Elastomeric product, in particular vehicle tyre

Abstract

The invention relates to an elastomeric product, in particular a vehicle tyre, the elastomeric product comprising filaments composed of a) recycled polyethylene terephthalate (PET) and b) at least one further material. The further material is selected from the group consisting of b1) recycled polymers and b2) bio-based polymers, wherein the recycled polymers b1) are preferably selected from the group consisting of polyesters, such as in particular 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, wherein polyethylene terephthalate (PET) is excluded from group b1), and wherein the bio-based polymers b2) 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, as well as celluloses, such as in particular rayon, wherein the elastomeric product comprises the above-mentioned filaments composed of materials a) and b) preferably in a plurality of yarns spun from the filaments, wherein the yarns from the filaments are used in particular as reinforcements.

Description

[0001] Description

[0002] Elastomeric product, in particular vehicle tires

[0003] The invention relates to an elastomeric product, in particular a vehicle tire, wherein the elastomeric product comprises filaments made of a) recycled polyethylene terephthalate (PET) and b) at least one further material.

[0004] It is known that elastomeric products contain filaments, with the filaments being spun into yarns and serving as reinforcements in the elastomeric product. The yarns can be twisted into reinforcing cords, as is particularly the case with vehicle tires, with the cords in turn being arranged in a plurality within a reinforcement layer.

[0005] Other technical rubber articles, such as belts, straps and hoses, also often contain reinforcements.

[0006] Polyethylene terephthalate (PET) is often used as a material for such textile reinforcements.

[0007] The aim is to resolve existing conflicts between sustainability and performance requirements when selecting materials for elastomer products, such as vehicle tires, or at least to achieve an improvement.

[0008] DE 102010017107 A1 discloses a reinforcement cord comprising at least one yarn made of recycled PET. The recycled PET can, in particular, originate from PET beverage bottles.

[0009] The object of the present invention is to provide an elastomeric product which is further improved in terms of sustainability without this having an adverse effect on the properties of the elastomeric product.

[0010] The object is achieved by the elastomeric product according to claim 1. Preferred embodiments of the invention emerge from the further claims and the following explanations.

[0011] 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 particularly preferred. Likewise preferred are embodiments in which a feature of one embodiment designated as preferred to any extent is combined with one or more further features of other embodiments designated as preferred to any extent.

[0012] The invention relates to an elastomeric product, in particular vehicle tires, wherein the elastomeric product

[0013] Filaments made of a) recycled polyethylene terephthalate (PET) and b) at least one further material, wherein the further material is selected from the group consisting of b1) recycled polymers and b2) bio-based polymers, wherein the recycled polymers b1) are preferably selected from the group consisting of polyesters, such as in particular polyethylene naphthalate (PEN),

[0014] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0015] Aramids, such as in particular m-aramid and p-aramid, wherein polyethylene terephthalate (PET) is excluded from group b1), and wherein the bio-based polymers b2) are preferably selected from the group consisting of polyesters, such as in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0016] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0017] Aramids, such as m-aramid and p-aramid in particular, as well as celluloses, such as rayon in particular. Because the elastomeric product has the material combination of filaments described above, it is more sustainable. At the same time, this material combination makes it possible to design the elastomeric products in such a way that no disadvantages arise in terms of properties, especially with regard to the requirements profile for the typical use of the elastomeric products.

[0018] The elastomeric product comprises the aforementioned filaments made of materials a) and b), in particular in one or more reinforcement members. The reinforcement members are surrounded, in particular, by one or more rubber compounds, also called rubber coating compounds.

[0019] The elastomeric product comprises the said filaments made of materials a) and b), preferably in a plurality of yarns spun from the filaments, wherein the yarns made of the filaments serve in particular as strength members.

[0020] The filaments of materials a) and b) are spun together into one yarn and / or are present in separate yarns.

[0021] Preferably, each yarn has a fineness of 100 to 5000 dtex.

[0022] The yarns of all embodiments are preferably twisted into reinforcement cords. Each reinforcement cord preferably has a total fineness of 100 to 10,000 dtex.

[0023] Individual games can be twisted to form a x1 cord or several games can be twisted together, for example two games to form a x2 cord or three cords to form a x3 cord.

[0024] The yarn and / or reinforcement cords are preferably present in large numbers within a reinforcement layer.

[0025] This allows the reinforcing properties of the reinforcements made from the filaments of materials a) and b) to be particularly effective. According to preferred embodiments, the elastomeric product is a vehicle tire.

[0026] 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, agricultural, passenger car and two-wheeler tires.

[0027] According to further preferred embodiments, the elastomeric product is a technical rubber article, such as in particular a conveyor belt, a belt, a strap or a hose.

[0028] Preferred is an elastomeric product, in particular vehicle tires, wherein the elastomeric product comprises the filaments of a) recycled PET in a first yarn A) and the filaments of b) at least one further material in a second yarn B).

[0029] This ensures that the elastomeric product is composed sustainably and, at the same time, the properties of the yarns can be individually adjusted, also with regard to the special features resulting from the respective materials when manufacturing the yarn from the filaments.

[0030] According to advantageous embodiments, the yarns A) and B) are twisted together to form a reinforcement cord C).

[0031] In this way, the properties of the cord, which is a so-called hybrid cord, can be optimally adjusted with regard to the requirement profile of the elastomeric product, whereby in particular a synergism results from the advantages of the properties of the game A) from the filaments of material a) and the game B) from the filaments of material b).

[0032] The elastomeric product, in particular a vehicle tire, preferably comprises a plurality of reinforcing cords C) within a reinforcement layer. This particularly effectively utilizes the reinforcing properties of the cord made of filaments a) and b). According to advantageous embodiments of the invention, yarns A) made of filaments of a) recycled PET) and yarns B) made of filaments of the further material b), where b) is selected from recycled and bio-based polyamides and aramids, with PA6.6 and p-aramid being particularly preferred, as well as rayon, are end-twisted together to form a hybrid cord C).

[0033] The targeted combination of materials a) and b) results in particularly advantageous properties, as illustrated below. Recycled PET a) contributes in particular to the favorable physical properties at comparatively low cost and optimized sustainability.

[0034] Particularly preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcement cords C) in the wound bandage and b) is preferably selected from recycled and bio-based polyamides, with PA6.6 being particularly preferred. The polyamides, in particular PA6.6, as material b) contribute to favorable shrinkage behavior of the cords C).

[0035] As a result, the vehicle tire is optimized particularly in terms of sustainability and costs, while at the same time exhibiting excellent properties, particularly with regard to the requirements at high speeds, such as 180 km / h or more.

[0036] An elastomeric product is also preferred, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcement cords C) in the carcass ply and b) is preferably selected from recycled and bio-based aramids, with p-aramid being particularly preferred. Aramids as material b) contribute to the strength of the cords C).

[0037] As a result, the vehicle tire is optimized particularly in terms of sustainability and costs, while at the same time exhibiting excellent properties, particularly in terms of durability and driving dynamics.

[0038] An elastomeric product is also preferred, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcing cords C), preferably in the carcass ply, and b) is rayon. Rayon, as material b), contributes in particular to the temperature stability of the cords C).

[0039] As a result, the vehicle tire is optimized particularly in terms of sustainability and costs, while at the same time exhibiting excellent properties, particularly in terms of durability.

[0040] According to further advantageous embodiments, the elastomeric product, in particular a vehicle tire, comprises one or more yarns A) in a first reinforcement cord A') and one or more yarns B) in a second reinforcement cord B').

[0041] Here, the yarns made of filaments from materials a) and b) are therefore present in separate reinforcement cords.

[0042] This allows materials a) and b) to be used in the respective reinforcement cords at different locations of the elastomeric product in a targeted manner with regard to the desired properties.

[0043] According to advantageous embodiments, the elastomeric product, in particular a vehicle tire, comprises the reinforcing cords A') and B') in the same component.

[0044] According to particularly advantageous embodiments, the elastomeric

[0045] Product, in particular a vehicle tire, the reinforcement cords A') and B') in different components.

[0046] This optimizes the elastomer product for sustainability. At the same time, materials a) and b) in the respective reinforcement cords can be used in different components of the elastomer product to achieve the desired properties.

[0047] Particularly preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcement cords A') in the carcass ply and / or the bead reinforcement and / or the wound bandage and / or at least one belt ply. In this case, the vehicle tire preferably has reinforcement cords B') in at least one other component, which is preferably also a carcass ply, a bead reinforcement, at least one belt ply, or a wound bandage.

[0048] Preferred is a vehicle tire which has reinforcement cords A') in the wound bandage and reinforcement cords B') in the carcass ply and / or the bead reinforcement.

[0049] Also preferred is a vehicle tire which has reinforcing cords A') in the bead reinforcement and reinforcing cords B') in the carcass ply and / or the wound bandage.

[0050] Also preferred is a vehicle tire which has reinforcement cords A') in at least one belt ply and reinforcement cords B') in the carcass ply.

[0051] Also preferred is a vehicle tire which has reinforcement cords A') in the carcass ply and reinforcement cords B') in the wound bandage.

[0052] For example, and preferably, the elastomeric product is thus a vehicle tire, wherein the vehicle tire has reinforcing cords A') in the carcass ply and reinforcing cords B') in the wound bandage, wherein the material b) is particularly preferably selected from polyamides, particularly preferably bio-based PA6.6, and aramids, particularly preferably p-aramid.

[0053] For example, and preferably, the elastomeric product is also a vehicle tire, wherein the vehicle tire has reinforcing cords B') in the carcass ply and reinforcing cords A') in at least one other component, in particular in the bead reinforcement and / or in the wound bandage, wherein the material b) is particularly preferably regenerated cellulose, in particular rayon.

[0054] For example, and preferably, the elastomeric product is also a vehicle tire, wherein the vehicle tire has reinforcement cords A') in the wound bandage and reinforcement cords B') in at least one other component, in particular in the bead reinforcement and / or the carcass ply, wherein the material b) is particularly preferably selected from polyamides, wherein bio-based PA6.6 is particularly preferred.

[0055] According to further advantageous embodiments of the invention, the elastomeric product is a vehicle tire which comprises the above-described reinforcing cords C) made of the yarns A) and B) in at least one first component and reinforcing cords A') comprising at least one yarn A) and / or reinforcing cords B') comprising at least one yarn B) in at least one other component.

[0056] Particularly preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcement cords C) in the wound bandage and b) in the reinforcement cords C) is particularly preferably selected from recycled and bio-based polyamides, with PA6.6 being very particularly preferred; and the vehicle tire additionally has reinforcement cords B') at least in the carcass ply, wherein b) in the reinforcement cords B') is particularly preferably regenerated cellulose, in particular rayon, or bio-based PA6.6.

[0057] Also preferred is an elastomeric product, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcement cords C) in the carcass ply and b) in the reinforcement cords C) are particularly preferably selected from recycled and bio-based aramids, with p-aramid being very particularly preferred; and the vehicle tire additionally has reinforcement cords B') at least in the wound bandage, wherein b) in the reinforcement cords B') are particularly preferably selected from polyamides, particularly preferably bio-based PA6.6, and aramids, particularly preferably p-aramid.

[0058] Materials a) and b) are explained in more detail below.

[0059] Material a) is recycled polyethylene terephthalate (PET). The other material b) is selected from the group consisting of b1) recycled polymers and b2) bio-based polymers, whereby the recycled polymers and polymers b1) are preferably selected from the group consisting of polyesters, such as in particular polyethylene naphthalate (PEN),

[0060] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0061] Aramids, such as in particular m-aramid and p-aramid, wherein polyethylene terephthalate (PET) is excluded from group b1), and wherein the bio-based polymers b2) are preferably selected from the group consisting of polyesters, such as in particular polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),

[0062] Polyamides, such as in particular PA6.6, PA5.6, PA4.6, PA4.10, PA6, PA6.12, PA10.10, PA12.12 and

[0063] Aramids, such as m-aramid and p-aramid, as well as celluloses, such as rayon.

[0064] PET is excluded from group b1) because recycled PET is already present as material a) and, according to the invention, a combination of filaments made of a) recycled PET and filaments made of b) at least one other sustainable material is present in the elastomeric product.

[0065] Recycled PET (material a)) and recycled polymers (material of subgroup b1 )) in general are known to the person skilled in the art.

[0066] In the context of the present invention, the term "recycled polymer" refers to a polymer obtained through at least one recycling process. This and the further statements regarding recycling also apply to PET.

[0067] The recycling process may be any recycling process known to the person skilled in the art, such as, in particular, chemical and / or mechanical recycling.

[0068] The starting materials for recycling are primarily bottles, clothing, and yarn waste. Mechanical recycling processes within the scope of the present invention also include heat treatments, such as remelting.

[0069] 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.

[0070] Furthermore, industrial yarn waste can also be recycled and used as material a) or b1), as is particularly the case with PA 6.6.

[0071] Depending on the type and similarity of the yarn waste to the required materials, chemical and / or mechanical recycling may be appropriate.

[0072] Recycled PET, which is primarily produced through mechanical recycling of bottles, differs from virgin PET due to additives, particularly the content of isophthalic acid (IPA). These additives, particularly IPA, are found, for example, in PET bottles.

[0073] While original PET has an isophthalic acid content of 0 wt.%, the IPA content in recycled PET can be up to 5 wt.%.

[0074] Therefore, an elastomeric product, in particular vehicle tires, is preferred, wherein the filaments made of a) recycled PET contain 0.12 to 5 wt.%, in particular 0.12 to 2.2 wt.%, of isophthalic acid (IPA).

[0075] The weight percentages (wt. %) refer to the filaments and thus, in the elastomeric product according to the invention, to the unrubberized and untreated form, in particular the unrubberized and untreated, i.e., in particular, the undipped, yarn. Recycled PET obtained from yarn waste through mechanical recycling also exhibits a higher polydispersity index compared to reference yarns that were not recycled.

[0076] Also preferred is an elastomeric product, in particular vehicle tires, wherein the filaments made of a) recycled PET have a degree of crystallization of 45 to 53.5%.

[0077] The degree of crystallization is determined according to ASTM D1505 as follows: First, the yarn density is determined using a density gradient column. The degree of crystallization is then calculated by interpolation using the literature values ​​for the density of 100% amorphous and 100% crystalline PET given below. The density of 100% amorphous PET is 1.333 g / cm³. 3 , while that of 100% crystalline PET is 1,455 g / cm 3 amounts.

[0078] With such a degree of crystallization, the filaments, especially in the form of yarns and thus strength members, have the necessary properties with regard to stretching and shrinking behavior, especially for the high requirements when used in the carcass ply of vehicle tires.

[0079] Also preferred is an elastomeric product, in particular vehicle tires, wherein the filaments made of a) recycled PET comprise 10 to 100 wt.%, preferably 30 to 100 wt.%, particularly preferably 50 to 100 wt.%, recycled PET.

[0080] According to preferred embodiments, the recycled PET is based entirely, i.e., 100% by weight, on recycled PET. This optimizes the elastomeric product according to the invention, particularly with regard to sustainability, while simultaneously offering excellent properties.

[0081] According to further preferred embodiments, the recycled PET is also based on 1 to 90 wt.% recycled PET and 10 to 99 wt.% petroleum-based PET. As a result, the elastomeric product according to the invention is 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.

[0082] Strength members comprising filaments made from a) recycled PET are preferably obtained by the following process, wherein the process comprises at least the following individual process steps: a01) providing at least one product made from 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 strength member, in particular a reinforcing cord.

[0083] The described process can also be carried out analogously for the recycled polymers of subgroup b1).

[0084] Strength members comprising filaments made from b1) recycled polymers can alternatively and preferably be obtained by the following process, wherein the process comprises at least the following individual process steps: a31) provision of waste, such as in particular old tires, yarn waste, and waste from the manufacture 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) conversion of the chemical starting substance to 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 polymerization of 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;

[0085] 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.

[0086] 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.

[0087] Old tires and yarn waste are particularly preferred.

[0088] The preferred monomers are in particular those from which polymers such as polyethylene terephthalate (PET) or polyamide 6.6 can be obtained by polycondensation.

[0089] “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.

[0090] In the case of PET as a “target polymer”, one monomer is terephthalic acid.

[0091] A polycondensable derivative of this would be, for example,

[0092] Methyl terephthalate. In particular, and for example, polycondensable derivatives are thus selected from carboxylic acid esters, preferably alkyl carboxylic acid esters, which are preferably selected from the group consisting of alkyl terephthalates, alkyl adipic acid esters, alkyl succinates, and alkyl sebacic acid esters.

[0093] The alkyl radical of all 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, propyl.

[0094] 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.

[0095] According to advantageous embodiments of the invention, a recycled polymer b1), particularly preferably recycled PA6.6, in particular from yarn waste, is used as material b).

[0096] According to advantageous embodiments, the elastomeric product comprises the filaments of a) recycled PET in the form of a PET yarn A), which is a so-called “regular PET yarn”.

[0097] In the context of the present invention, “regular PET yarn” is understood to mean 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 counts of less than 5 denier.

[0098] According to advantageous embodiments, the elastomeric product comprises the filaments made of a) recycled PET in the form of an HMLS-PET yarn A), wherein the HMLS yarn has a heat shrinkage of less than 8% and an elongation at 45 N of less than 0.0056% / denier at filament counts of less than 5 denier. The object underlying the invention is particularly well achieved by selecting filaments a) in the form of recycled HMLS-PET yarn.

[0099] 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.

[0100] 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.

[0101] The elastomeric product is preferably a vehicle tire that incorporates 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.

[0102] HMLS-PET yarns or reinforcement cords made of HMLS-PET yarns, which contain 10 to 100 wt.% recycled PET, are preferably obtained by the following process, wherein the process comprises at least the following individual process steps: a10) provision of PET chips which comprise 100 wt.% 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-state 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, wherein the obtained PET yarn is 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) optionally processing the yarn obtained in step a13) into a reinforcement cord.

[0103] Thus, an elastomeric product, in particular vehicle tires, is also preferred, wherein the elastomeric product comprises the filaments of a) recycled PET in the form of an HMLS-PET yarn A), wherein the HMLS yarn is produced by a process comprising at least the process steps a10) to a14).

[0104] 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.

[0105] 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.

[0106] In the present invention, the intrinsic viscosity is determined using an Ubbelohde capillary viscometer according to ASTM D4603.

[0107] 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.

[0108] 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.

[0109] Furthermore, the frequency of filament and yarn breakage is reduced, which allows a yarn with high tensile stiffness and high modulus to be obtained.

[0110] 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. Solid-state polymerization is also known in German as solid-phase condensation, as condensation occurs due to the removal of water.

[0111] In the context of the present invention, the term “bio-based polymer” of subgroup b2) means a polymer which is composed entirely or at least partially of monomers obtained from biomass.

[0112] 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.

[0113] According to advantageous embodiments of the invention, the bio-based polymer b2) is made entirely, i.e., 100 wt. %, from monomers derived from biomass. This optimizes the elastomeric product according to the invention, particularly with regard to sustainability, while simultaneously offering excellent properties.

[0114] 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.

[0115] According to further advantageous embodiments of the invention, the bio-based polymer b2) is partially produced, i.e. more than 0 wt.% and less than 100 wt.%, from monomers from biomass, in particular if a part of the monomers underlying the polymer is not accessible via biomass.

[0116] As a result, the elastomeric product according to the invention is 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.

[0117] 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.

[0118] 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).

[0119] 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.

[0120] PET is based on polymerization, in particular polycondensation of the starting monomers terephthalic acid and monoethylene glycol (MEG, also ethanediol).

[0121] Preferably, the bio-based PET is based on the polymerization of starting monomers produced from biomass to the extent of 30 to 100 wt.%.

[0122] According to advantageous embodiments, both monomers of the bio-based PET are obtained from biomass instead of from petroleum.

[0123] According to further advantageous embodiments, at least monoethylene glycol is obtained from biomass, in particular from plant raw materials such as sugar cane or molasses.

[0124] Polyamide 6.6 (PA6.6) is based on the polymerization, in particular polycondensation, of the starting monomers hexamethylenediamine and adipic acid.

[0125] Preferably, the bio-based PA6.6 is based on 50 to 100 wt.% of the polymerization of starting monomers produced from biomass.

[0126] According to advantageous embodiments, both monomers of the bio-based PA6.6 are obtained from biomass instead of petroleum.

[0127] Polyamide 5.6 is based on the polymerization, in particular polycondensation, of the starting monomers pentamethylenediamine (1,5-diaminopentane) and adipic acid. According to advantageous embodiments, both monomers of the bio-based PA5.6 are obtained from biomass instead of petroleum.

[0128] According to further advantageous embodiments, at least pentamethylenediamine is obtained from biomass instead of from petroleum.

[0129] Polyamide 4.6 is based in particular on the polymerization, in particular polycondensation, of the starting monomers hexamethylenediamine and succinic acid.

[0130] According to advantageous embodiments, both monomers of the bio-based PA4.6 are obtained from biomass instead of from petroleum.

[0131] According to further advantageous embodiments, at least succinic acid is obtained from biomass instead of from petroleum.

[0132] Polyamide 4.10 is based on the polymerization, in particular polycondensation of the starting monomers tetramethylenediamine and sebacic acid.

[0133] According to advantageous embodiments, both monomers of the bio-based PA4.10 are obtained from biomass instead of from petroleum.

[0134] According to further advantageous embodiments, at least tetramethylenediamine is obtained from biomass instead of from petroleum.

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

[0136] According to advantageous embodiments, the bio-based polymer is bio-based aramid.

[0137] 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).

[0138] 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. According to advantageous embodiments of the invention, a bio-based polymer b2), particularly preferably bio-based PA6.6 and / or p-aramid, is used as material b).

[0139] Strength members comprising filaments made of b2) bio-based polymers are preferably obtained by the following process, wherein the process comprises at least the following individual process steps: b21) producing or providing a starting composition comprising starting monomers which are produced completely or at least partially from biomass; b22) polymerizing the starting monomers contained in the starting composition to form a bio-based polymer; b23) forming the bio-based polymer into filaments, wherein the filaments are preferably processed, in particular spun, into a bio-based polymer yarn; b24) processing the filaments obtained in step b23), preferably in the form of a yarn, into a strength member, in particular a reinforcing cord.

[0140] Preferred is an elastomeric product, in particular vehicle tires, wherein the further material b) is selected from recycled PA6.6, bio-based PA4.10, bio-based PA4.6, bio-based p-aramid and bio-based PET.

[0141] As stated at the outset, an elastomeric product, in particular a vehicle tire, is particularly preferred, wherein the elastomeric product comprises the filaments of a) recycled PET in a first yarn A) and the filaments of b) at least one further material in a second yarn B).

[0142] Here, yarns A) and B) are preferably surrounded by different or the same rubber mixture, hereinafter referred to as the "rubbering mixture." Yarns A) and B) are preferably present in the described cords C), which are a hybrid cord composed of at least one yarn A) and at least one yarn B), or the cords A') and B').

[0143] The rubber coating mixture of games A) and / or B) 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 black, bio-based polymers, preferably bio-based polybutadiene, and wherein the rubber coating mixture is preferably substantially free of resorcinol.

[0144] 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.

[0145] 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.

[0146] 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).

[0147] Carbon blacks contain high levels of polycyclic aromatic hydrocarbons (PAHs). Carbon blacks have a PAH content of more than 200 mg / kg.

[0148] 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.

[0149] The PAH content is determined according to ASTM D-5186.

[0150] The pyrolysis carbon black 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.%.

[0151] The ash content refers only to the pyrolysis soot and is determined by thermogravimetric analysis (TGA) of the pyrolysis soot according to ASTM D1506.

[0152] The term “silica made from rice husk ash” is also known to those skilled in the art as “rice husk ash silica” (RHAS).

[0153] 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.

[0154] 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.

[0155] Bio-based polymers, preferably bio-based polybutadiene, means, analogous to the above statements, that at least one monomer of the polymer of the rubberizing mixture is obtained from biomass. Preferably, the rubberizing mixture is essentially free of resorcinol.

[0156] This is achieved in particular and preferably by selecting one or more of the following options:

[0157] I) The rubber 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;

[0158] 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

[0159] 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.

[0160] 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.

[0161] Due to the presence of at least one diene rubber, the rubber compound is particularly sulfur-vulcanizable.

[0162] All described reinforcements made of filaments a) and b) are preferably treated in a known manner before being coated with one or more rubber coating mixtures.

[0163] In particular, the strength members are activated for adhesion.

[0164] For this purpose, the formed reinforcements are further processed using a dip.

[0165] This gives the reinforcement, especially the yarn or cord, ideal physical properties and optimized adhesion to the rubber compound that is subsequently applied.

[0166] In particular, the dip may comprise a pre-dip and a RFL dip (resorcinol-formaldehyde latex) known in the art or an environmentally and health-friendly RFL-free alternative, as for example in DE

[0167] 102014211362 A1 , WO 2019015792 A1 , EP 3702521 A1 , EP 3702522 A1 or EP 3702523 A1.

[0168] The adhesion treatment by means of a dip can thus comprise, in particular, 1-bath or 2-bath processes (pre-dip and dip) known in the prior art.

[0169] During the dipping process, state-of-the-art equipment and conditions, such as dipping solution tanks, stress zones, and ovens, are used in succession. The reinforcement is stretched by 0 to 8%, particularly 0 to 3%.

[0170] In this case, reinforcements comprising filaments made of a) recycled PET are treated by means of an RFL dip according to advantageous embodiments.

[0171] Otherwise, the production of the elastomeric product, in particular vehicle tire, is carried out in a manner known to the person skilled in the art using devices known to the person skilled in the art.

[0172] In particular, an unvulcanized blank, in particular an unvulcanized vehicle tire, comprising filaments made of materials a) and b), including all described embodiments, is first prepared by stacking the corresponding components, which comprise unvulcanized rubber mixtures, on top of one another. The blank is then vulcanized.

[0173] 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.

[0174] 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 steel recycling process (scrap steel).

[0175] This further optimizes the elastomer product in terms of sustainability.

[0176] The invention is further explained below using some exemplary and particularly advantageous embodiments.

[0177] Example 1

[0178] First, textile reinforcements containing filaments from a) recycled PET are produced in the form of recycled HMLS-PET yarn. For this purpose, PET chips comprising 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.

[0179] 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.

[0180] 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).

[0181] The chips are processed into an undrawn yarn A) 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.

[0182] The yarn A) is produced with a fineness of 1100 dtex and 2 yarns are end-twisted together to form a x2 cord A').

[0183] The cords (A') are then pretreated with a pre-dip. The pre-dip 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.

[0184] The cords are then treated with a state-of-the-art RFL dip to activate adhesion. The dipped cords are then heat-treated at 170 to 250 °C.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] The reinforcements rubberized as described above are provided as a vulcanizable reinforcement layer, specifically in the form of a carcass ply. Furthermore, a vulcanizable reinforcement layer is provided as a wound bandage as a further component, wherein the wound bandage contains filaments of material b), specifically in the form of x2 cords B') made of yarns B) with a yarn count of 470 dtex, wherein material b) is particularly preferably selected from polyamides, with bio-based PA6.6 being very particularly preferred. The 470x2 cords of PA6.6 are also rubberized with a rubberizing mixture containing, among other ingredients, 100 phr of diene rubber, including at least 50 phr of polyisoprene, and 30 phr of pyrolysis carbon black. The rubber compound of the wound bandage can be different from the rubber compound of the carcass ply, with the expert selecting customary components with regard to the respective components and the resulting requirements.

[0189] The two unvulcanized components are combined with other components to form an unvulcanized green car tire.

[0190] The unvulcanized green tire is then vulcanized under normal conditions to produce a vehicle tire, which comprises filaments made of a) recycled PET in the carcass ply and filaments made of b) the other sustainable material, for example bio-based PA6.6, in the wound bandage.

[0191] 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.

Claims

Patent claims 1. Elastomeric product, in particular vehicle tires, wherein the elastomeric product filaments made of a) recycled polyethylene terephthalate (PET) and b) at least one further material, wherein the further material is selected from the group consisting of b1) recycled polymers and b2) bio-based polymers, wherein the recycled polymers b1) are preferably selected from the group consisting of polyesters, such as in particular 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, in particular m-aramid and p-aramid, wherein polyethylene terephthalate (PET) is excluded from group b1), and wherein the bio-based polymers b2) are preferably selected from the group consisting of polyesters, 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, in particular m-aramid and p-aramid, and celluloses, in particular rayon, wherein the elastomeric product preferably comprises the aforementioned filaments made from materials a) and b) in a plurality of yarns spun from the filaments, wherein the yarns made from the filaments serve in particular as strength carriers.

2. Elastomeric product, in particular vehicle tire, according to claim 1, wherein the elastomeric product comprises the filaments made of a) recycled PET in a first yarn A) and the filaments made of b) at least one further material in a second yarn B).

3. Elastomeric product, in particular vehicle tire, according to claim 2, wherein the Game A) and B) are twisted together to form a reinforcing cord C).

4. Elastomeric product according to claim 3, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcing cords C) in the coil bandage and b) is preferably selected from recycled and bio-based polyamides, wherein PA6.6 is particularly preferred.

5. Elastomeric product according to claim 3, wherein the elastomeric product is a vehicle tire, wherein the vehicle tire has reinforcing cords C) in the carcass layer and b) is preferably selected from rayon as well as recycled and bio-based aramids, wherein p-aramid is particularly preferred.

6. Elastomeric product, in particular vehicle tires, according to claim 2, wherein the elastomeric product comprises one or more Game A) in a first reinforcement chord A') and one or more Game B) in a second reinforcement chord B').

7. Elastomeric product, in particular vehicle tire, according to claim 6, wherein the elastomeric product has the reinforcing cords A') and B') in the same component.

8. Elastomeric product, in particular vehicle tire, according to claim 6, wherein the elastomeric product comprises the reinforcing cords A') and B') in different components, wherein the elastomeric product is preferably a vehicle tire, wherein the vehicle tire comprises reinforcing cords A') preferably in the carcass ply and / or the bead reinforcement and / or the coil bandage and / or at least one belt ply and reinforcing cords B') preferably in at least one other component, which is preferably also a carcass ply, a bead reinforcement, at least one belt ply and / or a coil bandage.

9. Elastomeric product according to claim 8, wherein the elastomeric product is a vehicle tire comprising reinforcing cords A') in the coil bandage and reinforcing cords B') in the carcass layer and / or the bead reinforcer.

10. Elastomeric product according to claim 8, wherein the elastomeric product is a vehicle tire comprising reinforcing cords A') in the bead reinforcement and reinforcing cords B') in the carcass layer and / or the coil bandage.

11. Elastomeric product according to claim 8, wherein the elastomeric product is a vehicle tire comprising reinforcing cords A') in at least one belt layer and reinforcing cords B') in the carcass layer.

12. Elastomeric product according to claim 8, wherein the elastomeric product is a vehicle tire comprising reinforcing cords A') in the carcass layer and reinforcing cords B') in the coil bandage.

13. Elastomeric product, in particular vehicle tires, according to one of the preceding claims, wherein the elastomeric product comprises the filaments made of a) recycled PET in the form of an HMLS-PET yarn A), wherein the HMLS yarn 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.

14. Elastomeric product, in particular vehicle tire, according to one of the preceding claims, wherein the filaments comprise a) recycled PET 10 to 100 wt.%, preferably 30 to 100 wt.%, particularly preferably 50 to 100 wt.% recycled PET.

15. Elastomeric product, in particular vehicle tire, according to one of the preceding claims, wherein the filaments made of a) recycled PET contain 0.12 to 5 wt.%, in particular 0.12 to 2.2 wt.%, isophthalic acid (IPA).

16. Elastomeric product, in particular vehicle tires, according to one of the preceding claims, wherein the filaments made of a) recycled PET have a degree of crystallinity of 45 to 53.5%.

17. Elastomeric product, in particular vehicle tires, according to one of the preceding claims, wherein the elastomeric product comprises the filaments made of a) recycled PET in the form of an HMLS-PET yarn A), wherein the HMLS yarn is produced by at least the following process steps: a10) provision of PET chips comprising 100 wt.% recycled PET from PET bottles or other PET products and optionally provision of chips made 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 with a viscosity of 10 to 100 wt.-% chips made from recycled PET, melting and extruding the PET chips for yarn spinning, subsequent chamfer spinning using a spinneret comprising a reheat with a buffer zone of the high-viscosity PET chips from step a11), and stepwise cooling of the unstretched chamfer, wherein the water content of the chips after drying is less than 30 ppm, the temperature of the reheat below the spinneret is 280 to 350 °C and the length of the buffer zone below the reheat during stepwise cooling is 20 to 100 mm; a13) oiling, drawing, heat curing and winding after stepwise cooling in step a12), yielding an HMLS-PET yarn which has a hot 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) optionally process the game obtained in step a13) into a reinforcement chord.

18. Elastomeric product, in particular vehicle tire, according to any one of claims 2 to 17, wherein the further material b) is selected from recycled PA6.6, bio-based PA4.10, bio-based PA4.6, bio-based p-aramid and bio-based PET.

19. Elastomeric product, in particular vehicle tires, according to any one of claims 2 to 18, wherein the elastomeric product comprises the filaments made of a) recycled PET in a first yarn A) and the filaments made of b) at least one further material in a second yarn B), wherein yarns A) and B) are surrounded by different or the same rubber compound, wherein the rubber compound of yarns A) and / or B) 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.