EP3956398A1 - Utilisation d'une composition élastomère thermoplastique pour la fabrication d'un revêtement de sol et revêtement de sol - Google Patents

Utilisation d'une composition élastomère thermoplastique pour la fabrication d'un revêtement de sol et revêtement de sol

Info

Publication number
EP3956398A1
EP3956398A1 EP20716454.2A EP20716454A EP3956398A1 EP 3956398 A1 EP3956398 A1 EP 3956398A1 EP 20716454 A EP20716454 A EP 20716454A EP 3956398 A1 EP3956398 A1 EP 3956398A1
Authority
EP
European Patent Office
Prior art keywords
rubber
tpe
particles
thermoplastic elastomer
covering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20716454.2A
Other languages
German (de)
English (en)
Inventor
Frieder Vielsack
Christian Wimmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gezolan AG
Original Assignee
Gezolan AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gezolan AG filed Critical Gezolan AG
Publication of EP3956398A1 publication Critical patent/EP3956398A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/06—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003
    • E01C13/065—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003 at least one in situ layer consisting of or including bitumen, rubber or plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • thermoplastic elastomer composition for the production of a floor covering and floor covering
  • the present invention relates to the use of a thermoplastic elastomer (TPE) for the production of a surface covering, in particular a running track covering or fall protection covering, in particular a running track covering or fall protection covering for sports, playgrounds and leisure areas.
  • TPE thermoplastic elastomer
  • the present invention also relates to a surface covering, in particular a running track surface or fall protection covering, in particular a running track surface or fall protection covering for sports, play and leisure areas, the surface covering having a TPE.
  • the commonly used adhesives based on lK PU are harmful or harmful to health.
  • running and fall protection surfaces are manufactured using a system made up of several components, in which at least two components, usually from different manufacturers, have to be mixed in the correct ratio, ie the rubber granulate has to be used in a certain ratio to the adhesive. This is labor-intensive and has sources of error.
  • the compatibility of all components to be used is always a challenge, since different rubbers also require different adhesives.
  • the adhesive used for the rubber granules it would be desirable for the adhesive used for the rubber granules to have elastic properties in addition to the adhesive property, so that a desired elongation at break and tensile strength is ensured. Furthermore, it would also be desirable that the granules used for the production of the surface covering themselves have adhesive properties.
  • PU polyurethanes
  • a TPE is used according to the invention for the production of a surface covering, ie the The present invention relates to the use of a TPE for the manufacture of a surface covering.
  • the present invention relates to a method for producing a surface covering, in which a TPE or a material containing TPE is applied as a surface or is applied to a surface.
  • the use according to the invention is always referred to below, even if the method mentioned is also meant.
  • a surface covering is understood to mean covering any surface.
  • the surface covering is a floor covering, more preferably a running track covering or fall protection covering, in particular a running track covering or fall protection covering for sports, playgrounds and leisure areas.
  • the surface covering can be used as the top surface covering of a fall protection covering or as a substructure for a further fall protection covering arranged on it.
  • a TPE is understood to mean one which consists of a polymer or a polymer mixture (blend), preferably a polymer mixture, and at its service temperature has properties which are similar to those of vulcanized rubber, but which at elevated temperatures like a thermoplastic material processes and can be processed.
  • the surface covering can consist of the TPE.
  • particles of TPE are preferably heated to a temperature above the melting point of the TPE and applied to a surface.
  • TPE the temperatures mentioned above the melting point of the TPE and the methods of application to a surface are also preferred here.
  • the TPE can also initially be presented separately and then processed with further components to form a surface covering, as is described in more detail below.
  • TPE tyrene-co-styrene-ethylene glycol dimethacrylate copolymer
  • a material containing TPE is used to produce the surface covering.
  • the material containing TPE can be a composite material or a two-component mixture, as described in more detail below.
  • the TPE or the TPE-containing material can be heated to a temperature above the melting point of the thermoplastic elastomer and applied to a surface.
  • the TPE is preferably heated to a temperature in a range from 140 ° C to 220 ° C.
  • a rubber-containing material can also be used in the use according to the invention for the manufacture of the surface covering.
  • the rubber-containing material is preferably in the form of rubber-containing particles.
  • the TPE is preferably used to fix the rubber-containing particles.
  • the particles containing the rubber with are (partially) coated with the thermoplastic elastomer and thus represent a composite material in the form of composite particles.
  • Particles contained in the rubber can be presented and at least partially coated with TPE.
  • TPE thermoplastic polyethylene
  • they can either be dipped into the melted TPE, or the TPE is rubbed onto the rubber particles in the form of a micro-granulate and then heat-treated with the rubber at a temperature above the melting point of the TPE .
  • a temperature in the range from 140 ° C. to 220 ° C. is used.
  • the particles containing the rubber treated in this way are then allowed to cool to room temperature. In this way, composite particles are obtained in which the particles contained in the rubber are at least partially coated with TPE.
  • (b) Another possibility for producing the composite particles is to first produce a flat extrudate from rubber, which is then coated with the TPE according to the invention and then made up or granulated to form the composite particles.
  • hot TPE can be applied to a hot flat extrudate of an already crosslinked rubber the.
  • the rubber of the flat extrudate can still be present uncrosslinked and can only be crosslinked after the TPE has been applied.
  • the last-mentioned variant has the advantage that the TPE bonds better with the rubber.
  • partially coated means that not the entire surface of the rubber-containing particle is coated with TPE, but preferably a sufficient amount of the surface so that when the TPE coating is re-melted, it is distributed over the surface of the particles, and the composite particles can be connected to one another to form a surface covering, but it is also conceivable that the surface of the particles containing the rubber is completely coated with TPE.
  • the composite particles are used to produce a surface covering, it is preferred that they are heated to a temperature above the melting point of the TPE and applied as a surface or applied to a surface, or vice versa.
  • either the rubber-containing particles or the TPE or both can contain one or more additives in the composite material that can be used according to the invention, which allow the TPE to be heated and melted by microwaves, induction or IR radiation.
  • the composite particles are preferably heated with the aid of a heating device, for example by means of a heating extruder. Corresponding heating techniques are described below. So the composite particles can be heated in a heater and then applied as a surface or applied to a surface.
  • a heat heater can be used for heating or, if the composite particles contain appropriate additives, an induction heater, microwave heater or IR radiant heater can be used.
  • the composite particles already applied as a surface or applied to a surface can also be heated by a suitably heated leveling roller or a self-propelled or remotely controlled heating and / or leveling robot.
  • the last-mentioned devices can also be heated by means of normal heating, induction, microwave radiation, or IR radiation. Further heating and laying techniques are described below.
  • the particles and particles of TPE containing the rubber are used to produce the surface covering.
  • the particles containing the rubber and the particles made of TPE are preferably presented as a two-component mixture.
  • the two-component mixture is preferably heated to a temperature above the melting point of the TPE and then applied as a surface or applied to a surface.
  • the temperature above the melting point of the TPE is preferably in the range from 140 ° C to 220 ° C, more preferably in the range from 160 ° C to 220 ° C.
  • the composite particles or the two-component mixture are preferably heated for a period of up to 10 minutes.
  • the composite particles or the two-component mixture can be applied as a surface or applied to a surface and then heated to a temperature above the melting point of the TPE. The TPE or the TPE coating is melted. After subsequent cooling to ambient temperature or to a temperature below the melting point of the TPE, the composite particles or the particles of the two-component mixture are connected or glued to one another.
  • the composite material can also first be heated to a temperature above the melting point of the TPE and then applied as a surface or applied to a surface.
  • surface coverings can be produced from composite particles that are connected / glued to one another or the particles of the two-component mixture.
  • a surface covering using the two-component mixture it is preferred that it is first heated in a heater.
  • a heating extruder in a laying machine can be used for this. Further heating and laying techniques are described below.
  • the TPE is preferably distributed evenly around the particles containing the rubber.
  • the heating and mixing are preferably carried out over a period of 2 to 6 minutes.
  • the hot laying compound produced in this way is applied as a surface covering.
  • the surface covering is allowed to cool down. This results in the rubber-containing particles sintering over the TPE.
  • the surface covering produced in this way is preferably used as a substructure material for a surface covering to be applied as a superstructure material.
  • the volume fraction of TPE for the composite particles or the two-component mixture that can be used according to the invention is preferably in the range from 3% by volume to 40% by volume, more preferably in the range from 5% by volume to 25% by volume on the total volume of particles containing TPE and rubber.
  • a melt is produced from the particles of the TPE, then in a step (b) the melt is mixed with the particles containing the rubber to form a laying compound, and then in a step (c) the laying compound is applied to a surface.
  • Step (a) is preferably carried out at a temperature in the range from 140 ° C to 220 ° C, preferably 160 ° C to 220 ° C.
  • Step (b) is preferably carried out at a temperature in the range from 140 ° C to 180 ° C, preferably 140 ° C to 160 ° C.
  • Step (a) is preferably carried out in a heating device, for example a heating extruder. Further heating and laying techniques are described below.
  • the rubber-containing particles and the TPE melt are then preferably mixed in a mixer.
  • particles containing rubber are formed, the surface of which is partially or completely coated with TPE. These coated particles are preferably applied directly afterwards as a hot laying compound as a surface covering.
  • the advantage of this variant is that the production of a melt from TPE can take place at higher temperatures than if the rubber-containing particles were already included are present.
  • a surface covering produced in this way is preferably used as a substructure material or superstructure material for a fall protection cover.
  • a surface covering produced in this way is preferably used as a substructure material for a fall protection covering.
  • the volume fraction of TPE in step (b) is preferably in the range from 3% by volume to 40% by volume, more preferably in the range from 5% by volume to 25% by volume, based on the total volume of TPE and particles containing rubber.
  • the rubber-containing particles can have various shapes, such as a spherical shape, a disk shape, a rod shape or even irregular shapes.
  • the bulk density of the particles is preferably in the range from 200 g / 1 to 800 g / 1, more preferably in a range from 300 g / 1 to 750 g / 1 and most preferably in a range from 400 g / 1 to 700 g / 1, measured according to ISO 697.
  • the average particle size is in the range from 0.5 mm to 20 mm and more preferably in a range from 2 mm to 12 mm, the average particle size being determined by sieve analysis.
  • At least 90% of the particles have a particle size in the range from 0.2 mm to 10 mm, more preferably 95% of the particles have a particle size in the range from 0.3 mm to 5 mm, and most preferably 100% of the particles Particles have a particle size in the range from 0.5 mm to 3 mm.
  • a set of sieves of different mesh sizes is arranged one above the other, the particle size being determined by the mesh size that sieve is determined which just lets the particles pass. This results in a subdivision into certain particle classes, while the sieve fractions occurring in the individual particle classes and the bottom plate contents denote the particle size distribution.
  • the TPE particles which can be used according to the invention preferably have an average particle size in the range from 2 mm to 6 mm and more preferably an average particle size in the range from 3 mm to 5 mm.
  • the average particle size is determined by means of sieve analysis.
  • the thickness of the surface covering which can be produced according to the invention is preferably in a range from 10 mm to 200 mm. If the surface covering is designed as a fall protection covering, its thickness is more preferably in a range from 30 mm to 150 mm and even more preferably in a range from 50 mm to 120 mm. If the surface covering is designed as a raceway covering, its thickness is preferably in the range from 10 mm to 20 mm.
  • the surface covering that can be produced according to the invention is preferably used as a floor covering for playgrounds, sports and leisure areas.
  • the surface covering can be used as a superstructure material on another surface covering, the latter being referred to as substructure material.
  • the surface covering can also be used as the substructure material.
  • the surface covering made from composite particles is preferably used.
  • the two-component mixture or the variant in which a melt of TPE is first used are preferably used to produce a substructure is produced, to which the rubber-containing particles are then added.
  • any laying machines or laying devices which have the functions of mixing, tempering, homogenizing, transporting, spreading, applying and smoothing are suitable for producing the surface covering that can be produced according to the invention.
  • a hot air process, induction process or an irradiation process with UV or IR radiation can be used in which the starting materials
  • TPE TPE, or TPE and rubber-containing particles
  • the surface covering on site from the TPE, or the TPE and the rubber-containing particles, or to produce the surface covering in the form of webs or plates and then bring it to the place of use.
  • machines similar to conventional asphalt paving machines can be used that have an attached or integrated material processing.
  • the TPE and the particles containing the rubber can be mixed cold, and then brought to the temperature at which the TPE melts, for example in an extruder.
  • a conventional nelle asphalt paving machine with separate material preparation or an asphalt paving machine combined with a thermal container system can be used.
  • the starting materials can be mixed with one another in an internal mixer in a certain mixing ratio, brought to the above-mentioned melting temperature of the TPE, homogenized and prepared for further processing. Further processing can be carried out using the following methods: thermal container system, twin screw extruder, single screw extruder, metal belts, smoothing ruler or a so-called roller die system.
  • a hot air process with a roller die system can also be used.
  • the two starting materials TPE, or TPE and rubber-containing particles
  • the two starting materials can be conveyed to a slot nozzle in a certain mixing ratio by pressure and pre-melting.
  • Hot air is preferably blown into the nozzle to melt the TPE, the rubber-containing particles being coated by the TPE.
  • the melted material is laid as web material by a roller die or a roller arrangement.
  • the roller gap can be varied in order to produce the surface covering in different thicknesses.
  • Extruders can also be used to produce the surface covering.
  • the TPE is preferably melted first, and the particles containing the rubber are fed in in several stages.
  • the screw length of the extruder can vary from 20-40D.
  • the screw geometry preferably consists of feeding zones, shear zones, ho- homogenization zones, compression zones and discharge zones. At the end of the screw there is preferably a tool with different tool nozzles, depending on the geometry of the extrudate to be obtained.
  • a turbo mixer can also be used for the production of the surface covering.
  • the starting materials TPE, or TPE and rubber-containing particles
  • TPE melting temperature of the TPE
  • Further processing can take place as mentioned under point (ii).
  • a turbo mixer with a cantilever arm can also be used.
  • the starting materials TPE, or TPE and rubber-containing particles
  • the turbo mixer is equipped with a cantilever arm system that allows the hot mixture to be transported to the respective processing location.
  • a smoothing tool is preferably used directly on site to smooth the surface covering.
  • the starting materials (TPE, or TPE and rubber-containing particles) are mixed with one another and applied to a surface on site.
  • the material applied to a surface is brought to the melting temperature of the TPE using an induction process. In the case of using particles containing rubber, these are coated with the TPE. This creates a homogeneous surface covering.
  • the starting materials (TPE or TPE and rubber containing particles) are mixed with one another and applied to a surface as a 2-component mixture on site.
  • the material is heated as described under (i) to (vii) and the material is brought to the melting temperature of the TPE using highly concentrated UV or IR light. Alternatively, the mixture is brought to the melting temperature of the TPE using the heat of crosslinking that is generated using highly concentrated UV or IR light. If particles containing rubber are used, these are coated with the TPE, creating a homogeneous surface covering.
  • a surface covering in the form of sheets or panels can also be produced in the factory, which is then transported to the place to be used.
  • the following options (I) - (V) are available for producing the surface covering:
  • the starting materials (TPE, or TPE and rubber-containing particles) are mixed with one another by means of a single-screw extruder or twin-screw extruder, brought to the melting temperature of the TPE, homogenized and then applied to a fabric.
  • the fabric is preferably a fabric made of polyethylene or polypropylene or a mixture thereof.
  • the starting materials (TPE, or TPE and rubber-containing particles) are mixed with one another in a turbo mixer, brought to the melting temperature of the TPE, homogenized and prepared for further processing in sheet or plate material.
  • the starting materials are mixed with one another in an internal mixer (tantalizing or interlocking rotor system), brought to the melting temperature of the TPE, homogenized and prepared for further processing. This is followed by the production of sheet or plate material.
  • the rubber of the rubber-containing particles is preferably a rubber based on cross-linked diene-rubber mixtures, cross-linked ethylene-propylene-diene rubber (EPDM), cross-linked styrene-butadiene rubber (SBR), cross-linked natural rubber (NR), cross-linked butyl rubber (IIR) or a mixture thereof.
  • EPDM cross-linked ethylene-propylene-diene rubber
  • SBR cross-linked styrene-butadiene rubber
  • NR cross-linked natural rubber
  • IIR cross-linked butyl rubber
  • the last-mentioned rubbers are preferably used in the manufacture of the composite particles.
  • the rubber-containing particles can also be made from recycled rubber, for example made from recycled old tires. It is preferred that the recycled rubber is used in the two-component mixture or in the variant in which a TPE melt is first produced, to which the rubber-containing particles are then added.
  • the rubber in the rubber-containing particles is preferably a crosslinked rubber.
  • the networking can be done by means of Sulfur or phenolic resins, or also take place peroxidically.
  • the crosslinking is particularly preferably carried out by means of sulfur, ie the crosslinked rubber is preferably a sulfur crosslinked rubber.
  • the particles containing the rubber can have a plasticizer, fillers and / or anti-aging agents in addition to the crosslinked rubbers mentioned above.
  • the proportion of rubber here is preferably in the range from 10% by weight to 50% by weight, more preferably in the range from 15% by weight to 25% by weight, based on the total weight of the rubber-containing particles.
  • Dutral® TER 4038 EP from Versalis, Vistalon 7500 TM from ExxonMobil or Nordel TM IP 4640 from Dow Chemical can be used as rubber.
  • the rubber-containing particles are used relatively freshly produced to produce the surface covering, i.e. it is preferred that the surface is not older than 4 hours, preferably not older than 2 hours. This ensures that both sulfur and / or sulfur-containing compounds and the unreacted (uncrosslinked) free double bonds of the vulcanized rubber mixture on the surface are available for adhesion to the TPE.
  • the rubber is very particularly preferably an EPDM rubber-based rubber.
  • An EPDM rubber is understood herein to be an ethylene-propylene-diene rubber which is a terpolymer, synthetic rubber.
  • EPDM is one of the statistical copolymers with a saturated polymer main chain structure and double bonds in the side chain, which are used for this can crosslink the EPDM rubber in the rubber mixture with the help of the vulcanization system.
  • EPDM is preferably produced using metallocene or Ziegler-Natta catalysts based on vanadium compounds and aluminum alkyl chlorides.
  • Unconjugated dienes are used as dienes, of which only one double bond is involved in polymer chain formation, so that further double bonds remain outside the direct backbone and can be crosslinked with sulfur, peroxidically or phenolically.
  • Dicyclopentadiene (DCP), 1,4-hexadiene or ethylidene norbornene (ENB, IUPAC: 5-ethylidene-2-norbornene) are used as the diene component, ENB being particularly preferred.
  • the services differ in terms of the speed of networking.
  • EPDM containing DCP have the lowest, EPDM containing ENB the highest reactivity.
  • the EPDM based rubber is preferably one that has been crosslinked with sulfur. In this way, bonds of the composition according to the invention to the sulfur atoms can be established.
  • the present invention also relates to a surface covering, in particular a running track covering or fall protection covering, in particular a running track covering or fall protection covering for sports, playgrounds and leisure areas, which has a thermoplastic elastomer. All features of the use according to the invention apply equally to the surface covering according to the invention.
  • the surface covering according to the invention is preferably one which can be or is produced by means of the use / method according to the invention.
  • the TPE can be any thermoplastic elastomer, as long as it sees an increase in its melting temperature. has friction-free flow behavior.
  • “shear-free flow behavior” is understood to mean that several particles of TPE flow into one another or fuse into one another when raised to a temperature above its melting point and also retain the flowed or fused shape when cooled to below the melting temperature. In other words The grain boundaries flow into one another and remain in this state when they cool down.
  • the TPE is preferably a blend of a thermoplastic and an elastomer.
  • the TPE is very particularly preferably a blend of a thermoplastic, an elastomer and a polymer containing double bonds.
  • the elastomer is preferably an ethylene- ⁇ -olefin block copolymer.
  • the thermoplastic is preferably a non-elastomeric polyolefin.
  • the double bond-containing polymer is preferably one with a molar part of double bonds in the range from 5 to 100 mol%, based on the number of moles of all monomer units of the double bond-containing polymer used for the polymerization.
  • the TPE comprises an ethylene- ⁇ -olefin block copolymer, a double bond-containing polymer with a molar fraction of double bonds in the range from 5 to 100 mol%, based on the molar number of all monomer units of the double-bond-containing polymer used for the polymerization , and a non-elastomeric polyolefin.
  • ethylene- ⁇ -olefin copolymers are characterized by the property of good flexibility and elasticity highlight.
  • ethylene- ⁇ -olefin random copolymers have some deficiencies such as poor heat resistance, relatively low melting point, insufficient compression set, poor abrasion resistance and poor processability. Therefore, random ethylene- ⁇ -olefin copolymers are not suitable for processing by injection molding. In comparison with random ethylene- ⁇ -olefin copolymers, the ethylene- ⁇ -olefin block copolymers used according to the invention do not have these deficits.
  • Ethylene- ⁇ -olefin block copolymers generally have good heat resistance, a higher melting point, an improved compression set, good elasticity and good abrasion resistance.
  • the ethylene- ⁇ -olefin block copolymers are therefore particularly suitable as elastomeric components for the TPE which can be used according to the invention. Due to the properties mentioned, ethylene- ⁇ -olefin block copolymers are suitable for processing in injection molding. Due to the higher melting point, the good heat resistance and the high abrasion resistance, they are ideally suited as a component of the TPE, which when used according to the invention in surface coverings, such as fall protection coverings, is subject to high exposure to weather and use. Ethylene- ⁇ -olefin block copolymers are also characterized by their low to no health hazard potential.
  • the ethylene- ⁇ -olefin block copolymer in the TPE which can be used according to the invention is preferably essentially free of olefinically unsaturated double bonds.
  • the ethylene- ⁇ -olefin block copolymer is defined and described in more detail below, and examples thereof are given. It is preferred that the ethylene- ⁇ -olefin block copolymer in the TPE which can be used according to the invention is a linear multi-block copolymer composed of polyethylene blocks and o ⁇ -olefin blocks.
  • a multiblock copolymer is understood to mean one which has two or more different blocks.
  • the polymer containing double bonds is preferably an unhydrogenated styrene block copolymer (SBC), an ethylene- ⁇ -olefin block copolymer containing double bonds or a crosslinkable, uncrosslinked diene rubber, preferably styrene-isoprene-styrene Block copolymer (SIS), uncrosslinked EPDM or isoprene rubber (IR).
  • SBC unhydrogenated styrene block copolymer
  • SIS ethylene- ⁇ -olefin block copolymer
  • IR isoprene rubber
  • the double bond-containing polymer is an unhydrogenated SBC
  • the polymer containing double bonds is a sulfur-crosslinkable, uncrosslinked diene rubber, for example EPDM
  • this has a molar proportion of double bonds in the range from 5 to 40 mol%, more preferably 7 to 20 mol%, based on the number of moles of all for the polymer ization used monomer units of the uncrosslinked diene rubber, preferably EPDMs.
  • the sulfur-crosslinkable, uncrosslinked diene rubber is made up of 100 mol% of diene monomers, such as isoprene rubber, which ideally only contains isoprene as the diene monomer, the mole fraction of double bonds is 100 mol% .
  • the polymer containing double bonds is preferably used uncrosslinked in the TPE which can be used according to the invention.
  • the non-elastomeric polyolefin can preferably have a melting point of 120 ° C or more. Furthermore, the non-elastomeric polyolefin is preferably one that has a melt index (190 ° C / 2.16 kg) in the range of 20 g / 10 min to 160 g / 10 min. Examples of and preferred embodiments of non-elastomeric polyolefins are described below.
  • the TPE which can be used according to the invention can have a phenolic resin.
  • the presence of a phenolic resin can further increase the adhesion properties of the TPE according to the invention to rubber. It is assumed that the reason for this lies in the reaction of the phenolic resin with remaining, unreacted double bonds of the rubber on the one hand and with double bonds in the double bond-containing polymer of the TPE which can be used according to the invention on the other hand.
  • the phenolic resin preferably has at least two units which can react with double bonds.
  • the phenolic resin is preferably an octylphenol-based phenolic resin. Phenolic resins and de- Ren preferred embodiments are also described below be.
  • the TPE which can be used according to the invention can also contain a plasticizer.
  • Plasticizers which can be used according to the invention are also listed below.
  • the TPE which can be used according to the invention can also have a crosslinking aid which serves to accelerate or catalyze the reaction between the double bonds of the double bond-containing polymer and the excess sulfur or sulfur-containing compound of the rubber.
  • the TPE which can be used according to the invention can also contain one or more of the following additives: stabilizers, auxiliaries and dyes.
  • the TPE according to the invention can also contain fillers. Examples of additives and fillers are also mentioned below.
  • the TPE which can be used according to the invention can also contain additives which enable the TPE to be heated and melted by microwaves, induction or IR radiation.
  • the TPE that can be used according to the invention is distinguished by improved adhesion to rubber.
  • the rubber preferably consists of crosslinked diene-rubber mixtures which can be crosslinked by means of sulfur or sulfur-containing compounds.
  • the TPE which can be used according to the invention can be produced by adding a mixture of an ethylene- ⁇ -olefin block co- polymer, a double bond-containing polymer with a Mo l fraction of double bonds in the range of 5 to 100 mol%, based on the number of moles of all monomer units of the double bond-containing polymer used for the polymerization, and a non-elastomeric polyolefin at a temperature above the melt - and / or softening point of the non-elastomeric polyolefin are mixed together.
  • partial crosslinking can occur in the TPE due to the reaction of double bonds of the polymer containing double bonds.
  • the inventors of the present invention found that the reaction of the double bonds with one another in the TPE that can be used according to the invention is only incomplete, so that there are still sufficient double bonds of the double bond-containing polymer, for example to react with the rubber.
  • the TPE can be produced by blending / mixing the components A, B, C, D, E, F, G and H mentioned below - if they are present in the TPE.
  • the mixture can shear using mixing systems known in rubber technology and plastics technology, such as kneaders, mecanicmi, z. B. internal mixers with interlocking or tangential rotor geometry, as well as in continuously mi regulating systems such as mixing extruders, z.
  • B. Mixing extruders with 2 to 4 or more shaft screws (eg twin screw extruder) take place.
  • the mixing temperature is high enough that component C (non-elastomeric polyolefin) can be converted into the plastic state, but because it is not damaged. This is ensured if a temperature above the melting or softening temperature of component C is chosen.
  • the mixing of the components - if they are present in the TPE - is particularly preferably carried out at a temperature in the range from 140 ° C to 220 ° C, preferably 160 ° C to 220 ° C.
  • the period of time for adding / mixing at the specified temperatures is in the range from 0.5 min to 4 min.
  • the composition is then cooled to room temperature.
  • components A, B, C, D, E, F, G and H - if they are included in the TPE - are preferably initially introduced together and at temperatures above the melting or softening temperatures of the component C intimately mixed.
  • a continuous mixing plant such as an extruder or a twin-screw extruder, is particularly preferred for production. The aforementioned procedure ensures that the composition is distributed as finely and evenly as possible of the components used after the end of production.
  • the TPEs that can be used according to the invention have very good properties, in particular very good UV resistance, low friction and, at the same time, very good elastic properties (compression set, elongation at break and tensile strength). Furthermore, the TPE according to the invention have no tendency to oil out plasticizers. They also have a excellent adhesion to rubber, especially sulfur-crosslinked rubber, and flow without shear when increasing to the melting temperature. In addition, the TPEs mentioned contribute to the elastic properties of the resulting surface covering or do not counteract them. In contrast to previously used adhesives, such as polyurethanes, the TPEs that can be used in accordance with the invention have a low to no health hazard potential.
  • Component A Ethylene- ⁇ -olefin block copolymer
  • An ethylene- ⁇ -olefin block copolymer is understood in accordance with the invention to mean a multiblock copolymer which is produced by polymerizing at least two different types of monomers.
  • the at least two different types of monomers are ethylene monomer and ⁇ -olefin monomers (hereinafter referred to as "repeating units" with respect to the polymer) or several different ⁇ -olefin monomers are used.
  • a multiblock copolymer is understood to mean a polymer which has two or more chemically different areas or segments (also referred to as "blocks") which are preferably connected to one another in a linear manner, ie a polymer which has chemically different blocks which In a preferred embodiment, the blocks differ in terms of the amount or type of comonomer used therein (the comonomer different from ethylene), the density of the crystalline fraction, the crystal size, the type or grade the tacticity (isotactic or syndiotactic), the degree of branching, the homogeneity and other chemical or physical properties.
  • the multiblock copolymer can be composed according to the following formula:
  • n is at least 1, preferably an integer greater than 1, for example 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or higher is.
  • A represents a hard segment and B a soft segment of the polymer. Segments A and B are preferably linked in a linear fashion. Segments A and B are described in more detail below. Segments A and B are preferably random along the line In other words, the multiblock copolymer usually does not have the structure AAA-AA-BBB-BB. The multiblock copolymers preferably do not have a third type of block besides the segments A and B.
  • Each of the segments elements A and B preferably has statistically distributed repetition units.
  • the ethylene- ⁇ -olefin block copolymer preferably comprises a plurality of ethylene, i. the ethylene content, based on the total repeating units of the polymer, is at least 50 mol%, more preferably at least 60 mol%, even more preferably at least 70 mol% and most preferably at least 80 mol%.
  • the proportion of -olefin, based on the total repeating units of the polymer is preferably in the range of 10 mol% to 20 mol%, more preferably 15 mol% to 20 mol%.
  • the content of different repeat units can be measured by means of nuclear magnetic resonance (NMR).
  • a “hard” segment A is understood to mean blocks of polymerized repeat units in which ethylene is present in an amount greater than 95% by weight, more preferably greater than 98% by weight, based on the total weight of the polymer.
  • the comonomer content (the comonomer other than ethylene) in the hard segments is less than 5% by weight, more preferably less than 2% by weight based on the total weight of the polymer. In some embodiments, this is hard Segment made entirely of ethylene.
  • a "soft" segment B is understood as meaning blocks of polymerized repeat units in which the comonomer content (content of repeat units which are different from ethylene) is greater than 5% by weight, more preferably greater than 8% by weight, is even more preferably greater than 10% by weight and even more preferably greater than 15% by weight based on that Total weight of polymer.
  • the comonomer content in the soft segment can be greater than 20% by weight, more preferably greater than 25% by weight, even more preferably greater than 30% by weight, even more preferably greater than 35% by weight. %, even more preferably greater than 40% by weight, even more preferably greater than 45% by weight, even more preferably greater than 50% by weight and most preferably greater than 60% by weight.
  • the soft segments B are in the multiblock copolymer preferably in a proportion of 1 wt .-% to 99 wt .-%, from 5 wt .-% to 95 wt .-%, from 10 wt .-% to 90 wt %, from 15% by weight to 85% by weight, from 20% by weight to 80% by weight, from 25% by weight to 75% by weight, from 30% by weight to 70 wt%, from 35 wt% to 65 wt%, from 40 wt% to 60 wt%, from 45 wt% to 55 wt%, based on the Total weight of the polymer.
  • the hard segments A can be present in the same area.
  • the weight proportions of soft and hard segments can be calculated on the basis of data obtained from differential calorimetry (DSC) or nuclear magnetic resonance (NMR).
  • ethylene- ⁇ -olefin block copolymers which can be used according to the invention and their processes for production are also described in WO 2006/101966 A1.
  • the ethylene- ⁇ -olefin block copolymers also have a density in the range from 0.86 g / cm 3 to 0.91 g / cm 3 .
  • the molecular weight distribution M w / M n in the case of the ethylene- ⁇ -olefin block copolymers is preferably in a range from 1.5 to 8.0, more preferably in a range from 1.7 to 3.5.
  • the weight average molecular weight M w of the ethylene- ⁇ -olefin Block copolymers preferably range from 10,000 to 2,500,000, more preferably from 20,000 to 500,000, and most preferably from 20,000 to 350,000.
  • the determination of the weight-average molecular weight M w and the molecular weight distribution M w / M n is preferably carried out by means of gel permeation chromatography (GPC).
  • the ethylene- ⁇ -olefin block copolymers used in accordance with the invention are preferably polymers which comprise ethylene and at least one C3-C20 ⁇ -olefin.
  • the ⁇ -olefins used to produce the ethylene o ⁇ -olefin block copolymer used according to the invention are preferably monounsaturated compounds, such as monounsaturated C3-C20 aliphatic compounds, or aromatic compounds that have a monounsaturated radical, such as a vinyl unit , exhibit.
  • monounsaturated C3-C20 aliphatic compounds can be straight-chain, branched or cyclic compounds. Examples of monounsaturated compounds or aromatic compounds that have a monounsaturated radical are as follows:
  • olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof, 1-butene and 1-octene being particularly preferred.
  • ethylene- ⁇ -olefin block copolymers are used which are essentially free of olefinically unsaturated double bonds.
  • the molar proportion of olefinically unsaturated double bonds is preferably less than 0.5 mol%, more preferably less than 0.1 mol% and particularly preferably less than 0.01 mol%, based on the number of moles of all for the Polymerization used monomer units of the ethylene- ⁇ -olefin block copolymer.
  • the ethylene-o ⁇ -olefin block copolymer does not contain any olefinically unsaturated double bonds.
  • the ethylene- ⁇ -olefin block copolymer is composed only of repeat units derived from the polymerization of ethylene and monounsaturated ⁇ -olefins.
  • Ethylene- ⁇ -olefin block copolymers described above are available for example under the brand name INFUSE TM from The Dow Chemical Company.
  • Component B polymer containing double bonds with a molar proportion of double bonds in the range from 5 to 100 mol%
  • the polymer containing double bonds can have double bonds in the main chain or in the side chain.
  • the polymer containing double bonds can be an unhydrogenated styrene block copolymer (SBC), a sulfur-crosslinkable, uncrosslinked diene rubber or an ethylene- ⁇ -olefin block copolymer containing double bonds.
  • SBC unhydrogenated styrene block copolymer
  • the SBC has at least one polyolefin block in addition to at least one polystyrene block, it being possible for the polyolefin block to be made up of, for example, butadiene or isoprene.
  • the unhydrogenated SBC is a linear triblock copolymer.
  • SBS polystyrene-block-polybutadiene-block-polystyrene
  • SIS polystyrene-block-polyisoprene-block-polystyrene
  • SIBS polystyrene-block-poly (isoprene-co-butadiene) -block-polystyrene
  • SBS polystyrene-block-poly (isoprene-co-butadiene) -block-polystyrene
  • SIBS polystyrene-block-poly (isoprene-co-butadiene) -block-polystyrene
  • the polymer containing double bonds is very particularly preferably an SIS.
  • SBS is, for example, Kraton® D (Kraton)
  • SIS is available, for example, from Kuraray as Hybrar®.
  • the diene rubbers to be understood as double bond-containing polymers include both homopolymers of dienes and random copolymers of at least two dienes, as well as random copolymers of different olefinic monomers, for example one or more mono-olefins with one or more dienes.
  • olefin-diene rubbers can also be found for the random rubber copolymers of one or more monoolefins with one or more dienes.
  • the distinction between homopolymers of dienes, statistical copolymers of dienes and random copolymers of olefins and dienes is not made. All of the above variants are referred to as diene rubbers.
  • Preferred diene rubbers containing double bonds are those which are sulfur-crosslinkable. It is also preferred that the diene rubbers are present in the TPE which can be used according to the invention without crosslinking.
  • Preferred diene rubbers are copolymers of one or more olefins and a diene.
  • the olefins used here are preferably ethylene, propylene or butylene, where ethylene and propylene are preferred.
  • Non-conjugated dienes are preferably used as dienes, so that the polymer produced has a double bond in the side chain.
  • Dicyclopentadiene (DCP), 1,4-hexadiene or ethylidene norbornene (ENB, IUPAC: 5-ethylidene-2-norbornene) are used as diene components.
  • the dienes differ in terms of the rate of crosslinking. EPDM containing DCP have the lowest, EPDM containing ENB the highest reactivity.
  • the diene rubber is preferably used uncrosslinked.
  • a particularly prominent representative is uncrosslinked ethylene-propylene-diene rubber (EPDM).
  • EPDM is a terpolymer, synthetic rubber.
  • EPDM is one of the statistical copolymers with a saturated polymer backbone. They are preferably prepared using metallocene or Ziegler-Natta catalysts based on vanadium compounds and aluminum alkyl chlorides.
  • the aforementioned dienes are used as dienes.
  • This type of random diene rubbers can be crosslinked with sulfur, phenolically or peroxide, whereby according to the invention they are preferably used uncrosslinked or only partially crosslinked or are present in the TPE which can be used according to the invention.
  • a further preferred diene rubber is a homopolymer which is polymerized from a diene, preferably a conjugated diene, polymerized.
  • a particularly preferred example of this is isoprene rubber (IR), a synthetically produced variant of natural rubber. It differs from this primarily in the somewhat lower chemical purity. This is because the catalysts used for the polymerization are less effective than the naturally occurring enzymes.
  • the purity of natural rubber is preferably more than 99.9%, whereas in the case of the synthetically produced IR - depending on the catalyst used - it is only about 92% to 97%.
  • IR can also be crosslinked peroxide, phenolic or with sulfur.
  • the diene rubber based on homopolymers is preferably used uncrosslinked or partially crosslinked, or is present in the TPE uncrosslinked or partially crosslinked.
  • ethylene- ⁇ -olefin block copolymers containing double bonds ethylene- ⁇ -olefin block copolymers similar to component A described above can be used which, in addition to the ethylene and the ⁇ -olefin, also have a diene.
  • the diene is preferably only incorporated into the polymer chain via one of the double bonds, i.e. the other double bond is still present in the resulting polymer.
  • ethylene- ⁇ -olefin block copolymers can also be used in which no monounsaturated ⁇ -olefins but only dienes are used for their preparation as ⁇ -olefins.
  • dienes that can be used here are: 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 5-methyl-1,4-hexadiene, 3, 7-Dimethyl-l, 6-octadiene, 3, 7-dimethyl-l, 7-octadiene, isomer mixtures of dihydromyricene and dihydroocines, monocyclic aliphatic dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene , 1, 5-cyclooctadiene and 1, 5-cyclododecadiene, polycyclic aliphatic dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo- (2, 2, 1) -hepta- 2,5-diene
  • ethylene-olefin block copolymers which are copolymerized from ethylene, C3-C20 o ⁇ -olefin and one or more dienes.
  • olefins propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene, propylene and 1-octene being particularly preferred.
  • Preferred dienes here are: 1,4-pentadiene,
  • the ethylene content is preferably in the range from 20% by weight to 90% by weight and more preferably in the range from 60% by weight to 90% by weight.
  • the diene content is preferably in the range from 0.1 to 10% by weight.
  • the ⁇ -olefin content is preferably in the range of 10 wt% to 80 wt%, and more preferably in the range from 10% to 40% by weight. The contents are based in each case on the total weight of the polymer.
  • the polymer containing double bonds is preferably used in an amount such that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the polymer containing double bonds (component B) in the TPE which can be used according to the invention is in the range from 10: 1 to 2: 1, more preferably in the range of 7: 1 to 4: 1.
  • Component C non-elastomeric polyolefin
  • the non-elastomeric polyolefin employed in the present invention can be anything suitable for making TPE.
  • the non-elastomeric polyolefin is preferably a thermoplastic.
  • Non-elastomeric polyolefins are, for example, copolymers made from polyethylene, such as HDPE (high density polyethylene), MDPE (medium density polyethylene), LDPE (low density polyethylene), LLDPE (linear low density polyethylene), VLDPE (very low density polyethylene); a homopolymer of polyethylene or propylene; a random copolymer of propylene and ethylene; and combinations thereof.
  • the non-elastomeric polyolefin is particularly preferably a polyethylene.
  • Commercially available polyethylenes are, for example, PE ExxonMobil LD655 from ExxonMobil or PE Queo 0230 from Borealis AG.
  • Polyolefins suitable for the invention are above all those which are suitable for processing by injection molding. Suitable polyolefins are those with good flow properties and rigidity.
  • the non-elastomeric polyolefin can have an elongation at break according to ISO 527-1, -2 in the range from 1% to 500%, preferably in the range from 10% to 300%, more preferably> 50%. Furthermore, it preferably has a Shore hardness (Shore D, 15 s) in the range from 30 to 50. Furthermore, the non-elastomeric polyolefin is preferably one which has a melt index (190 ° C. / 2.16 kg) in the range of 20 g / 10 min to 160 g / 10 min.
  • the non-elastomeric polyolefin is preferably used in an amount such that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the non-elastomeric polyolefin (component C) in the TPE which can be used according to the invention is in the range from 3: 1 to 0, 5: 1, more preferably in the range of 2: 1 to 1: 1.
  • Component D phenolic resin
  • Phenolic resins are used when the TPE which can be used according to the invention is to build up further bonds between the rubber in addition to the connections between the excess sulfur or sulfur-containing compounds of the crosslinking system of the rubber.
  • the phenolic resins can react with double bonds of the rubber and double bonds of the double bond-containing polymer of the TPE which can be used according to the invention.
  • Phenolic resins which can be used according to the invention are preferably those which can form a bond with two different double bonds with elimination of water at at least two points on the phenolic resin. It can also be bro- mated or chlorinated phenolic resins are used. In the latter case, there is no elimination of water, but the elimination of hydrogen chloride or hydrogen bromide.
  • phenolic resins with sufficiently high reactivity at mixed temperatures of at least 180 ° C. are preferably used.
  • Phenolic resins suitable for crosslinking are known to those skilled in the art, and are usually obtained by reacting phenol with aldehydes (phenol-formaldehyde resin).
  • Phenolic resins suitable for this purpose are, for example, the reaction products of octylphenol with formaldehyde, e.g. SP-1045 H (SP-1045, HRJ-10518 H from Schenectady International Inc.) is suitable, which is an octylphenol-formaldehyde resin containing methylol groups, or in the case of brominated phenolic resins, brominated octylphenolic resins, for example those with the trade names SP- 1055 or SP-1056.
  • Suitable Cl-containing Lewis acids are known to the person skilled in the art. Preference is given to using SnCl2 or chloroprene rubber.
  • the at least one phenolic resin is preferably used - if present - in an amount that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the phenolic resin (component D) in the TPE which can be used according to the invention is in the range from 12: 1 to 5: 1, more preferably in the range 10: 1 to 7: 1.
  • Component E crosslinking aid
  • Crosslinking auxiliaries can be used to accelerate and catalyze the formation of bonds between the TPE which can be used according to the invention and the rubber.
  • Inorganic acids such as SnCl2 and / or ZnO, are preferably used here.
  • halogen-containing elastomers such as chloroprene rubber can also be used.
  • ZnO is particularly preferably used because it also acts as a catalyst.
  • the crosslinking auxiliary is preferably - if present - used in an amount that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the crosslinking auxiliary (component E) in the TPE which can be used according to the invention is in the range from 40: 1 to 10: 1 , more preferably in the range of 30: 1 to 15: 1.
  • Component F plasticizer
  • Plasticizers suitable according to the invention are technical or medicinal mineral or white oils, native oils, such as, for example, soybean or rapeseed oil.
  • Mixtures of the substance classes described can also be used as suitable plasticizers.
  • plasticizer is Shell Catenex T 145 S from Shell.
  • the plasticizer is preferably used - if present - in an amount such that the weight ratio of ethylene-a-olefin block copolymer (component A) to the plasticizer (component F) in the TPE that can be used according to the invention is in the range of 2.5: 1 to 0.5: 1, more preferably in the range 2: 1 to 1: 1 and even more preferably in the range 1.6: 1 to 1.2: 1.
  • Component G Stabilizers, auxiliaries and colorants (additives)
  • Suitable additives are, for example, processing aids, metal soaps, fatty acids and fatty acid derivatives, factice ([artificial word]: rubber-like substance that is obtained, for example, by the action of sulfur or sulfur chloride on drying oils; used to stretch rubber), aging, UV or Ozone protection agents such as ozone protection waxes, antioxidants, e.g. polycarbodiimides (e.g.
  • Rhenogran®, PCD-50 substituted phenols, substituted bisphenols, dihydroquinolines, diphenylamines, phenylnaphthylamines, paraphenylenediamines, benzimidazoles, paraffin waxes, titanium dioxide, litophones, pigments, microcrystalline waxes, pigments Zinc oxide, iron oxide, ultramarine blue, chromium oxide, antimony sulfite; Stabilizers such as heat stabilizers, weathering stabilizers; Oxidation protection agents, e.g. p-dicumyldiphenylamine (e.g. Naugard® 445), styrenated diphenylamine (e.g.
  • Vulcanox® DDA zinc salt of methyl mercaptobenzimidazole (e.g. Vulcanox® ZMB2), polymerized 1,2-dihydro-2, 2, 4-trimethylquinoline (e.g. Vulcanox® HS), thiodiethylene bis (3, 5-di-tert-butyl-4-hydroxy) hydrocinamate, thiodiethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] (e.g. Irganox® 1035), lubricants, mold release agents, anti-flame agents (flame retardants), adhesive Mediators, markers, minerals, and crystallization accelerators and retarders.
  • Vulcanox® ZMB2 zinc salt of methyl mercaptobenzimidazole
  • HS polymerized 1,2-dihydro-2, 2, 4-trimethylquinoline
  • Vulcanox® HS thiodiethylene bis (3, 5-di-tert-butyl-4-hydroxy
  • processing aids and stabilizers can be used as processing aids and stabilizers: Antistatic agents, antifoam agents, lubricants, dispersants, release agents, anti-blocking agents, radical scavengers, antioxidants, biocides, fungicides, UV stabilizers, other light stabilizers, metal deactivators, and also additives such as foaming aids, blowing agents, flame retardants, smoke gas suppressors, impact resistance modifiers, adhesives, anti-fogging agents, dyes, color pigments, color masterbatches, viscosity modifiers and anti-aging agents.
  • UV or IR crosslinking systems or microwave-active agents are also used as additives.
  • UV stabilizers and antioxidants are particularly preferably used as auxiliaries.
  • additives are preferably used in an amount such that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the sum of all additives (component G) is in the range from 60: 1 to 15: 1 which can be used according to the invention , more preferably in the range of 50: 1 to 20: 1.
  • Component H filler
  • Suitable fillers are, for example, carbon black, chalk (calcium carbonate), kaolin, silica, talc (magnesium silicate), aluminum oxide Hydrate, aluminum silicate, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, barium sulfate, zinc carbonate, calcined kaolin (e.g. Polestar® 200 P), calcium oxide, magnesium oxide, titanium oxide, aluminum oxide, zinc oxide, silanized kaolins, silanized silicate, coated chalk, treated kaolins, Fumed silica, hydrophobized fumed silica (e.g.
  • Aerosil® 972 synthetic amorphous precipitated silica, carbon black, graphite, nanoscale fillers such as carbon nanofibrils, nanoparticles in platelet form or nanoscale silicon dioxide hydrates and minerals.
  • a calcium carbonate preferably from Bassermann Minerals (Omyacarb 5 Gu), is particularly preferably used as the filler.
  • the filler is preferably used in an amount such that the weight ratio of ethylene- ⁇ -olefin block copolymer (component A) to the filler (component I) in the TPE which can be used according to the invention is in the range from 3: 1 to 0.5: 1 is preferably in the range from 2: 1 to 1: 1.
  • the present application also relates to the following aspects:
  • TPE thermoplastic elastomer
  • Aspect 2 The method of aspect 1, wherein the TPE or the TPE-containing material is at a temperature above the The melting point of the TPE is heated and applied to a surface.
  • Aspect 3 The method of aspect 2, wherein the temperature is in a range from 140 ° C to 220 ° C.
  • Aspect 4 The method according to one of Aspects 1 to 3, wherein a material containing rubber is additionally used to produce the surface covering.
  • Aspect 5 The method of aspect 4, wherein the rubber-containing material is in the form of rubber-containing particles.
  • Aspect 6 The method of aspect 5, wherein the TPE is used to fix the rubber-containing particles.
  • Aspect 7 The method according to Aspect 5 or 6, wherein the particles containing the rubber are coated with the TPE (part) and thus constitute composite particles.
  • Aspect 8 The method according to aspect 7, wherein for the production of the surface covering, the composite particles are heated to a temperature above the melting point of the TPE and applied to a surface, or vice versa.
  • Aspect 9 The method according to Aspect 5 or 6, wherein the particles containing the rubber and particles of the TPE are used to produce the surface covering.
  • Aspect 10 The method according to aspect 9, wherein the particles containing the rubber and the particles containing the TPE are presented as a two-component mixture.
  • Aspect 11 The method according to aspect 10, wherein the two-component mixture is heated to a temperature above the melting point of the TPE and then applied to a surface.
  • Aspect 12 The method according to any one of aspects 3 to 11, wherein the temperature above the melting point of the TPE is in the range of 160 ° C to 220 ° C.
  • Aspect 13 The method according to aspect 9, wherein in a step (a) a melt is produced from the particles of the TPE, then in a step (b) the melt is mixed with the particles containing the rubber to form a laying compound, and then in one Step (c) the laying compound is applied to a surface.
  • Aspect 14 The method of aspect 13, wherein steps (a) and (b) are carried out at a temperature in the range from 140 ° C to 220 ° C, preferably 160 ° C to 220 ° C.
  • Aspect 15 The method according to any one of Aspects 1 to 14, wherein the rubber of the particles containing the rubber is a rubber based on crosslinked diene rubber mixtures, crosslinked ethylene-propylene-diene rubber (EPDM), crosslinked styrene-butadiene rubber ( SBR), crosslinked natural rubber (NR), crosslinked butyl rubber (IIR) or a mixture thereof or wherein the rubber-containing particles are made from recycled rubber.
  • EPDM crosslinked ethylene-propylene-diene rubber
  • SBR crosslinked styrene-butadiene rubber
  • NR crosslinked natural rubber
  • IIR crosslinked butyl rubber
  • Aspect 16 The method according to any one of aspects 1 to 15, wherein the TPE exhibits shear-free flow behavior when it is increased to its melting temperature.
  • Aspect 17 The method according to any one of aspects 1 to 16, wherein the TPE is an ethylene- ⁇ -olefin block copolymer, a double bond-containing polymer with a molar fraction of double bonds in the range from 5 to 100 mol%, based on the number of mols all monomer units of the double bond-containing polymer used for the polymerization, and a non-elastomeric polyolefin.
  • the TPE is an ethylene- ⁇ -olefin block copolymer, a double bond-containing polymer with a molar fraction of double bonds in the range from 5 to 100 mol%, based on the number of mols all monomer units of the double bond-containing polymer used for the polymerization, and a non-elastomeric polyolefin.
  • the number or the molar fraction of double bonds in the polymer containing double bonds is derived or calculated from the number of moles / number of monomer units used for the polymerization and the double bonds still remaining in the polymer after the polymerization.
  • the density is determined in accordance with DIN EN ISO 1183-1.
  • the Shore hardness is determined in accordance with DIN EN ISO 868 and DIN ISO 7619-1.
  • Tensile strength is the maximum mechanical tensile stress that a material can withstand before it breaks / tears. It is calculated in the tensile test from the maximum tensile force achieved based on the original cross-section of the (standardized) specimen and stated in N / mm 2 .
  • the elongation at break is a material parameter that indicates the permanent elongation of the break in relation to the initial measuring length.
  • the elongation at break is one of many parameters in materials testing and characterizes the deformability of a material. It is the permanent change in length DI related to the initial measurement length Do of a specimen in the tensile test after a break. This change in length is given in%.
  • the compression set is a measure of how (thermoplastic) elastomers behave with long-lasting, constant compression and subsequent relaxation. According to DIN ISO 815, the compression set (DVR, compression set) is measured at constant deformation. This represents the deformation portion of the test material.
  • the compression set is an important factor to consider before using a material for a particular purpose.
  • the permanent deformation, the compression set (compression set) is an important parameter, especially for the use of seals and backing plates made of elastomers.
  • a cylindrical test specimen is compressed by, for example, 25% and stored for a certain time at a certain temperature.
  • the temperature and the medium (mostly air, but also oils and other working fluids) for the compression set test depend on the material to be tested, its intended use and the test setup (e.g. 24 h at 70 ° C).
  • Li height of the specimen during the test (spacer)
  • L2 height of the specimen after the test. Furthermore, the tensile strength in N / mm 2 , the elongation at break in% and the modulus in MPa according to DIN ISO 53504 / ISO 37 were measured.
  • the tear resistance is determined in N / mm 2 in accordance with DIN ISO 34.
  • the abrasion of the TPE is measured by rubbing a 6 mm high cylinder with a diameter of 16 mm over 40 m of sandpaper with a grain size of 60 with a contact pressure of 10 N.
  • the adhesion of the TPE to EPDM (here EPDM 062.1040 from GEZOLAN AG) is determined as follows: A 2 mm thick EPDM plate measuring 3 cm ⁇ 6 cm is encapsulated with the TPE on two sides. To determine the absolute adhesion (insert), the force (in N) required to separate the EPDM from the TPE along the 3 cm edge is measured in a tensile testing machine. To determine the relative adhesion (S2), so-called S2 test bars are cut out and clamped in a tensile testing machine. The force per area (N / mm 2 ) is determined which is required to separate the EPDM from the TPE.
  • the melt index is determined in accordance with ISO 1133.
  • Table 1 shows the abbreviations used for the components used in the examples:
  • Examples 1 and 2 Production of a TPE which can be used according to the invention and which, when increased to its melting temperature, exhibits shear-free flow behavior:
  • TPEs with the components shown in Tables 2 and 3 are produced according to the above-mentioned production process.
  • the DbhP used is one which is polymerized to 30% by weight of styrene and 70% by weight of isoprene units, ie has 78 mol% of double bonds.
  • the non-elastomeric polyolefin used in Example 1 has a melt index (190 ° C. / 2.16 kg) of 150 g / 10 min.
  • the non-elastomeric polyolefin used in Example 2 has a melt index (190 ° C. / 2.16 kg) of 30 g / 10 min.
  • a twin-screw extruder is used to mix the components used. The mechanical measured values are given in Table 4.
  • Comparative Example 1 Production of a TPE with SBC instead of an ethylene- ⁇ -olefin block copolymer which does not flow without shear when it is raised to its melting temperature:
  • the DbhP used is one which is polymerized to 30% by weight from styrene and 70% by weight from isoprene units, ie has 78 mol% of double bonds.
  • Example 3 Preliminary tests on the flow behavior of the TPE according to Example 1 and Comparative Example 1:
  • a TPE In order for a TPE to be used as an "adhesive" to connect rubber particles to a surface covering, it must have a shear-free flow behavior when it melts.
  • preliminary tests are carried out with particles of the TPE according to Example 1 and a TPE according to Comparative Example 1: In each case, a granulate with a filling height of about 1 cm is filled into a small aluminum dish. The small dishes with the granules are placed in an oven at 130 ° C. The small dishes with the hot granules are then removed from the oven and attached to the The bowls are then emptied.
  • Fig. 1 shows the bowl with the TPE granules according to In game 1 before the heat treatment described.
  • Fig. 2 shows the bowl with the TPE granules according to Example 1 after the temperature treatment described above.
  • Fig. 3 shows the emptied contents of the bowl in which the granules of Example 1 was used, from the upper side.
  • 4 shows the emptied contents of the bowl with the granules of Example 1 from the lower side.
  • the granules of Example 1 are glued, i.e. the grain boundaries are gone. This clearly shows that the TPE according to Example 1 enables shear-free flow during melting.
  • Fig. 5 shows the bowl with the granules according to comparative example 1 after the temperature treatment. You can see from this picture that the grain boundaries have not flowed, but that the granules are still loose. This is also the case when the granules are emptied from the aluminum bowl occupied, as shown in Fig. 6. Shear-free flow is therefore not possible with a TPE that contains an SBC as an elastomer, ie other particles cannot be glued to such TPEs and therefore no surface covering can be produced from glued rubber granulate.
  • Example 4 Production of webs or plates of a surface covering according to the invention by means of an extruder system
  • a QSM90 extruder cross-pin mixing extruder or a single-screw extruder with a length / diameter ratio of 16: 1 - 20 is used for the continuous production of a floor covering from a thermoplastic elastomer (TPE) and vulcanized, elastomeric material (EPDM) : 1 continuously with a predefined granulate mix of TPE and EPDM (weight ratio 1: 3.5 - 1: 8 (TPE: EPDM), preferably in the range 1: 4 - 1: 6.6).
  • TPE thermoplastic elastomer
  • EPDM vulcanized, elastomeric material
  • the TPE is one according to Example 1, as described above.
  • the TPE granules have a cylindrical, drop-like shape and a size of approx. 2 - 5 mm.
  • the rubber granulate 062.1040 from GEZOLAN AG is used as EPDM.
  • the EPDM granules have a size of approx. 1 - 4 mm.
  • the working temperature of the extruder is set to 160 ° C to 220 ° C, the conveying speed to 250 kg / h to 400 kg / h.
  • the elastomer material leaves the extruder via a perforated nozzle with a cylindrical bore, each of which has a diameter of 6 to 10 mm.
  • the resulting strand is cut off at a distance of 25 to 45 mm to form shaped pieces.
  • the cut pieces fall directly onto a conveyor belt and from there are directly transferred into a metal mold with dimensions of 205 mm x 205 mm x 12 mm. ported.
  • the still hot material is brought into its final shape by means of a smoothing device and / or a pressure roller and then cooled. After cooling, a finished floor slab is removed from the Me tallform and used for laying.
  • the fittings are dropped directly into the gap of a two-roll calender that can be heated and cooled.
  • the gap width is between 6 and 8 mm, ie a constant line pressure acts on the fittings.
  • the tem peration of the rolls by cooling and heating devices is designed in such a way that the mass is only heated by friction to such an extent that its temperature in the calender is always around 125 ° C.
  • the surface temperatures of the rollers are therefore in the range from 40 to 110 ° C.
  • a roller length of 1.20 m and a diameter of 400 mm are used.
  • the material web leaving the calender is fed directly to a continuously operating cooling device, in which the cooling takes place at normal temperatures of 20 ° C to 35 ° C.
  • the membrane surface leaves the cooling station as a finished product. Post-treatment of the surfaces is not absolutely necessary, but can be done if necessary.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne l'utilisation d'un élastomère thermoplastique (TPE) pour la fabrication d'un revêtement de surface, en particulier un revêtement de piste de course ou un revêtement de protection contre les chutes, en particulier un revêtement de piste de course ou un revêtement de protection contre les chutes pour les terrains de sport, de jeu et de loisirs. L'invention concerne également un revêtement de surface, notamment un revêtement de piste de course ou un revêtement de protection contre les chutes, notamment un revêtement de piste de course ou un revêtement de protection contre les chutes pour terrains de sport, de jeu et de loisirs, le revêtement de surface comprenant un TPE.
EP20716454.2A 2019-04-17 2020-03-31 Utilisation d'une composition élastomère thermoplastique pour la fabrication d'un revêtement de sol et revêtement de sol Withdrawn EP3956398A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019110213.8A DE102019110213A1 (de) 2019-04-17 2019-04-17 Verwendung einer thermoplastischen Elastomerzusammensetzung zur Herstellung eines Bodenbelags und Bodenbelag
PCT/EP2020/059165 WO2020212138A1 (fr) 2019-04-17 2020-03-31 Utilisation d'une composition élastomère thermoplastique pour la fabrication d'un revêtement de sol et revêtement de sol

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EP3956398A1 true EP3956398A1 (fr) 2022-02-23

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Publication number Priority date Publication date Assignee Title
KR19990029014A (ko) * 1996-05-15 1999-04-15 고사이 아끼오 열가소성 엘라스토머 조성물 파우더 및 이를 성형하여수득한 성형체
GB2340497B (en) * 1998-06-03 2003-01-08 Genshaw Ltd Construction materials
DE602006004493D1 (de) * 2005-03-17 2009-02-12 Dow Global Technologies Inc Ethylen / alpha-olefin block-copolymere
WO2007071438A1 (fr) * 2005-12-23 2007-06-28 Dsm Ip Assets B.V. Utilisation d'élastomères thermoplastiques dans des revêtements de sol pour des logements pour animaux
US7863378B2 (en) * 2006-08-31 2011-01-04 Asahi Kasei Chemicals Corporation Thermoplastic elastomer composition and modifier composition using the same
WO2011156215A2 (fr) * 2010-06-09 2011-12-15 Mannington Mills, Inc. Composition de revêtement de sol contenant du polymère renouvelable
DE102010036122A1 (de) * 2010-09-01 2012-03-01 Nora Systems Gmbh Bodenbelag
US20170081807A1 (en) * 2015-09-22 2017-03-23 Christopher Tetrault Poured in place surface cooling technology
SI3394363T1 (sl) * 2015-12-22 2021-08-31 Nora Systems Gmbh Talna obloga, ki vsebuje termoplastični elastomer in postopek za proizvodnjo le-te
CN107227027B (zh) * 2017-07-20 2020-05-19 广东创弘材料科技有限公司 热塑性复合弹性体及其制备方法、用途
CN109553868A (zh) * 2018-12-05 2019-04-02 袁进 一种高耐磨tpv地板包胶料及其制备方法

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