weight of the aqueous dispersion. Among the possible aqueous dispersions for adhesion activation, three specific embodiments are particularly suitable.

[0045] On the one hand, a process according to the invention is preferred, wherein the aqueous dispersion comprises:

[0046] (h1) at least one rubber latex, in a mass fraction of 4 to 50%, preferably 4.5 to 25%, based on the dry weight of the aqueous dispersion,

[0047] (h2) at least one protected isocyanate, in a mass fraction of 0.1 to 4.5%, preferably 0.2 to 4%, based on the dry weight of the aqueous dispersion,

[0048] (h3) at least one filler, in a mass fraction of 0.02 to 20%, preferably 0.3 to 15%, based on the dry weight of the aqueous dispersion.

[0049] Alternatively, a process according to the invention is preferred, wherein the aqueous dispersion comprises:

[0050] (11) at least one rubber latex, in a mass fraction of 4 to 50%, preferably 4.5 to 25%, based on the dry weight of the aqueous dispersion,

[0051] (12) at least one protected isocyanate, in a mass fraction of 0.1 to 10%, preferably 0.2 to 4.5%, based on the dry weight of the aqueous dispersion,

[0052] (13) at least one wax, in a mass fraction of 0.3 to 30%, preferably 0.5 to 15%, based on the dry weight of the aqueous dispersion.

[0053] Alternatively, a process according to the invention is preferred, wherein the aqueous dispersion comprises: (j1) at least one rubber latex, in a mass fraction of 4 to 40%, preferably 4.5 to 20%, based on the dry weight of the aqueous dispersion, wherein the rubber latex is not a polyisoprene rubber latex,

[0054] (j2) at least one protected isocyanate, in a mass fraction of 0.1 to 10%, preferably 0.2 to 4.5%, based on the dry weight of the aqueous dispersion

[0055] (j3) at least one polyisoprene rubber latex, preferably in a mass fraction of 1 to 20%, preferably 2 to 15%, based on the dry weight of the aqueous dispersion.

[0056] With all the described embodiments concerning the aqueous dispersion, in particular those at least marked as preferred, in combination with the selection of the sustainable materials of the textile reinforcement, it has surprisingly been possible to provide an environmentally and health-friendly process with which more sustainable and at the same time optimized composite materials can be produced.

[0057] Even if another application method is possible, the aqueous dispersion is preferably applied as a dip. Therefore, a method according to the invention is preferred, wherein the treatment in step b) comprises immersing the textile reinforcement in the aqueous dispersion, wherein the treatment preferably also comprises hot-stretching the immersed textile reinforcement.

[0058] As already stated, the textile reinforcement produced or provided in step a) comprises filaments, wherein the filaments contain one or more materials selected from the group consisting of a1) recycled polymers and a2) bio-based polymers, wherein the recycled and bio-based polymers are preferably selected from the group consisting of

[0059] Polyesters, such as in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12,

[0060] PA10.10, PA12.12 and

[0061] Aramids, especially m-aramid and p-aramid.

[0062] Surprisingly, it has been found that the process according to the invention can be achieved by combining the selection of the aqueous dispersion for adhesion activation and the materials mentioned, in particular with the selection of the polymers from the group consisting of

[0063] Polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0064] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0065] Aramids, especially m-aramid and p-aramid, are more sustainable and at the same time more health and environmentally friendly and the composite materials produced with them have optimized durability.

[0066] In principle, the textile reinforcement can also comprise different filaments that differ in terms of material, whereby preferably all filaments contain one or more materials that are selected from the above-mentioned group.

[0067] Furthermore, a filament can contain exactly one of the materials mentioned or several of the materials mentioned, preferably in a homogeneous mixture.

[0068] Furthermore, a filament can contain one or more of the materials mentioned and at the same time at least one further material, such as in particular petroleum-based polyesters, such as in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0069] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0070] Aramids, such as in particular m-aramid and p-aramid. According to advantageous embodiments of the invention, however, the filaments of the textile reinforcement do not contain any other materials, in particular no other materials based on petroleum.

[0071] The filaments of the textile reinforcement are preferably in the form of a multifilament yarn. In the context of the present invention, the term "yarn" is also used for "multifilament yarn."

[0072] In the process according to the invention for producing a vulcanizable composite material, the textile reinforcements are thus preferably produced or provided in the form of one or more yarns.

[0073] A method according to the invention is preferred, wherein the one or more yarns each have a yarn fineness in the range of 100 to 5000 dtex.

[0074] Particularly preferred values ​​for the fineness of a yarn depend in particular on the type of elastomeric product and the resulting desired property profile.

[0075] It has been found to be advantageous in the context of the present invention if the yarn count for the use of the composite material produced in bicycle tires is from 100 to 1500 dtex, in car and VAN tires from 300 to 4000 dtex and, for example, in truck and agricultural tires from 500 to 5000 dtex.

[0076] A process according to the invention is also preferred, wherein the one or more yarns are each twisted at 100 to 600 T / m. Here, too, particularly preferred values ​​for the twist of a yarn depend in particular on the type of elastomeric product and the resulting desired property profile.

[0077] In addition, the expert knows how to appropriately match the yarn count and twist. Preferably, one or more yarns are twisted to form a reinforcement cord. In the case of a single yarn, this results in a 1-strand cord, while in the case of, for example, two yarns twisted together, a 2-strand cord is obtained.

[0078] In the case of a x2 cord, the two yarns are preferably first twisted individually in one direction (for example, in the S direction) and then twisted together in the opposite direction (in the same example, in the Z direction) at approximately the same speed to form the cord. It is irrelevant whether the twisting is carried out first in the S or Z direction. Production is carried out primarily using ring twisters or cabling machines.

[0079] A method according to the invention is preferred, wherein the one or more yarns in the case of an x2 cord or x3 cord each have a twist factor in the range from 100 to 300, preferably in the range from 150 to 250.

[0080] In the case of an x1 cord, it is preferred that the yarn has a twist factor of 20 to 100, particularly preferably 20 to 60, most preferably 30 to 50.

[0081] The twist factor a is a value known to the expert and is calculated from the twist level in T / m (“turns per meter”) and the fineness in tex:

[0082] In the process according to the invention for producing a vulcanizable composite material, the textile reinforcements are preferably produced or provided in the form of a reinforcing cord made of one or more yarns.

[0083] Also preferred is a method according to the invention, wherein the reinforcing cord comprises two or more yarns, wherein the reinforcing cord preferably has a total fineness in the range of 200 to 10,000 dtex.

[0084] Especially for the production of composite materials for use as

[0085] For belt bandages, carcass plies, bead reinforcements and belt plies of vehicle tires, methods according to the invention are preferred in which all processes are carried out as explained above.

[0086] In the context of the present invention, the term "recycled polymer" refers to a polymer obtained by at least one recycling process. The recycling process can be any recycling process known to the person skilled in the art, such as, in particular, chemical and / or mechanical recycling.

[0087] In the context of the present invention, mechanical recycling processes also include temperature treatments, such as remelting.

[0088] In the context of the present invention, chemical recycling refers to any type of chemical processing of waste and the subsequent recovery of new products or raw materials from it. This can also mean complete chemical degradation into molecules in which the material source, i.e., the chemical nature of the waste, is no longer directly recognizable, and subsequent synthesis from these molecules to polymers, which are then used as recycled polymers in textile reinforcements in the process according to the invention.

[0089] Furthermore, industrial yarn waste can also be recycled and used as material for the textile reinforcement in step a), as is particularly the case with PET and PA 6.6.

[0090] Depending on the type and similarity of the yarn waste to the required materials, chemical and / or mechanical recycling may be appropriate.

[0091] In the context of the present invention, the term “bio-based polymer” means a polymer which is composed entirely or at least partially of monomers obtained from biomass.

[0092] The polymer can be produced entirely from monomers derived from biomass. This optimizes the process according to the invention and the composite materials produced thereby, as well as the elastomeric products produced therefrom, particularly with regard to sustainability while simultaneously offering excellent properties.

[0093] However, the polymer can also be made only partially from monomers from biomass, especially if some of the monomers underlying the polymer are not accessible via biomass.

[0094] As a result, the process according to the invention and the composite materials according to the invention produced therewith and the elastomeric products according to the invention produced therefrom are optimized with regard to the flexibility and sustainability required depending on the availability of starting materials while at the same time having very good properties.

[0095] As is known to those skilled in the art, the proportion of bio-based materials, i.e. the proportion of renewable raw materials in the polymer, can be determined according to ASTM D 6866 (C-14 method).

[0096] In the following, further particular embodiments of the method according to the invention are described which are distinguished with regard to the selection of the material of the reinforcements and which are consequently based on corresponding process steps as sub-steps of the production of textile reinforcements in step a).

[0097] According to a first advantageous embodiment of the method according to the invention, the textile reinforcement in step a) comprises filaments which contain at least recycled PET, wherein method step a) comprises at least the following individual method steps: a01) providing at least one product made of PET, wherein the product is selected in particular from bottles and clothing and yarn waste; a02) mechanical and / or chemical recycling of the PET product from step a01); a03) forming the recycled PET from step a02) into filaments, wherein the filaments are preferably processed, in particular spun, into a yarn; a04) processing the filaments obtained in step a03), preferably in the form of a yarn, into a reinforcement cord, in particular a reinforcement cord.

[0098] The object underlying the invention is particularly well achieved by the selection of recycled PET, in particular PET recycled from bottles or clothing or yarn waste.

[0099] According to advantageous embodiments, in step a03) a PET yarn is obtained which is a so-called “regular PET yarn”.

[0100] In the context of the present invention, “regular PET yarn” is understood to mean in particular a yarn which has a heat shrinkage of greater than or equal to 8% and an elongation at 45 N of greater than 0.0056% / denier with filament finenesses of less than 5 denier.

[0101] According to a further advantageous embodiment of the method according to the invention, the textile reinforcement in step a) comprises filaments which contain at least recycled PET, wherein the method step a) comprises at least the following individual method steps: a10) provision of PET chips which comprise 100% by weight recycled PET from PET bottles or other PET products and optionally provision of chips made of original, i.e. petroleum-based, PET; a11) pre-crystallization, crystallization and solid-phase polymerization of the PET from step a10), whereby highly viscous PET chips with an intrinsic viscosity of 0.85 to 1.15 dl / g are obtained;a12) drying, optionally mixing the chips made of recycled PET with chips made of original PET, whereby PET chips are obtained which comprise 10 to 100 wt.% chips made of recycled PET, melting and extruding the PET chips for yarn spinning, subsequent yarn spinning by means of a spinneret comprising a post-heating with a buffer zone of the highly viscous PET chips from step a11), and gradually cooling the undrawn yarn, wherein the water content of the chips after drying is less than 30 ppm, the temperature of the post-heating below the spinneret is 280 to 350 °C and the length of the buffer zone below the post-heating during the step-by-step cooling is 20 to 100 mm;a13) oiling, drawing, heat-curing, and winding after the gradual cooling in step a12), thereby obtaining a PET yarn from filaments consisting entirely or partially of recycled PET, the PET yarn obtained being an HMLS PET yarn having a hot shrinkage of less than 8% and an elongation at 45 N of less than 0.0056% / denier for filament counts of less than 5 denier; a14) processing the yarn obtained in step a13) into a reinforcement cord;

[0102] The problem underlying the invention is solved particularly well by the selection of recycled HMLS-PET yarn.

[0103] The abbreviation "HMLS" is familiar to those skilled in the art and stands for "high modulus low shrinkage." An "HMLS yarn" is thus understood to be a yarn that has a high modulus and low shrinkage. For the purposes of the present invention, an HMLS yarn is defined as having, as stated above, a heat shrinkage of less than 8% and an elongation at 45 N of less than 0.0056% / denier with filament counts of less than 5 denier.

[0104] The HMLS-PET yarn preferably has a hot shrinkage of 4 to 8% and an elongation at 45 N of 0.002 to 0.0056% / denier at filament finenesses of less than 5 denier, particularly preferably 3 to 5 denier.

[0105] The elastomeric product according to the invention is preferably a vehicle tire comprising the HMLS-PET yarn A) in the carcass ply. This optimizes flatspot behavior (= reversible plastic flattening of the ground contact patch during parking) and prevents extensive sidewall constriction.

[0106] The heat shrinkage of yarns is determined in the present invention using the hot air shrinkage method according to ASTM D885. The test conditions are: temperature 177 °C, load 0.05 g / den, duration 10 min.

[0107] The elongation at 45 N is determined in the context of the present invention using an Instron tensile tester according to ASTM D885: Instron 5564 device, clamp: C-clamp, 2714-004 with pneumatic activation, load capacity 1 kN (one kiloNewton), test conditions: gauge length 250 mm, crosshead speed 300 mm / min, preload 0.05 gf / Den (gram-force per denier), air pressure 0.4 to 0.6 MPa, conditioning of the samples before the test: 24 hours at 24 ± (plus or minus) 2 °C, 55 ± 5% humidity.

[0108] In the present invention, the intrinsic viscosity is determined using an Ubbelohde capillary viscometer according to ASTM D4603.

[0109] Pre-crystallization, crystallization, and solid-state polymerization (SSP) in step a11 achieve further polymerization and thus a reduction in the proportion of shorter polymer molecules, thereby achieving molecular chain growth. This results in increased intrinsic viscosity. This improves the drawability of the material, while also improving the tensile stiffness and modulus (stiffness) of the yarn.

[0110] By combining the pre-crystallization and crystallization with the temperature of the post-heating below the spinneret of 280 to 350 °C and the length of the buffer zone below the post-heating during the stepwise cooling of 20 to 100 mm in step a12), the crystallization rate can be adjusted such that a high spinning speed and a high tensile rate can be selected during the spinning process.

[0111] Furthermore, the frequency of filament and yarn breakage is reduced, which allows a yarn with high tensile stiffness and high modulus to be obtained.

[0112] Solid-state polymerization (SSP) is a process in which raw PET chips are placed in a reactor and heated to polymerize. This increases the molecular chain length and intrinsic viscosity. The intrinsic viscosity of recycled PET chips is 0.55 to 0.75 dl / g.

[0113] The term solid-phase polymerization is also called solid-phase condensation in German, since condensation occurs when water is removed.

[0114] According to preferred embodiments, the recycled PET of the above-mentioned embodiments—from the processes according to steps a01) to a04) and a10) to a14)—is based entirely, i.e., 100% by weight, on recycled PET. As a result, the process according to the invention and the composite materials according to the invention produced therewith, as well as the elastomeric products according to the invention produced therefrom, are optimized particularly with regard to sustainability while simultaneously exhibiting very good properties.

[0115] According to further preferred embodiments, the recycled PET can also be based on 1 to 90 wt.% recycled PET and 10 to 99 wt.% petroleum-based PET. As a result, the process according to the invention and the composite materials according to the invention produced thereby, as well as the elastomeric products according to the invention produced therefrom, are particularly optimized with regard to the balance between sustainability and simultaneously excellent properties. At the same time, the properties of the manufactured products can be adjusted as needed by carefully selecting the proportion of recycled PET.

[0116] In the case of the method according to steps a01) to a04), according to this embodiment, in particular in step a03), petroleum-based PET is added in appropriate proportions during the forming of the filaments and / or during the forming of the filaments into the yarn.

[0117] Recycled PET, which is primarily produced through mechanical recycling of bottles, differs from original (virgin, non-recycled) PET due to additives, particularly the content of isophthalic acid (IPA). These additives, particularly IPA, are found, for example, in PET bottles.

[0118] While original PET has an isophthalic acid content of 0 wt.%, the IPA content in recycled PET can be up to 5 wt.%.

[0119] In particular, in the recycled PET used in the present invention, it is, for example, and in particular, 1.2 to 5 wt.%, particularly preferably 1.2 to 2.2 wt.%.

[0120] The weight data in percent (wt.%) refer to the PET and thus in the reinforcement according to the invention to the ungummed and untreated, ie in particular undipped, yarn.

[0121] Recycled PET obtained from yarn waste by mechanical recycling has a higher polydispersity index compared to reference yarns that were not recycled.

[0122] According to a further advantageous embodiment of the method according to the invention, the textile strength member in step a) comprises filaments which contain at least bio-based polymer, wherein method step a) comprises at least the following individual method steps: a21) producing or providing a starting composition comprising starting monomers which are produced completely or at least partially from biomass; a22) polymerizing the starting monomers contained in the starting composition to form a bio-based polymer; a23) forming the bio-based polymer into filaments, wherein the filaments are preferably processed, in particular spun, into a bio-based polymer yarn; a24) processing the filaments obtained in step a23), preferably in the form of a yarn, into a strength member, in particular a reinforcing cord.

[0123] In the context of the present invention, “made entirely from biomass” means that 100% by weight of the starting monomers were obtained directly from biomass.

[0124] In the context of the present invention, “at least partly produced from biomass” means that more than 0 wt.% of the starting monomers were obtained directly from biomass.

[0125] According to preferred embodiments, 10 to 100 wt.%, particularly preferably 30 to 100 wt.%, of the starting monomers are produced from biomass. This means that, according to these preferred embodiments, 10 to 100 wt.%, particularly preferably 30 to 100 wt.%, of the bio-based polymer is based on the polymerization of starting monomers produced from biomass.

[0126] Particularly preferably, the bio-based polymer is selected from the group consisting of polyethylene terephthalate (PET), polyamide 6.6 (PA 6.6), polyamide (PA 5.6), polyamide 4.6 (PA 4.6), polyamide 4.10 (PA 4.10) and aramid.

[0127] PET is based on polymerization, in particular polycondensation of the starting monomers terephthalic acid and monoethylene glycol (MEG, also ethanediol).

[0128] Preferably, the bio-based PET is based on the polymerization of starting monomers produced from biomass to the extent of 30 to 100 wt.%.

[0129] According to advantageous embodiments, both monomers of the bio-based PET are obtained from biomass instead of from petroleum.

[0130] According to further advantageous embodiments, at least monoethylene glycol is obtained from biomass, in particular from plant-based raw materials such as sugar cane or molasses. Polyamide 6.6 (PA6.6) is based on the polymerization, in particular polycondensation, of the starting monomers hexamethylenediamine and adipic acid.

[0131] Preferably, the bio-based PA6.6 is based on 50 to 100 wt.% of the polymerization of starting monomers produced from biomass.

[0132] According to advantageous embodiments, both monomers of the bio-based PA6.6 are obtained from biomass instead of petroleum.

[0133] Polyamide 5.6 is based on the polymerization, in particular polycondensation of the starting monomers pentamethylenediamine (1,5-diaminopentane) and adipic acid.

[0134] According to advantageous embodiments, both monomers of the bio-based PA5.6 are obtained from biomass instead of petroleum.

[0135] According to further advantageous embodiments, at least pentamethylenediamine is obtained from biomass instead of from petroleum.

[0136] Polyamide 4.6 is based in particular on the polymerization, in particular polycondensation, of the starting monomers hexamethylenediamine and succinic acid.

[0137] According to advantageous embodiments, both monomers of the bio-based PA4.6 are obtained from biomass instead of from petroleum.

[0138] According to further advantageous embodiments, at least succinic acid is obtained from biomass instead of from petroleum.

[0139] Polyamide 4.10 is based on the polymerization, in particular polycondensation of the starting monomers tetramethylenediamine and sebacic acid.

[0140] According to advantageous embodiments, both monomers of the bio-based PA4.10 are obtained from biomass instead of from petroleum.

[0141] According to further advantageous embodiments, at least tetramethylenediamine is obtained from biomass instead of petroleum. According to further advantageous embodiments, at least sebacic acid is obtained from biomass instead of petroleum.

[0142] According to advantageous embodiments, the bio-based polymer is bio-based aramid.

[0143] According to preferred embodiments, the bio-based aramid is based to 50 to 100 wt.% on the polymerization, in particular polycondensation, of starting monomers produced from biomass (monomers from biomass).

[0144] According to preferred embodiments, the bio-based aramid is based entirely, i.e. 100 wt.%, on the polymerization, in particular polycondensation, of monomers from biomass.

[0145] According to a further advantageous embodiment of the method according to the invention, the textile reinforcement in step a) comprises filaments which contain at least recycled polymer, wherein the method step a) comprises at least the following individual method steps: a31) provision of waste, such as in particular old tires, yarn waste, and waste from the production of semi-finished vehicle tires and other technical rubber articles; a32) pyrolysis of the waste from step a31), whereby a pyrolysis oil containing at least one chemical starting substance is obtained;a33) converting the chemical starting substance into at least one monomer, wherein the monomer is preferably selected from the group consisting of p-phenylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, terephthalic acid, monoethylene glycol, adipic acid, succinic acid, sebacic acid and polycondensable derivatives of these monomers, and polymerizing the monomer to a recycled polymer; a34) forming the recycled polymer into filaments, wherein the filaments are preferably processed, in particular spun, into a polymer yarn; a35) processing the filaments obtained in step a34), preferably in the form of a yarn, into a strength member, in particular a reinforcing cord;

[0146] In the context of the present invention, “waste” is understood to mean in principle all waste that is suitable as starting substances for the process steps.

[0147] The waste is preferably old tires, yarn waste, especially from yarn production, and waste from the manufacture of semi-finished vehicle tires and other technical rubber articles.

[0148] Old tires and yarn waste are particularly preferred.

[0149] The preferred monomers are in particular those from which polymers such as polyethylene terephthalate (PET) or polyamide 6.6 can be obtained by polycondensation.

[0150] “Polycondensable derivatives of these monomers” are understood to mean monomers whose basic structure is similar to the monomers mentioned and which lead to the same target polymers through analogous polycondensation.

[0151] In the case of PET as a “target polymer”, one monomer is terephthalic acid.

[0152] A polycondensable derivative of this would be, for example,

[0153] Methyl terephthalate.

[0154] In particular and for example, polycondensable derivatives are thus selected from carboxylic acid esters, preferably carboxylic acid alkyl esters, which are preferably selected from the group consisting of

[0155] Terephthalic acid alkyl esters, adipic acid alkyl esters, succinic acid alkyl esters, sebacic acid alkyl esters. The alkyl radical of all of the above-mentioned carboxylic acid alkyl esters is, for example, and preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl, particularly preferably methyl, ethyl, and propyl.

[0156] According to further preferred embodiments of the invention, the monomer in step a33) is selected from the group consisting of p-phenylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, terephthalic acid, monoethylene glycol, adipic acid, succinic acid and sebacic acid.

[0157] In all described embodiments, it is conceivable and preferred that additional steps are carried out in the process step of forming the polymers into filaments and / or the filaments into yarns, such as in particular the addition of a further polymer, preferably from one of the other described preferred processes for producing textile strength members according to step a).

[0158] This method preferably produces textile reinforcements that contain at least two different polymers, preferably in a homogeneous mixture. Thus, the process according to the invention is particularly optimized with regard to sustainability, and at the same time, the properties of the resulting composite materials and elastomer products can be tailored to specific needs through targeted material selection.

[0159] According to particularly advantageous embodiments of the method according to the invention, the textile reinforcement in step a) thus comprises filaments, wherein the filaments contain at least one material selected from the group consisting of recycled polyethylene terephthalate (rPET), recycled polyethylene naphthalate (rPEN), bio-based polyethylene terephthalate (bioPET), recycled PA6.6, bio-based PA6.6, bio-based PA5.6, bio-based PA4.6, bio-based PA4.10, bio-based aramid.

[0160] The crosslinkable rubberizing mixture preferably contains at least one component selected from the group consisting of bio-based fillers, preferably silica produced from rice husk ash, recycled fillers, preferably pyrolysis carbon blacks, bio-based polymers, preferably bio-based polybutadiene, and wherein the rubberizing mixture is preferably substantially free of resorcinol.

[0161] This further increases the sustainability as well as the environmental and health friendliness of the process according to the invention as well as of the produced composite material and the produced elastomeric product, while at the same time the physical properties of the produced composite material and the produced elastomeric product are at a very good level.

[0162] Pyrolysis carbon blacks are known to the person skilled in the art, for example from US 2010249353 A1, and are obtained by pyrolysis of scrap tires in the absence of oxygen.

[0163] Pyrolysis carbon black differs from industrial carbon blacks, especially ASTM carbon blacks such as N660, in that it has a higher ash content and a lower content of polycyclic aromatic hydrocarbons (PAHs).

[0164] Carbon blacks contain high levels of polycyclic aromatic hydrocarbons (PAHs). Carbon blacks have a PAH content of more than 200 mg / kg.

[0165] The PAH content of the pyrolysis carbon blacks used in the present invention is preferably less than 50 ppm (mg / kg), more preferably less than 40 ppm, most preferably less than 30 ppm, and again preferably less than 10 ppm. The lower limit is in the range of 0.1 mg / kg, which represents the detection limit for PAHs. In principle, the PAH content should be as low as possible.

[0166] The PAH content is determined according to ASTM D-5186.

[0167] The pyrolysis soot used in the present invention preferably has an ash content of 5 to 30 wt.%, particularly preferably 10 to 30 wt.%, and most preferably 10 to 20 wt.%. According to a preferred embodiment of the invention, the ash content is 15 to 20 wt.%. The ash content refers only to the pyrolysis soot and is determined by thermogravimetric analysis (TGA) of the pyrolysis soot according to ASTM D1506.

[0168] The term “silica made from rice husk ash” is also known to those skilled in the art as “rice husk ash silica” (RHAS).

[0169] This is silica extracted from the inorganic combustion residues (ash) of rice husks. The ash obtained from rice husks has a comparatively high silica content of more than 80% by weight and is therefore particularly suitable for the extraction of silica.

[0170] Preferably, the silica produced from rice husk ash contained in the rubber mixture has a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m 2 / g, particularly preferably from 35 to 350 m 2 / g, most preferably from 75 to 320 m 2 / g and again particularly preferred from 120 to 235 m 2 / g, and a CTAB surface area (according to ASTM D 3765) of 30 to 400 m 2 / g, particularly preferably from 30 to 330 m 2 / g, most preferably from 70 to 300 m 2 / g and again particularly preferred from 110 to 230 m 2 / g, on.

[0171] Bio-based polymers, preferably bio-based polybutadiene, means, analogous to the above statements, that at least one monomer of the polymer of the rubber coating mixture is obtained from biomass.

[0172] Preferably, the gumming mixture is substantially free of resorcinol.

[0173] This is achieved in particular and preferably by selecting one or more of the following options:

[0174] I) The gumming compound is free of reinforcing resins and contains 0 phr of methylene acceptors and methylene donors, which implies that the compound is free of resorcinol; II) the gumming compound is free of methylene acceptors and contains 0 phr of methylene acceptors, which implies that the compound is free of resorcinol

[0175] III) the gumming mixture contains a suitable substance as a substitute for resorcinol in combination with a methylene donor, as preferred and for example at least one novolak resin which has alkyl urethane units and an etherified melamine resin, as described for example in EP 2 432 810 B1 or WO 2021197648 A1.

[0176] Otherwise, the rubberizing mixture can be any suitable rubberizing mixture known to those skilled in the art for encasing reinforcements, especially textile reinforcements. The rubberizing mixture preferably contains at least one diene rubber, especially if the rubberizing mixture does not already contain a bio-based polymer, especially polybutadiene.

[0177] Due to the presence of at least one diene rubber, the rubber compound is particularly sulfur-vulcanizable. The resulting vulcanizable composite material is thus suitable for a wide variety of elastomeric products, particularly vehicle tires.

[0178] The vulcanizable composite materials produced by the process according to the invention can be used in blanks, for example in blanks for vehicle tires.

[0179] Consequently, a method according to the invention is also preferred, additionally comprising the step: d) producing an unvulcanized blank, in particular an unvulcanized vehicle tire blank, comprising the vulcanizable composite material.

[0180] The invention also relates to a method for producing an elastomeric product, in particular a vehicle tire, or a vulcanized composite material, comprising the steps of the method according to the invention for producing a vulcanizable composite material, and additionally at least one of the steps: e) vulcanizing the vulcanizable composite material to obtain a vulcanized composite material, and / or f) vulcanizing the unvulcanized blank to obtain an elastomeric product.

[0181] The invention also relates to the vulcanizable composite material produced by the process according to the invention, the vulcanized composite material producible therefrom and the corresponding elastomeric products, each of which results in the advantages discussed above.

[0182] The invention thus also relates to a vulcanizable composite material for the production of elastomeric products, in particular vehicle tires, preferably produced or producible by the process according to the invention for producing a vulcanizable composite material, comprising: i) at least one textile reinforcement which is adhesion-activated with an aqueous dispersion, and ii) a crosslinkable rubberizing mixture which surrounds the textile reinforcement, wherein the aqueous dispersion is substantially free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and is free of free formaldehyde and formaldehyde-releasing substances, wherein the textile reinforcement comprises filaments, wherein the filaments contain one or more materials which are selected from the group consisting of a1) recycled polymers and a2) bio-based polymers,wherein the recycled and bio-based polymers are preferably selected from the group consisting of,

[0183] Polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0184] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0185] Aramids, especially m-aramid and p-aramid.

[0186] Since the adhesion activation produced by means of the aqueous dispersion is a complex coating whose structure cannot inherently be described precisely, it is necessary to define the textile reinforcements used in the vulcanizable composite material according to the invention via the adhesion activation experienced.

[0187] Therefore, a vulcanizable composite material according to the invention is preferred, wherein the textile reinforcement is adhesively activated with the aqueous dispersion on all sections surrounded by the crosslinkable rubber mixture.

[0188] The invention also relates to a vulcanized composite material produced by vulcanization of the vulcanizable composite material according to the invention, preferably with the method according to the invention for producing a vulcanized composite material.

[0189] The invention also relates to an elastomeric product, in particular vehicle tires, comprising a vulcanized composite material according to the invention, preferably produced by the process according to the invention for producing an elastomeric product.

[0190] For the purposes of the present invention, vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck tires, agricultural tires, passenger car tires, and two-wheel tires. According to further preferred embodiments, the elastomeric product is a technical rubber article, such as, in particular, a conveyor belt, a strap, a belt, or a hose.

[0191] An elastomeric product is preferred, wherein the elastomeric product is a vehicle tire which comprises the vulcanized composite material in the carcass ply and the textile reinforcement preferably comprises filaments, wherein the filaments contain one or more materials selected from the group consisting of polyesters or polyamides.

[0192] Also preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire which comprises the vulcanized composite material in the wound bandage and the textile reinforcement preferably comprises filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides, wherein the filaments particularly preferably contain PA6.6 or a combination of PA6.6 and p-aramid or PET or PA4.6.

[0193] Also preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire which comprises the vulcanized composite material in the bead reinforcement and the textile reinforcement preferably comprises filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides, particularly preferably PA6.6 and PA6, and polyesters, particularly preferably PET, and aramids, particularly preferably p-aramid.

[0194] An elastomeric product is also preferred, wherein the elastomeric product is a vehicle tire which, on the one hand, has the vulcanized composite material in a first embodiment in the wound bandage and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides, wherein the filaments particularly preferably contain PA6.6, and, on the other hand, has the vulcanized composite material in a further embodiment in the carcass ply and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyesters, wherein the filaments particularly preferably contain PET or PEN.

[0195] An elastomeric product is also preferred, wherein the elastomeric product is a vehicle tire which, on the one hand, has the vulcanized composite material in a first embodiment in the belt layer and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides and aramids, wherein the filaments particularly preferably contain PA6.6 and / or PA6 and / or p-aramid, and, on the other hand, has the vulcanized composite material in a further embodiment in the carcass layer and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides, wherein the filaments particularly preferably contain PA6.6 and / or PA6.

[0196] Also preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire comprising at least one reinforcement cord, preferably at least one x2 and / or at least one x3 reinforcement cord, wherein at least one first yarn of the reinforcement cord comprises filaments of bio-based nylon and at least one further yarn comprises filaments of bio-based aramid. For example, and preferably, the vehicle tire comprises the reinforcement cord in the wound bandage.

[0197] According to advantageous developments of the invention, the elastomeric product contains recycled steel in the form of reinforcements. For example, the elastomeric product is a vehicle tire that contains recycled steel in the form of reinforcements in a component, such as at least one belt ply and / or at least one bead core and / or at least one carcass ply.

[0198] In the context of the present invention, “recycled steel” is understood to mean steel which has been produced completely, ie to 100% by weight, or at least partially, ie to 1 to 99.99% by weight, preferably 50 to 99.99% by weight, by a recycling process for steel (scrap steel).

[0199] This further optimizes the elastomer product in terms of sustainability.

[0200] The invention is further explained below with reference to some exemplary and particularly advantageous embodiments of the process according to the invention and the products according to the invention obtained therefrom.

[0201] Example 1

[0202] First, textile reinforcements are produced from recycled HMLS-PET yarn according to step a). For this purpose, PET chips, which comprise 100 wt.% recycled PET from PET bottles or other PET products, are provided as starting material in step a10), and the process is carried out according to steps a11) to a14), including the solid-state polymerization as described above.

[0203] The raw PET chips are pre-crystallized according to step a11) for 0.5 to 1.5 hours at a temperature of 150 to 180 °C and then crystallized for 4 to 6 hours at a temperature of 200 to 230 °C and finally reacted for 30 to 35 hours in an SSP reactor at a wall temperature of 200 to 220 °C.

[0204] The entire system of devices is operated in a nitrogen atmosphere, with the oxygen content of the nitrogen maintained at 30 to 70 ppm and the dew point preferably lower than - 70 °C (lower than minus 70 °C).

[0205] The chips are processed into an undrawn yarn according to step a12) and then processed into an HMLS yarn according to step a13), the yarn having a hot shrinkage of 2.3% and an elongation at 45 N of 0.0008% / denier at filament counts of less than 5 denier.

[0206] The yarn is produced with a count of 1667 dtex, and two yarns are end-twisted together to form a 2-strand cord. The cords are then pre-dipped with a pre-dip solution. The pre-dip solution has the following composition: 95.26% w / w water, 0.90% w / w Denacol EX313 (an epoxy compound), and 3.84% w / w Grilbond IL-6 (a polyisocyanate compound). The pre-dipped cords are then heat-treated at 210 to 250°C.

[0207] Thereafter, the cords are treated according to step b) with an aqueous dispersion for adhesion activation, wherein the aqueous dispersion contains neither free resorcinol or resorcinol precondensates nor free formaldehyde or formaldehyde-releasing substances, and otherwise contains the following components: 47.3 wt.% water, 35.67 wt.% VP latex (copolymer of butadiene, styrene and 2-vinylpyridine, contains approx. 15% wt.% vinylpyridine bound in the polymer, aqueous dispersion, 41% wt.%), 6.3 wt.% SBR latex (styrene-butadiene copolymer, aqueous dispersion, 41% wt.%), 4.33 wt.% protected isocyanate (Grilbond IL-6: caprolactam-protected 4,4'-methylene-diphenyl diisocyanate, aqueous dispersion, 60% wt.% (EMS-GRILTECH)), 0.13 wt.% Ammonia (ammonium hydroxide, aqueous solution, 25 wt.%), 0.34 wt.% polymer with carboxylic acid functional groups (Aerodur 950L: polyacrylate, aqueous solution, 50 wt.% in water (BASF)); 1.54 wt.-% epoxy compound (Denacol EX313: glycerol-based polyglycidyl ether (Nagase Chemtex); 4.4 wt.% wax (Hydrowax-Q: aqueous paraffin dispersion, 54% wt.% (Sasol). The dipped cords are then heat-treated at 170 to 250 °C.

[0208] The adhesion-activated textile reinforcement is then fully embedded in a crosslinkable rubber compound. The crosslinkable rubber compound contains, among other ingredients, 100 phr of diene rubber, at least 50 phr of polyisoprene, and 30 phr of pyrolysis carbon black.

[0209] As part of a conventional vulcanization system, the crosslinkable rubber compound also comprises 2.4 phr of sulfur, as well as at least one novolak resin containing alkyl urethane units, an etherified melamine resin, and other conventional components. The term phr (parts per hundred parts of rubber by weight) used in the present invention is the standard quantity used in the rubber industry for compound formulations. The dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all rubbers present in the compound, which adds up to 100.

[0210] The vulcanizable composite material produced as described above is combined with other components to form a carcass ply, forming an unvulcanized green car tire. The unvulcanized green tire is then vulcanized under standard conditions to produce a vehicle tire comprising the vulcanized composite material in the carcass ply.

[0211] The resulting exemplary car tire is a particularly advantageous embodiment of a product according to the invention, in which the advantages of the present invention are particularly evident. The car tire is manufactured in a particularly health- and environmentally-friendly, sustainable manner, or its composition is particularly sustainable, while simultaneously being characterized by optimal durability in ferry service.

[0212] Example 2

[0213] According to another example (Example 2), in step a), textile reinforcements are produced using substeps a21) to a24), wherein the textile reinforcements contain filaments made of 100 wt.% bio-based PET. For this purpose, both PET monomers are produced from biomass and then formed into filaments. Bio-based PET yarns with a fineness of 1500 denier are produced from the filaments, which are then end-twisted into a 2-strand cord, see Example 1 above.

[0214] Otherwise, the process according to the invention is carried out as described in Example 1.

[0215] The exemplary passenger car tire obtained according to Example 2 is also a particularly advantageous embodiment of a product according to the invention, in which the advantages of the present invention are particularly evident. Example 3

[0216] According to another example (Example 3), in step a), textile reinforcements are produced using substeps a21) to a24), wherein the textile reinforcements contain filaments made of 32.2 wt.% bio-based PET. For this purpose, the PET monomer monoethylene glycol (MEG) is produced from biomass and then polymerized together with the monomer terephthalic acid from petroleum-based sources and formed into filaments. Bio-based PET yarns with a fineness of 1500 denier are produced from the filaments, which are then end-twisted into a 2-strand cord, see Example 1 above.

[0217] Otherwise, the process according to the invention is carried out as described in Example 1. The exemplary passenger car tire obtained according to Example 3 is also a particularly advantageous embodiment of a product according to the invention, in which the advantages of the present invention are particularly evident.

Claims

Patent claims 1. A method for producing a vulcanizable composite material, comprising the steps of: a) producing or providing a textile reinforcement, b) treating the textile reinforcement with an aqueous dispersion to activate the adhesion of the textile reinforcement and to obtain an adhesion-activated textile reinforcement, and c) incorporating the adhesion-activated textile reinforcement into a crosslinkable rubber compound to obtain the vulcanizable composite material, wherein the aqueous dispersion is substantially free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and is free of free formaldehyde and formaldehyde-releasing substances, wherein the textile reinforcement in step a) comprises filaments, the filaments containing one or more materials selected from the group consisting of a1) recycled polymers and a2) bio-based polymers.wherein the recycled and bio-based polymers are preferentially selected from the group consisting of, Polyesters, especially polyethylene terephthalate (PET) and Polyethylene naphthalate (PEN), Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and Aramids, especially m-aramid and p-aramid.

2. The method of claim 1, wherein the aqueous dispersion comprises: (x1 ) at least one rubber latex, preferably in a mass fraction of 4 to 60% based on the dry weight of the aqueous dispersion, and (x2) at least one protected isocyanate, preferably in a mass fraction of 0.1 to 10% based on the dry weight of the aqueous dispersion.

3. A method according to claim 1 or 2, wherein the aqueous dispersion comprises: (y1 ) at least one compound containing an epoxy group, preferably in a mass fraction of up to 6% based on the dry weight of the aqueous dispersion, and / or (y2) at least one polymer with carboxylic acid functional groups, preferably in a mass fraction of up to 15% based on the dry weight of the aqueous dispersion.

4. A method according to any one of claims 1 to 3, wherein the aqueous dispersion comprises one of the following components: (z1) at least one filler, preferably in a mass fraction of 0.02 to 20% based on the dry weight of the aqueous dispersion, preferably with the proviso that the aqueous dispersion does not comprise a polymer with carboxylic acid functional groups, or (z2) at least one polyisoprene rubber latex, preferably in a mass fraction of 1 to 20% based on the dry weight of the aqueous dispersion, preferably with the proviso that the aqueous dispersion comprises at least one rubber latex which is not a polyisoprene rubber latex, or (z3) at least one wax, preferably in a mass fraction of 0.3 to 30% based on the dry weight of the aqueous dispersion.

5. A method according to any one of claims 1 to 4, wherein the textile reinforcement in step a) comprises filaments containing at least recycled PET, wherein process step a) comprises at least the following individual process steps: a01) provision of at least one PET product, wherein the product is selected in particular from bottles and clothing and yarn waste; a02) mechanical and / or chemical recycling of the PET product from step a01); a03) forming the recycled PET from step a02) into filaments, wherein the filaments are preferably processed into a yarn, in particular spun; a04) processing the filaments obtained in step a03), preferably in the form of a skein, into a reinforcement, in particular a reinforcing cord.

6. A method according to any of the preceding claims, wherein the textile reinforcement in step a) comprises filaments containing at least recycled PET, wherein process step a) comprises at least the following individual process steps: a10) provision of PET chips comprising 100 wt% recycled PET from PET bottles or other PET products and optionally provision of chips from virgin PET; a11) pre-crystallization, crystallization and solid-state polymerization of the PET from step a10), thereby obtaining high-viscosity PET chips with an intrinsic viscosity of 0.85 to 1.15 dl / g; a12) Drying, optionally mixing the chips made from recycled PET with chips made from virgin PET, thereby obtaining PET chips comprising 10 to 100 wt% recycled PET chips, melting and extruding the PET chips for yarn spinning, subsequent spinning using a spinneret comprising a reheating with a buffer zone of the high-viscosity PET chips from step a11), and stepwise cooling of the unstretched yarn, wherein the water content of the chips after drying is less than 30 ppm, the temperature of the reheating below the spinneret is 280 to 350 °C and the length of the buffer zone below the reheating during stepwise cooling is 20 to 100 mm;a13) Oiling, drawing, heat curing and winding after the stepwise cooling in step a12), yielding a PET yarn from filaments which are wholly or partly made from recycled PET, wherein the PET yarn obtained is an HMLS-PET yarn which has a heat shrinkage of less than 8% and an elongation at 45 N of less than 0.0056% / Den at filament finenesses of less than 5 Den; a14) Processing the yarn obtained in step a13) into a reinforcing cord.; 7. A method according to any of the preceding claims, wherein the textile reinforcement in step a) comprises filaments containing at least bio-based polymer, wherein process step a) comprises at least the following individual process steps: a21) producing or providing a starting composition comprising starting monomers that are wholly or at least partially produced from biomass; a22) polymerizing the starting monomers contained in the starting composition to form a bio-based polymer; a23) forming the bio-based polymer into filaments, wherein the filaments are preferably processed, in particular spun, into a bio-based polymer yarn; a24) Processing the filaments obtained in step a23), preferably in the form of a game, into a reinforcing cord, in particular a reinforcing cord.

8. A method according to any of the preceding claims, wherein the textile reinforcement in step a) comprises filaments containing at least recycled polymer, wherein process step a) comprises at least the following individual process steps: a31) provision of waste, such as in particular used tires, yarn waste, and waste from the manufacture of semi-finished products of vehicle tires and other technical rubber articles; a32) pyrolysis of the waste from step a31), whereby a pyrolysis oil containing at least one chemical starting material is obtained; a33) conversion of the chemical starting material to at least one monomer and polymerization of the monomer to a recycled polymer; a34) forming of the recycled polymer into filaments, wherein the filaments are preferably processed into a polymer yarn, in particular spun;a35) Processing the filaments obtained in step a34), preferably in the form of a game, into a reinforcing element, in particular a reinforcing cord.; 9. Method according to one of the preceding claims, wherein the textile reinforcement in step a) comprises filaments, the filaments comprising at least one material selected from the group consisting of recycled polyethylene terephthalate (rPET), recycled polyethylene naphthalate (rPEN), bio-based polyethylene terephthalate (bioPET), recycled PA6.6, bio-based PA6.6, bio-based PA5.6, bio-based PA4.6, bio-based PA4.10, bio-based aramid.

10. Method according to any of the preceding claims, wherein the crosslinkable rubber compound contains at least one component selected from the group consisting of bio-based fillers, preferably silica produced from rice hull ash, recycled fillers, preferably pyrolysis carbon black, bio-based polymers, preferably bio-based polybutadiene, and wherein the rubber compound is preferably substantially free of resorcinol.

11. Method according to any of the preceding claims, further comprising the step: d) producing an unvulcanized blank, in particular an unvulcanized vehicle tire blank, comprising the vulcanizable composite material.

12. A method for producing an elastomeric product, in particular a vehicle tire, or a vulcanized composite material, comprising the steps of the method according to any one of claims 1 to 11, and additionally at least one of the steps: e) vulcanizing the vulcanizable composite material to obtain a vulcanized composite material, and / or f) vulcanizing the unvulcanized blank to obtain an elastomeric product.

13. Vulcanizable composite material for the manufacture of elastomeric products, in particular vehicle tires, comprising: i) at least one textile reinforcing layer which is adhesion-activated with an aqueous dispersion, and ii) a crosslinkable rubber compound which surrounds the textile reinforcing layer, wherein the aqueous dispersion is essentially free of free resorcinol and resorcinol precondensates, in particular resorcinol-formaldehyde precondensates, and is free of free formaldehyde and formaldehyde-releasing substances, wherein the textile reinforcement comprises filaments, the filaments containing one or more materials selected from the group consisting of (a1) recycled polymers and (a2) bio-based polymers, wherein the recycled and bio-based polymers are preferably selected from the group consisting of Polyesters, especially polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and Aramids, especially m-aramid and p-aramid.

14. Vulcanized composite material produced by vulcanizing the vulcanizable composite material according to claim 13.

15. Elastomeric product, in particular vehicle tires, comprising a vulcanized composite material according to claim 14.

16. Elastomeric product according to claim 15, wherein the elastomeric product is a vehicle tire which has the vulcanized composite material in the carcass layer and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyesters.

17. Elastomeric product according to claim 15 or 16, wherein the elastomeric product is a vehicle tire which has the vulcanized composite material in the coil bandage and the textile reinforcement preferably has filaments, wherein the filaments contain one or more materials which are selected from the group consisting of polyamides, wherein the filaments particularly preferably contain PA6.6.

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