Patent Publication Number: US-2011054080-A1

Title: Method for producing coated rubber particles and coated rubber particles

Description:
FIELD OF THE INVENTION 
     The invention relates to a process for the coating of rubber particles, produced from used tyres, to the coating composition, and to the coating process and to the coated rubber particle, and also to its use as infill in artificial turf or for other floorcoverings, for example in the construction of sports facilities. The coating of rubber surfaces is also possible. 
     PRIOR ART 
     EP 1 416 009 (Mulsener Recycling—and handelgesellschaft mbgH) describes a loose, flowable granulated-rubber material, covered with a binder based on polyurethane. The binder can optionally also be coloured. The diameter of the rubber particles is from 0.5 mm to 2.5 mm, and the average layer thickness of the coating is from 5 micrometres to 20 micrometres, and at some locations the thickness of the layer can be up to 35 micrometres. There is no disclosure of mechanical or chemical properties of the coated rubber particles. 
     DE 196 31 251 (ContiTech Holdings) describes a granulated-rubber product coated with a flame-retardant binder covering. The binder used comprises a rubber, and the flame retardant used comprises inorganic flame retardants, such as magnesium hydroxide or aluminium hydroxide. The granulated-rubber products provided with the low-flammability coating are processed to give low-flammability rubber workpieces. 
     DE 24 55 679 (Bayer AG) describes the coating of rubber particles whose diameter is from 0.5 to 6 mm with a binder based on polyisocyanates, these coated particles being further processed to give elastic floorcoverings. 
     DE 25 24 877 (Schramm) describes a floorcovering, for example for floors of animal stalls, composed of coated particles, the covering being hardened in situ. No further information is given in relation to the physical properties of the coating. 
     DE 21 10 327 (Allwelt) describes a production process for elastic sports floors composed of granulated material derived from used tyres and of binder. Granulated material and binder are mixed and hardened to give the floor. 
     The four last-mentioned patent publications do not describe any granular, flowable product which could be used as infill for artificial turf, efforts being instead mainly directed towards the crosslinking of the coated particles obtained to give a solid floorcovering. 
     DE 196 38 312 (Martin) describes a jointless insulation material composed of granulated rubber material and of a binder, where the binder used comprises an epoxy resin or a (meth)acrylate resin. 
     WO 2002/18706 (Fieldturf Inc.) describes a transportable, modular artificial turf element composed of turf surface element and base element and of infill for the turf surface element. The infill can be composed of rubber particles not specified in any great detail, or of sand or of a mixture composed of sand and rubber particles. No coating of the rubber particles is mentioned. 
     WO 2002/060290 (Groundscape Technologies LLC) describes a material composed of vulcanized rubber particles, and of a first, coloured coating layer, which covers the vulcanized rubber particles, and of a second coating layer, which protects the coloured coating layer from abrasion. The second coating layer comprises, as binder, a polyacrylate, a polyurethane or a styrene/butadiene rubber. 
     US 2002/0128366 (Coffey) describes a process for the production of coloured particles composed of vulcanized rubber, encompassing the following steps: an aqueous pigment dispersion is added to the as yet uncoloured vulcanized rubber particles, and the two constituents are mixed until the rubber particles have been coloured, and then an elastomer latex is added, and mixing is repeated, and the latex is permitted to set. The elastomer used comprises either a styrene/butadiene rubber or a polybutadiene rubber. 
     DISADVANTAGES OF THE PRIOR ART 
     A disadvantage of the prior art cited is that no physical and/or chemical data are disclosed which provide evidence of the long-term weathering resistance required for artificial-turf-infill materials. Data are moreover lacking in relation to the abrasion resistance of the coated rubber particles, this being an important property for problem-free play on the sports facilities equipped with artificial-turf-infill materials, because an excessive level of abrasion leads to a high level of dusting, and an excessive proportion of agglomerated particles leads to uncontrolled and unpredictable ball-bounce performance. 
     A further intention was to develop a simple coating process for the granulated-rubber materials, in order to comply with requirements for low-cost production. 
     OBJECT 
     In view of the prior art cited above, with its disadvantages, the objects were then to provide a further production process for the production of a free-flowing granulated-rubber material. The process is intended to be simple and to be readily capable of scale-up and to minimize solvent use. The process is moreover intended to be inexpensive. 
     DIN V 18035-7 (preliminary standard) sets out the technical requirements placed upon an artificial-turf surface for sports facilities. The said standard is applicable to a wide variety of types of sport, examples being football, hockey, American football and tennis. 
     The fill materials have to have a certain level of resistance when exposed to moisture, and to the resultant leaching of in particular aqueous solutions comprising heavy metals, since DIN V 18035-7 (preliminary standard) provides that there can be means provided for the moistening of the artificial-turf surface, in order to improve sports characteristics and risk-prevention characteristics, and in order to reduce wear. 
     Line 19 of Table 6 of the standard says that elastic fillers can by way of example be composed of EPDM vulcanizate and/or recycled rubber. The grain size range is intended to be from 0.5 to 4 mm, and the proportion of constituents below 0.5 mm here is intended to be less than 1%. The grains are intended to be of angle-cut shape. 
    
    
     ACHIEVEMENT OF OBJECT 
     The objects are achieved via a process of Claim  1  or of Claim  2 . Other advantageous embodiments are protected by the dependent claims. 
     The objects are achieved via a multicomponent system for the coating of granulated-rubber products in a fluidized-bed apparatus, a solids mixer, or in a drum mixer. This system is composed of a binder component based on epoxy resin and of an anhydride hardener. The crosslinking reaction can be promoted by various catalysts. 
     The hardening of the coating takes place in the temperature range from 60 degrees Celsius to 150 degrees Celsius, preferably in the temperature range from 80 degrees Celsius to 120 degrees Celsius. 
     The mixture can also be heated by infrared sources, and the heating can also take place in a second step. 
     It is moreover possible to use the mixture of the invention not only to coat rubber particles but also to coat rubber surfaces or rubber coverings. 
     Constitution of the Coating 
     The binder component can be composed of one or more epoxy resins. Those that can be used here are the traditional bisphenol A resins, bisphenol F resins, bisphenol AF resins, cycloaliphatic epoxy resins and epoxy resins based on hydrogenated bisphenol A. Solid resins can usefully be dissolved in reactive diluents, examples being aliphatic monoglycidyl ethers, cresyl glycidyl ether, p-tert-butylphenol glycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether etc. and in low-viscosity, liquid epoxy resins. This binder component can be a mixture composed of the substances mentioned, but can also comprise pigments, fillers, additives, antioxidants, UV absorbers, solvents, flow control agents, and catalysts. However, it is preferable to use a cycloaliphatic epoxy resin known as Epikote® Resin 760 from Hexion. 
     The anhydride hardener can comprise maleic-anhydride-modified polymers based on a variety of chemicals and/or methylhexahydrophthalic anhydride (Epikure®, Curing Agent 868, Hexion), methyltetrahydrophthalic anhydride (Epikure® Curing Agent 866, Hexion). 
     Maleic-anhydride-modified polymers are polyalkenylenes, preferably based on 1,3-butadiene, isoprene, 2,3-di-methyl-1,3-butadiene and chloroprene. 
     Homo- or copolymers of the abovementioned monomers can be used, but preference is given to homopolymers, especially those of 1,3-butadiene. The polyalkenylenes can have 1,4 linkage or 1,2 linkage. However, it is equally possible to use a mixture composed of 1,2 and 1,4 linkages, where the arrangements assumed by the 1,4 linkage can be cis or trans arrangements. It is very particularly preferable to use a polybutadiene having about 75% of 1,4-cis double bonds, about 24% of 1,4-trans double bonds and about 1% of 1,2 double bonds (Polyoil, Degussa). 
     It is also possible to use polyalkenylenes which are composed of at least one of the abovementioned monomeric dienes and one or more vinyl compounds and/or alkenes. Examples of suitable vinyl compounds are styrenes or substituted styrenes, vinyl ethers, and, respectively, esters of acrylic or methacrylic acid. Examples of suitable alkenes are ethene, propene, butene or isobutene. Natural oils can also be modified with maleic anhydride, examples being coconut oil, palm oil, castor oil, olive oil, peanut oil, rapeseed oil, soya oil, sunflower oil, poppy oil, linseed oil, wood oil, etc. 
     The maleic-anhydride-modified polymers can comprise from 1 to 20 percent by weight of maleic anhydride. The preferred content of maleic anhydride is from 7 to 14 percent by weight. 
     POLYVEST® OC 800 S is a maleic-anhydride-modified Polyoil 110 from Degussa and is obtainable with this name from Evonik Degussa GmbH. 
     POLYVEST® OC 800 S contains randomly distributed succinic anhydride units. This makes the polybutadiene, which is initially non-polar, more polar and accessible to various chemical reactions. POLYVEST® OC 800 S has good electrical insulation properties and low-temperature properties. POLYVEST® OC 800 S is soluble in aliphatics, aromatics, and ethers, and is compatible with long-oil alkyd resins, colophony, resin esters and zinc resinates. It can be used as crosslinking agent component in 2C systems, as polymeric chalk activator for rubber mixtures, and in particular for EPDM mixtures and for water-soluble, oxidatively drying binders. 
     The hardener component can optionally be formulated to be solvent-free or solvent-containing, in the form of clear coat or filled system. 
     Further components that can therefore optionally be added to the hardener component are organic and/or inorganic pigments, wetting agents, dispersing agents, lubricants, organic and/or inorganic fillers, antioxidants, UV absorbers, UV stabilizers, IR absorbers, flow aids or flow control agents. 
     The solvent used can comprise solvents conventional in the coatings industry, examples being esters composed of organic carboxylic acids and of aliphatic alcohols, e.g. ethyl acetate, propyl acetate, butyl acetate or methoxypropyl acetate. 
     It is equally possible to use aliphatic and aromatic hydrocarbons, ketones and ethers. 
     Catalysts can be used to accelerate the crosslinking reaction. 
     These catalyst can be added, prior to the application process, as third component of the mixture composed of binder component and of hardener component. 
     Admixture to the binder component or hardener component is also possible. Tertiary amines can be used as catalyst, examples being triethylamine, cyclohexyldimethylamine, benzyldimethylamine, N-methylimidazole, organic titanates, zirconates, and zinc carboxylates and bismuth carboxylates. 
     
       
         
           
               
            
               
                   
               
               
                 Binder component 
               
            
           
           
               
               
            
               
                   
                 Component A 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 A1 
                 A2 
                 A3 
                 A4 
                 A5 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Epikote Resin 760 
                 73.2 
                 36.4 
                 44.2 
                 40.4 
                 30.3 
               
               
                 Tegomer E-Si 2330 
                 — 
                 2.6 
                 — 
                 — 
                 1.4 
               
               
                 Methoxypropyl acetate 
                 — 
                 9 
                 7 
                 10 
                 12 
               
               
                 Tego Dispers 650 
                 — 
                 — 
                 — 
                 — 
                 0.4 
               
               
                 Blanc fixe micro 
                 13.2 
                 32 
                 9.8 
                 27.6 
                 32.9 
               
               
                 Kronos 2190 
                 10 
                 15 
                 30 
                 15 
                 15 
               
               
                 Heliogen Green L 8730 
                 2 
                 3 
                 6 
                 3 
                 0.5 
               
               
                 Hostaperm Yellow H3G 
                 0.6 
                 1 
                 2 
                 3 
                 — 
               
               
                 Hostaperm Yellow H5G 
                 — 
                 — 
                 — 
                 — 
                 6.5 
               
               
                 Wingstay L 
                 1 
                 1 
                 1 
                 1 
                 1 
               
               
                   
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
            
               
                   
               
               
                 Hardener component 
               
            
           
           
               
               
            
               
                   
                 Component B 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 B1 
                 B1 
                 B2 
                 B3 
                 B4 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Epikure Curing Agent 868 
                 10 
                 10 
                 10 
                 30 
                 15 
               
               
                 Polyvest OC 800 S 
                 60 
                 60 
                 90 
                 70 
                 — 
               
               
                 Polyvest EP OC 1000 S 
                 — 
                 — 
                 — 
                 — 
                 85 
               
               
                 Blanc fixe micro 
                 11 
                 11 
                 — 
                 — 
                 — 
               
               
                 Kronos 2190 
                 15 
                 15 
                 — 
                 — 
                 — 
               
               
                 Heliogen Green L 8730 
                 3 
                 3 
                 — 
                 — 
                 — 
               
               
                 Hostaperm Yellow H3G 
                 1 
                 1 
                 — 
                 — 
                 — 
               
               
                   
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
            
               
                   
               
               
                 Mixing ratio 
               
            
           
           
               
               
            
               
                   
                 Coating:hardener 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 A1:B1 
                 A2:B1 
                 A3:B2 
                 A4:B3 
                 A5:B4 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Mixing ratio 
                 1:4 
                 1:2 
                 1:2 
                 1:1 
                 1:1 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
            
               
                   
               
               
                 Catalyst 
               
            
           
           
               
               
            
               
                   
                 Coating:hardener 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 A1:B1 
                 A2:B1 
                 A3:B2 
                 A4:B3 
                 A5:B4 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 100% by weight of 
                 3.2 
                 1.5 
                 2.2 
                 1.3 
                 1.2 
               
               
                 Epikure 
               
               
                   
               
            
           
         
       
     
     The particles to be coated comprise rubber particles which are preferably obtained by recycling of used tyres. The size of the rubber particles is from 0.1 mm to 10 mm, preferably from 0.5 mm to 7.5 mm and particularly preferably from 0.4 mm to 4 mm. 
     Since, by virtue of the production process, the rubber particles do not have a regular shape, the above values are to be understood purely as guideline values. 
     The thickness of the coating is from 1 μm to 100 μm, preferably from 2 μm to 50 μm and very particularly preferably from 5 μm to 25 μm. 
     Since, by virtue of the production process, the rubber particles do not have a regular shape, the above values are to be understood purely as guideline values. In particular, coatings which locally have significantly greater thickness can be produced via filling of cavities of the rubber particles. 
     The components can be applied in premixed form or by way of a multicomponent mixing system, for example a 2C mixing and spraying system. The coating material needed for the coating process, composed of component A and of component B and of catalyst component, can be applied once or in a plurality of steps. After application of each individual layer, coating can continue immediately, or a crosslinking step (time, heat) can be inserted. 
     Working of the Invention 
     A mixture A composed of a
         cycloaliphatic epoxy resin, using from 10% by weight to 80% by weight of cycloaliphatic epoxy resin, preferably from 20% by weight to 40% by weight of cycloaliphatic epoxy resin and very particularly preferably 30% by weight of cycloaliphatic epoxy resin,   of amounts of from 0.1% by weight to 5.9% by weight of silicone oil,   of amounts of from 0.1% by weight to 2.9% by weight of a wetting and dispersing agent,   of antioxidant,   of barium sulphate,   using from 1% by weight to 50% by weight of barium sulphate, preferably from 20% by weight to 45% by weight of barium sulphate and very particularly preferably from 30% by weight to 40% by weight of barium sulphate,   of titanium dioxide,   of further pigments, and   of solvent, about 10% by weight -20% by weight (where the other components give a total of 100% by weight)
 
and a mixture B composed of an
   aliphatic anhydride,   using from 1% by weight to 50% by weight of aliphatic anhydride, preferably from 5% by weight to 20% by weight of aliphatic anhydride and very particularly preferably from 5% by weight to 15% by weight of aliphatic anhydride, and   of an MA-modified polybutadiene,   using from 99% by weight to 50% by weight of MA-modified polybutadiene, preferably from 90% by weight to 65% by weight of MA-modified polybutadiene and very particularly preferably 85% by weight of MA-modified polybutadiene
 
are mixed in a ratio of from 10 parts by weight of mixture A:1 part by weight of mixture B to 1 part by weight of mixture A:10 parts by weight of mixture B, and catalyst is admixed with this mixture and this material is mixed with the granulated-rubber material at from 80 degrees Celsius to 120 degrees Celsius in a drum mixer. It is also possible to set other mixing ratios and to omit the premixing of the coating components, and to add them simultaneously to the initial charge of granulated-rubber material. The table states the preferred mixing ratios.
       

     Preparation of Mixture A 
     The mixture A is prepared as follows:
         30.3% by weight of Epikote Resin 760 (cycloaliphatic epoxy resin, Hexion),   1.4% by weight of Tegomer E-Si 2330 (silicone oil, Evonik Degussa GmbH),   12% by weight of methoxypropyl acetate (solvent),   0.4% by weight of Tego Dispers 650 (wetting and dispersing agent, Evonik Degussa GmbH),   32.9% by weight of Blanc fixe micro (barium sulphate filler, Sachtleben),   15% by weight of Kronos 2190 (TiO 2  pigment, Kronos),   0.5% by weight of Heliogen Green L 8730 (pigment, BASF),   6.5% by weight of Hostaperm Yellow H5G (pigment, Clariant), and   1% by weight of Wingstay L (antioxidant; Eliokem) are dispersed and ground in a bead mill until the grains are appropriately fine.       

     Preparation of Mixture B 
     The mixture B is prepared and stored under nitrogen. For this,
         15 parts by weight of Epikure Curing Agent 868 (aliphatic anhydride, Hexion)   are mixed, with stirring, with   85 parts by weight of Polyvest EP OC 1000 S (specific MA-modified polybutadiene from Evonik)   until the resultant formulation is homogeneous.       

     The formulations of the invention have excellent properties, examples being abrasion values, prior to and after exposure to light and weathering, and elasticity prior to and after exposure to light and weathering, and are resistant to the effects of weathering. The formulations of the invention moreover have excellent colourfastness after exposure to light and weathering, and also excellent stability when subjected to temperature changes, and when subjected to high temperatures, for example at 50 degrees Celsius over a period of 4 weeks. The formulations of the invention moreover dry easily. 
     In a further embodiment, the flowable particles of the invention can, for example in situ, be provided with an adhesive or polymerizing or crosslinking layer which permits the particles to be cast into a matrix of any desired shape and to be hardened. The polymer matrix used can comprise polyurethane resins or epoxy resins. Any desired colour effects can be achieved through different colourings of matrix and granulated-rubber material.