EP2094789A1

EP2094789A1 - Layer materials with improved adhesion comprising elastic polyurethane binder and plastics granules

Info

Publication number: EP2094789A1
Application number: EP07822475A
Authority: EP
Inventors: Markus SCHÜTTE; Berend Eling; Bernd Bruchmann; Daniel SCHÖNFELDER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-11-15
Filing date: 2007-11-12
Publication date: 2009-09-02
Also published as: US20090318607A1; JP2010509480A; WO2008058919A1

Abstract

The present invention relates to a polyurethane binder for production of elastic layer materials comprising plastics granules, where the polyurethane binder comprises hyperbranched polymer, and to a process for production of these polyurethane binders. The present invention further relates to elastic layer materials obtainable via mixing of this polyurethane binder and plastics granules, and also, if appropriate, other auxiliaries and additives, and hardening of the mixture, to a process for production of these layer materials, and to the use of the inventive layer materials as floorcoverings for sports surfaces, e.g. playing areas, athletics tracks and sports halls, and for children's play areas, and for walkways.

Description

Laminates with improved adhesion, containing an elastic polyurethane binder and plastic granules.

description

The present invention relates to a polyurethane binder for the production of elastic laminates containing plastic granules, wherein the polyurethane binder hyperbranched polymer, and a method for producing such polyurethane binders. Further, the present invention relates to elastic laminates obtainable by mixing such a polyurethane binder and plastic granules and optionally further auxiliaries and additives and curing the mixture, a process for producing such laminates and the use of the laminates of the invention as floor coverings for sports surfaces, such as fields, athletics tracks and sports halls , for children's playgrounds and for sidewalks.

Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular combination specified, but also in other combinations, without departing from the scope of the invention.

The production of elastic laminates containing rubber or plastic particles, using suitable binders is already known.

Thus, in DE 1 534 345 water-permeable, elastic floor coverings for sports fields are described, wherein the chemical composition of the binder used is not further explained. The use of two-component polyurethane binders for bonding elastic particles is described in DE 1 955 267 and DE 1 720 059, as well as in DE 2 156 225 and DE 2 215 893. Moisture-curing one-component polyurethane binders for this application are described, for example, in DE 2021 682, DE 2 228 11, DE 2 427 897, DE 2 447 625 and DE 2 821 001. Mainly for cost reasons are usually used as plastic particles Gummigranulatteilchen.

The mechanical strength of such laminates is usually limited by the low adhesion of polyurethane binder and rubber. Heavy use, for example due to frequent use or the use of spikes, can lead to partial destruction or premature wear of the composite material.

To improve the adhesion between Gummigranulatteilchen and binder proposes DE 2 455 679, in a first step, the rubber granules with a To coat paste from hydroxyl-containing polyethers, mineral fillers and / or pigments and then mix with the polyisocyanate binder and cure.

A disadvantage of this method is that it is a two-stage process with increased work, are increased only slightly at the elongation at break and tensile strength.

The object of the invention was therefore to provide a polyurethane binder for the production of elastic laminates containing plastic granules, which allows without additional processing steps in the production of the laminate improved adhesion of the binder and the plastic granules, which shows, for example, by increased tensile strength.

It was a further object of the invention to provide a process for producing such binders.

Another object of the present invention was to provide elastic laminates which have a longer life and a higher load capacity than laminates of the prior art.

The object of the invention is achieved by a polyurethane binder for the production of elastic laminates containing plastic granules, wherein the polyurethane binder contains a hyperbranched polymer. Furthermore, the object according to the invention is achieved by an elastic laminate obtainable by mixing a polyurethane binder according to the invention with the plastic granules and curing the mixture.

For the purposes of the present invention, plastics are understood to mean thermosetting, elastomeric and thermoplastic plastics.

Thermosetting plastics are plastics that exhibit irreversible and tight crosslinking via covalent bonds. Thermosetting plastics are steel-elastic at low temperatures, and even at higher temperatures they can not flow viscously, but behave elastically with very limited deformability. The shear modulus does not fall below 10 ² kp / cm ² at any temperature. The thermosetting plastics include, among others, the technically important groups of substances of diallyl phthalate resins, epoxy resins, urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins, phenol-formaldehyde resins and unsaturated polyester resins.

Elastomeric plastics are polymers with rubber-elastic behavior, which can be repeatedly stretched at 20 ⁰ C at least to 1, 5 times their length, and After canceling the compulsion required for the stretch immediately return approximately their initial dimensions.

Thermoplastics are polymeric materials which are soft or hard at service temperature and have a flow transition range above the service temperature. Thermoplastic plastics consist of linear or branched polymers, which in the case of amorphous thermoplastics above the glass transition temperature (Tg), in the case of (partially) crystalline thermoplastic polymers above the melting temperature (T _m ) are in principle fluid.

Plastic granules used are preferably elastomeric plastics. Vulcanized rubber compounds are particularly preferably used as elastomeric plastics, for example butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), styrene-isoprene-butadiene rubber (SIBR), acrylonitrile-butadiene rubber. Rubber (NBR), chloroprene rubber (CR), isobutene-isoprene rubber (NR), EPDM and natural rubber (NR), both pure or as blends with one another, blended with vulcanization accelerators and / or crosslinking agents based on sulfur or peroxide and more commonly used Practice vulcanized. EPDM is a rubber made by terpolymerizing ethene and larger proportions of propylene and a few percent of a third diene monomer in which the diene monomer provides the double bonds needed for subsequent sulfur vulcanization. The diene monomers predominantly cis, cis-1, 5-cyclooctadiene (COD), exo-dicyclopentadiene (DCP), endo-dicyclopentadiene (EDCP) u. 1, 4-hexadiene (HX) u. V. A. 5-Ethylidene-2-norbornene (ENB) Use. Particularly preferred elastomers are vulcanized styrene-butadiene rubber, styrene-butadiene rubber blends with e.g. EPDM or EPDM used.

The elastomers optionally contain commercially available fillers, such as carbon blacks, silica, chalk, metal oxides, plasticizers, antioxidants, antiozonants and / or thermoplastic polymers, such as styrene-containing thermoplastics, for example polystyrene or polystyrene acrylonitrile (SAN), ethylene vinyl acetate (EVA), polyethylene, polypropylene, polycarbonate , thermoplastic polyurethane (TPU), polyvinyl chloride (PVC) or thermoplastic elastomers based on styrene-butadiene-styrene block copolymers or styrene-isoprene-styrene block copolymers or blends of said thermoplastics with one another.

The plastic granules used in the process according to the invention may be of any size and shape. However, elastic granules of rubber or plastic waste in the particle sizes of 0.5 to 60 mm, preferably 1 to 10 mm, are preferably used. Such waste arises z. B. in the tire innovation and in the production of technical rubber or plastic articles. Waste from tire retreading is preferred for financial reasons.

A polyurethane binder is to be understood as meaning a mixture which comprises at least 50% by weight, preferably at least 80% by weight and in particular at least 95% by weight, of an isocyanate-containing prepolymer, hereinafter referred to as isocyanate prepolymer, and hyperbranched polymer. In this case, the isocyanate prepolymer and the hyperbranched polymer may be present in the form of a purely physical mixture, or the hyperbranched polymer may be bound to the isocyanate prepolymer by covalent bonding. Covalent bonding of the hyperbranched polymer to the polymer matrix of the isocyanate prepolymer is preferred.

The viscosity of the polyurethane binder of the invention is preference, in the range of 500 to 4000 mPa.s, more preferably of 1000 to 3000 mPa.s, measured at 25 ⁰ C in accordance with DIN 53 018th

The prepolymers containing isocyanate groups can be prepared by reacting polyisocyanates (a) with isocyanate-reactive compounds (b), hyperbranched polymer (c) and optionally chain extenders and / or crosslinkers (d), the polyisocyanate (a) being present in excess is used.

As polyisocyanates (a) it is possible to use all aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates known from the prior art and any desired mixtures thereof. Examples are 4,4 ^', 2,4' and 2,2'-diphenylmethane diisocyanate, the mixtures of monomeric socyanaten Diphenylmethandii- and higher-nuclear homologues of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), Isophorondiisocya- nat (IPDI) , 1, 5-naphthalene diisocyanate (NDI), 2,4,6-toluene triisocyanate and 2,4- and 2,6-toluene diisocyanate (TDI), or mixtures thereof.

Preferably 2,4-Toluoldiiisocyanat, 2,6-Toluoldiiisocyanat, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate and higher nuclear homologues of diphenylmethane diisocyanate (polymer-MDI) and mixtures of these isocyanates, uretonimine in particular a mixture of 2,4 '- Diphenylmethandiisocyanat and 4,4'-diphenylmethane diisocyanate used as the polyisocyanate (a).

As isocyanate-reactive compounds (b), all compounds having at least two isocyanate-reactive hydrogen atoms can be used. Preferably, polyesterols, polyetherols, or mixtures of polyols etherols with polyols which have a tertiary amine group in particular Polyethe- role used.

Polyols having tertiary amino groups can be obtained, for example, by reaction of secondary amines such as ethylenediamine with alkylene oxides, for example, ethylene oxide or propylene oxide.

Suitable polyetherols are bound by known methods, for example by anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and with the addition of at least one starter molecule containing 2 to 5, preferably 2 to 4 and more preferably 2 to 3, in particular 2 reactive hydrogen atoms bound, or by cationic Polymerization with Lewis acids, such as antimony pentachloride or boron trifluoride etherate, prepared from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical. Further, as catalysts, it is also possible to use multimetal cyanide compounds, so-called DMC catalysts. Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide and preferably ethylene oxide and 1, 2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures. Preference is given to using 1,2-propylene oxide, ethylene oxide or mixtures of 1,2-propylene oxide and ethylene oxide.

Suitable starter molecules are preferably water or dihydric and trihydric alcohols, such as ethylene glycol, 1, 2- or 1, 3-propanediol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, glycerol and trimethylolpropane.

The preferred polyether polyols, more preferably polyoxypropylene or polyoxypropylene polyoxyethylene polyols, have a functionality of from 2 to 5, more preferably from 2 to 3, and molecular weights from 400 to 9,000, preferably 1,000 to 6,000, more preferably 1,500 to 5,000, and especially from 2,000 to 4,000 g / mol. The polyether polyol used is particularly preferably polypropylene glycol having a weight-average molecular weight of from 1500 to 2500 g / mol.

For the purposes of the invention, hyperbranched polymers (c) used are any polymers having a weight-average molecular weight of greater than 500 g / mol, whose main chain is branched, and which have a degree of branching (DB) of greater than or equal to 0.05. Preference is given to hyperbranched polymers (c) having a weight-average molecular weight of greater than 800 g / mol, more preferably greater than 1000 g / mol and in particular greater than 1500 g / mol and a degree of branching of 0.1 and greater. The degree of branching of the hyperbranched polymers (c) according to the invention is particularly preferably from 0.2 to 0.99 and in particular from 0.3 to 0.95 and very particularly from 0.35 to 0.75. To define the degree of branching, see H. Frey et al., Acta Polym. 1997, 48, 30. Preferred hyperbranched polymers (c) are those based on ethers, amines, esters, carbonates, amides, urethanes and ureas and their mixed forms, such as, for example, ester amides, amidoamines, ester carbonates, urea-urethanes, etc. In particular, as hyperbranched polymers (c) hyperbranched polymers can be used. ethers, polyesters, polyesteramides, polycarbonates or polyestercarbonates. Such polymers and processes for their preparation are described in EP 1 141083, in DE 102 11 664, in WO 00/56802, in WO 03/062306, in WO 96/19537, in WO 03/54204, in WO 03/93343, in US Pat WO 05/037893, in WO 04/020503, in DE 10 2004 026 904, in WO 99/16810, in WO 05/026234 and DE 102005009166.

In one embodiment, the hyperbranched polymers (c) according to the invention have different functional groups. Preferably, these functional groups are capable of reacting with isocyanates and / or with reactive groups of the plastic granules, for example a rubber granulate, or else interacting with the plastic, for example rubber.

The functional groups which are reactive with isocyanates are, for example, hydroxyl, amino, mercapto, epoxy, carboxyl or acid anhydride groups, preferably hydroxyl, amino, mercapto or acid anhydride groups.

The functional groups which can react with the reactive groups of the plastic, for example rubber, are, for example, groups which are capable of free-radical polymerization, such as olefinic double bonds, triple bonds or activated double bonds, for example vinyl groups, (meth) acrylate groups, maleic or fumaric acid groups or their derivatives containing groups.

The functional groups that can interact with the plastic, for example rubber, are units that do not react covalently with the solid, but interactions via positively or negatively charged groups, through electronic donor or acceptor bonds, via coordinative interactions , via hydrogen bonding via van der Waals bonds or hydrophobic interactions.

Hydrogen bond or donor and acceptor bond forming moieties may include, for example, hydroxyl, amino, mercapto, epoxy, carboxyl or acid anhydride groups, carbonyl groups, ether groups, olefinic double bonds, conjugated double bonds, triple bonds, activated double bonds, for example (Meth ) acrylate groups or maleic or fumaric acid or derivatives thereof containing groups. Van der Waals bonds or hydrophobic interaction-generating elements can be, for example, linear or branched alkyl, alkenyl or alkynyl radicals of the chain length Ci-C120 or aromatic systems having 1-10 ring systems which are also reactive with heteroatoms, such as nitrogen, phosphorus, Oxygen or sulfur can be substituted. Also suitable are linear or branched polyether elements based on ethylene oxide, propylene oxide, butylene oxide, styrene oxide or mixtures thereof, as well as polyethers based on tetrahydrofuran or butanediol.

In a preferred embodiment, the hyperbranched polymers (c) have both isocyanate-reactive groups and groups which react or interact with the solid, for example the ester, ether, amide and ester groups obtained via the coupling of the monomers or carbonate structures as well as hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, vinyl groups, (meth) acrylic double bonds, maleinic double bonds and / or long-chain branched or unbranched alkyl radicals.

In general, the hyperbranched polymers (c) according to the invention have an acid number according to DIN 53240, Part 2 of 0 to 50, preferably 1 to 35 and particularly preferably 2 to 20 and in particular 2 to 10 mg KOH / g.

The hyperbranched polymers (c) furthermore generally have a hydroxyl number according to DIN 53240, Part 2 of 0 to 500, preferably of 10 to 500 and particularly preferably of 10 to 400 mg KOH / g.

Next hyperbranched polymers of the invention (c) typically have a glass transition temperature (measured by the method ASTM D3418 - 03 with DSC) -60 to 100 ⁰ C, preferably from -40 to 80 ⁰ C.

The high-functionality, hyperbranched polymers (c) according to the invention are preferably amphiphilic polymers. The amphiphilia is preferably obtained by incorporation of hydrophobic residues into a hydrophilic, hyperbranched polymer, for example a hyperbranched polymer based on a polyester. Such hydrophobic residues preferably have more than 6, more preferably more than 8 and less than 100, and most preferably more than 10 and less than 50 carbon atoms.

The hydrophobization can in the esterification, for example, by total or partial replacement of di- and / or polycarboxylic acids or di- and / or polyols by mono-, di- and / or polycarboxylic acids containing such a hydrophobic radical, or mono-, di- and / or polyols containing such a hydrophobic radical. Examples of such mono-, di- or polycarboxylic acids containing a hydrophobic radical are aliphatic carboxylic acids such as octanoic acid, decanoic acid, Dode- canic acid, tetradecanoic acid, fatty acids, such as stearic acid, oleic acid, lauric acid, palmitic acid, linoleic acid, linolenic acid, aromatic carboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, cycloaliphatic carboxylic acids, such as cyclohexanedicarboxylic acid, carbonic acids, such as octanedioic acid, decanedioic acid, dodecanedioic acid, Tetradecanedioic acid and dimer fatty acids. Examples of mono-, di- or polyols containing a hydrophobic radical are aliphatic alcohols, such as the isomers of octanol, decanol, dodecanol, tetradecanol, fatty alcohols, such as stearyl alcohol, oleyl alcohol, unsaturated alcohols, such as allyl alcohol, crotyl alcohol, aromatic alcohols such as benzyl alcohol, cycloaliphatic alcohols such as cyclohexanol and monofatty acid glycerols, such as, for example, glycerol monostearate, glycerol monooleate, glyceryl monopalmeate.

The hyperbranched polymers (c) generally have an HLB value of 1 to 20, preferably 3 to 20 and particularly preferably 4 to 20. If, for the construction of the inventive highly functional, highly branched and hyperbranched polymers (c) alkoxylated lierte Alcohols are used, the HLB value is preferably 5 to 8.

The H L B value is a measure of the hydrophilic and lipophilic content of a chemical compound. The determination of the HLB value is described, for example, in W.C. Griffin, Journal of the Society of Cosmetic Chemists, 1949, 1, 311 and W.C. Griffin, Journal of the Society of Cosmetic Chemists, 1954, 5, 249.

For polyester and hydrophobized polyesters, the HLB value indicates the ratio of the number of ethylene oxide groups multiplied by 100 to the number of carbon atoms in the lipophilic moiety and is determined by the method of CD. Moore, M. Bell, SPC Soap, Perfum. Cosmet. 1956, 29, 893 calculated as follows:

HLB = (number of ethylene oxide groups) ^* 100 / (number of carbon atoms in the lipophilic part of the molecule)

In a particularly preferred embodiment, the hyperbranched polymer (c) used is a hyperbranched polyester d1) which is obtained by esterification of α-β-unsaturated carboxylic acids or derivatives thereof with a polyhydric alcohol to give the polyester. Dicarboxylic acids or their derivatives are preferably used as α-β-unsaturated carboxylic acids or derivatives thereof, the double bond in a particularly preferred embodiment being adjacent to each of the two carboxyl groups. Such particularly preferred α-β-unsaturated carboxylic acids or their derivatives are, for example, maleic anhydride, maleic acid dichloride, fumaric acid, fumaric acid, itaconic acid, itaconic acid, and / or maleic acid, preferably maleic acid, maleic anhydride or maleic acid dichloride, more preferably maleic anhydride. The α-ß unsaturated carboxylic acids or their derivatives, alone, as a mixture with each other, or together with other carboxylic acids, preferably di- or polycarboxylic acids or derivatives thereof, particularly preferably dicarboxylic acids or derivatives thereof, for example adipic acid. In the following, the expression "α-β-unsaturated carboxylic acids or their derivatives" also means mixtures containing two or more α-β-unsaturated carboxylic acids or mixtures containing one or more α-β-unsaturated carboxylic acids and further carboxylic acids.

Polyester (c1) based on maleic anhydride are described, for example, in DE 102004026904, WO 2005037893. The polyfunctional alcohol used is preferably a polyetherol or polyesterol, for example as described under (b), or mixtures of different polyols. In this case, the total mixture of the alcohols used has an average functionality of 2.1 to 10, preferably from 2.2 to 8 and particularly preferably from 2.2 to 4.

In the reaction of the α-ß unsaturated carboxylic acids or their derivatives with the polyhydric alcohol, the ratio of the reactive partners in the reaction is preferably chosen so that a molar ratio of molecules with acid groups or derivatives thereof reactive groups to molecules with acid groups or their Derivatives of 2: 1 to 1: 2, more preferably from 1, 5: 1 to 1: 2, most preferably from 0.9: 1 to 1: 1, 5 and in particular of 1: 1. The reaction is carried out under reaction conditions under which react acid groups or their derivatives and acid groups or their derivatives reactive groups with each other.

The preparation of the particularly preferred hyperbranched polyesters is carried out by reacting the α-ß unsaturated carboxylic acids or their derivatives with the polyhydric alcohol, preferably at temperatures of 80 to 200 ⁰ C, more preferably at 100 to 180 ⁰ C. The preparation of the particularly preferred hyperbranched Polyester in substance or in solution. Suitable solvents are, for example, hydrocarbons such as paraffins or aromatics. Particularly suitable paraffins are n-heptane, cyclohexane and methylcyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Further suitable solvents are ethers, such as, for example, dioxane or tetrahydrofuran and ketones, for example methyl ethyl ketone and methyl isobutyl ketone.

The pressure conditions in the preparation of the particularly preferred polyester (d) by reacting α-ß unsaturated carboxylic acids or their derivatives with the polyhydric alcohol are not critical per se. You can work at significantly reduced pressure, for example at 1 to 500 mbar. The process for their preparation can also be carried out at pressures above 500 mbar. Also, the reaction at atmospheric pressure is possible, but it is also possible with an implementation slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar. For reasons of simplicity, the reaction is preferred at atmospheric pressure. Also preferred is the reaction at reduced pressures. The reaction time is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours and particularly preferably 1 to 12 hours.

The particularly preferred hyperbranched polyesters (d) obtained have a weight-average molecular weight determined by means of PMMA-calibrated GPC of from 1,000 to 500,000 g / mol, preferably from 2,000 to 200,000 g / mol, particularly preferably from 3,000 to 120,000 g / mol , on.

In a further particularly preferred embodiment, the hyperbranched polymer used is a hydrophobized hyperbranched polyester (c2). This process is analogous to the preparation of the hydrophobized hyperbranched polyester (c2) as in the preparation of the hyperbranched polyester (d), all or part of the α-.beta.-unsaturated carboxylic acids or their derivatives are hydrophobic bisiert. Preferred α-β-unsaturated carboxylic acids are maleic acid, maleic anhydride and fumaric acid, particularly preferably maleic anhydride. This hydrophobization may be carried out after or preferably before reacting with the alcohol to form the polyester. Hydrophobizing agents which can be used are preferably hydrophobic compounds containing at least one C-C double bond, such as linear or branched polyisobutylene, polybutadiene, polyisoprene and unsaturated fatty acids or derivatives thereof. The reaction with the hydrophobizing agents is carried out by methods known to the person skilled in the art, the hydrophobizing agent being added to the double bond in the vicinity of the carboxyl group, as described, for example, in German Offenlegungsschriften DE 195 19 042 and DE 43 19 671. Such particularly preferred hydrophobized hyperbranched polyesters (c2) and their preparation are described, for example, in the earlier application with the file reference DE

102005060783.7 described. Polyisobutylene having a molecular weight of from 100 to 10,000 g / mol, more preferably from 500 to 5,000 g / mol and in particular from 550 to 2,000 g / mol, is preferably used. Hyperbranched polyesters (c2) which contain an adduct of reactive polyisobutylene and maleic anhydride, so-called polyisobutylene succinic acid (PIBSA), or alkenylsuccinic acid are particularly preferred hydrophobized, hyperbranched polyesters (c2).

In a further particularly preferred embodiment, the hyperbranched polymer (c) used is mixtures comprising a hyperbranched polyester (d) and a hydrophobized hyperbranched polyester (c2). If, for the preparation of the isocyanate prepolymer according to the invention, the use of a polyesterol as component (b) is greater than 50% by weight, based on the total weight of component (b), the content of hyperbranched polyester (d) is preferably greater than 5% by weight. , Particularly preferably greater than 20 wt .-%, most preferably greater than 50 wt .-% and in particular 100 wt .-%, based on the total weight of the hyperbranched polymer (c).

If a polyetherol is used as component (b) to a greater part than 50% by weight, based on the total weight of component (b), of the hydrophobized hyperbranched polyester (c2), the content of the isocyanate prepolymer is preferably greater than 10% by weight. , Particularly preferably greater than 30 wt .-%, most preferably greater than 60 wt .-% and in particular 100 wt .-%, based on the total weight of the hyperbranched polymer (c).

The hyperbranched polymers (c) according to the invention are preferably in one

Amount of 0.001 to 50 wt .-%, particularly preferably 0.01 to 30 wt .-% and in particular 0.1 to 10 wt .-%, based on the total weight of the polyisocyanates (a), the isocyanate-reactive compounds (b ), the hyperbranched polymer (c), and optionally the chain extender and / or crosslinking agent (d) in the isocyanate prepolymer.

Optionally, chain extenders and / or crosslinkers (d) can also be used. The addition of the chain extenders and / or crosslinkers (d) may be before, together with or after the addition of the polyols. As chain extenders and / or crosslinking agents (d), substances having a molecular weight of preferably less than 400 g / mol, particularly preferably from 60 to 350 g / mol are used, chain extenders having 2 isocyanate-reactive hydrogen atoms and crosslinking agent 3 isocyanate-reactive hydrogen atoms , These can be used individually or in the form of mixtures. If chain extenders are used, 1, 3 and 1, 2-propanediol, dipropylene glycol, tripropylene glycol 1, 3 butanediol are particularly preferred.

If chain extenders, crosslinking agents or mixtures thereof are used, these are expediently used in amounts of from 1 to 60% by weight, preferably from 1.5 to 50% by weight and in particular from 2 to 40% by weight, based on the weight of polyisocyanates (a), isocyanate-reactive compounds (b), hyperbranched polymers (c) and chain extenders and / or crosslinking agents (d) are used.

The isocyanate prepolymers are obtainable by reacting polyisocyanates (a), for example at temperatures of 30 to 100 ⁰ C, preferably at about 80 ⁰ C, with isocyanate-reactive compounds (b) and hyperbranched Po lymer (c) and optionally chain extender and / or crosslinking agent (d) are reacted to the prepolymer. In this case, polyisocyanate (a), isocyanate-reactive compound (b), and hyperbranched polymer (c) and optionally chain extenders and / or crosslinking agents (d) are preferably present in a ratio of isocyanate groups to isocyanate-reactive groups of from 1.5: 1 to 15: 1, preferably 1, 8: 1 to 8: 1 mixed together. For the preparation of the prepolymers, particular preference is given to mixing polyisocyanates and the compound with isocyanate-reactive groups and chain extenders and / or crosslinking agents in a ratio such that the NCO content of the prepolymer produced is in the range from 1.0 to 20, in particular from 2 to 15 wt .-%, based on the total weight of the Isocyanatprepolymers produced, is. Subsequently, volatile isocyanates may preferably be separated, preferably by thin film distillation. The viscosity of the Isocyanatprepo- mers is preferably 1000 to 3000 mPa.s at 25 ⁰ C. Inventive natprepolymere isocyanate based on toluene diisocyanate in this case have typically has a viscosity from 1000 to 1500 mPa.s, whereas Isocyanatprepoly- invention mers on the basis of of diphenylmethane diisocyanate typically have a viscosity of 2000 to 3000 mPa.s, each at 25 ⁰ C.

Furthermore, the preparation of the isocyanate group-containing prepolymer can be carried out stepwise. For this purpose, in a first step, the isocyanate-reactive compound (b) and hyperbranched polymer (c) and optionally chain extender and / or crosslinking agent (d) with 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate up to an NCO Content of 2-5 wt .-%, based on the obtained prepolymer reacted. In a second step, the prepolymer thus prepared is mixed with isocyanates from the diphenylmethane diisocyanate series or derivatives thereof, for example 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate and higher nuclear homologues of diphenylmethane diisocyanate (polymer MDI) and / or at room temperature liquid, modified diphenylmethane diisocyanates, in particular by diphenylmethane diisocyanates modified by carbodiimide, urethane, allophanate, isocyanurate, urea and / or biuret groups, until the NCO content of the prepolymer produced has a value corresponding to the values given above , having. As a result, the content of monomeric isocyanate having a molecular weight of less than 249 g / mol can be kept low. These incrementally prepared polyisocyanate prepolymers typically have a viscosity in the range of 2000 to 3000 mPa.s at 25 ⁰ C.

The time of addition of the hyperbranched polymer (c) to the binder can be arbitrary. For example, in the preparation of isocyanate prepolymers, the hyperbranched polymer (c) can be reacted or mixed directly with the polyisocyanate (a) or else only after the reaction of the polyisocyanate (a) with the isocyanate-reactive compound (b) and optionally the chain extender and / or crosslinking agent (d) are added.

As further additives, in addition to the isocyanate prepolymer containing hyperbranched polymer, other additives such as surfactants, plasticizers, inorganic fillers such as sand, kaolin, chalk, barium sulfate, silica, oxidation stabilizers, dyes and pigments, stabilizers, e.g. against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, emulsifiers, flame retardants, anti-aging agents, adhesion promoters and reinforcing agents may be added.

The content of the binder of free, monomeric isocyanates having a molecular weight of less than 249 g / mol in the binder is preferably less than 1% by weight, more preferably less than 0.5% by weight and in particular less than 0.1% by weight, based on the total weight of the polyurethane binder.

To produce the laminates, the plastic granules in amounts of from 1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on 1 part by weight of the polyurethane binder in a conventional manner, optionally with the addition of the below-mentioned auxiliary and Additives, for example in a compulsory mixer, mixed.

The curing of the mixture can be carried out by addition of further isocyanate-reactive compounds (b) and / or chain extenders or crosslinkers (d) and hyperbranched polymer (c), the so-called two-component process. Alternatively, the curing can be carried out exclusively by the action of water, the so-called one-component process. Curing preferably takes place exclusively by the action of water, particularly preferably by atmospheric moisture. Accelerated curing can be achieved by spraying with water or by steaming. If the preparation of the laminate according to the invention takes place in the one-component process, preference is given to using no chain extender or crosslinking agent (d) for the preparation of the isocyanate-containing prepolymer.

The hardening process can be accelerated by admixing catalysts customary in polyurethane chemistry, for example tertiary amines and organic metal compounds, for example to binders. Examples of suitable catalysts are amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tri-butylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine , N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiminoethyl ether, bis - (dimethylaminopropyl) urea, dimethylpiperazine, 1, 2 Dimethylimidazole, 1-azabicyclo- (3,3,0) -octane and preferably 1,4-diaza-bicyclo- (2,2,2) -octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N- Ethyldiethanolamine and dimethylethanolamine. Also suitable as catalysts are organic metal compounds, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and Tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, for example dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates, such as bismuth (III) neodecanoate, Bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof. The organic metal compounds can be used alone or in combination with basic amines. As a preferred catalyst Dimorphinodi- methyl ether is used alone or in mixtures.

The time of catalyst addition is not limited. For example, the catalyst may already be contained in the binder or is added during mixing with the plastic granules. If the catalyst is dimorphinodimethyleter, this is preferably already present in the binder.

Preferably, 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-% catalyst or catalyst combination, based on the weight of the isocyanate-reactive component (b), the hyperbranched polymer (c) and optionally the chain extension and / or crosslinking agent (d) is added.

In a further, preferred embodiment, the plastic granules are prepared in a first step with at least part of the hyperbranched polymer c) to be used and optionally at least part of the isocyanate-reactive compounds b) and / or chain extenders and / or crosslinkers d) and optionally further additives in a known manner, preferably in a compulsory mixer, mixed. Preferably, in the first step, only the hyperbranched polymer c) and optionally further additives are mixed with the plastic granules.

Subsequently, the component a) and the optionally remaining amount of isocyanate-reactive component b), of the hyperbranched polymer c) and of the chain extender and / or crosslinking agent d), preferably in the form of an isocyanate prepolymer, are added to this mixture in a second step. added and also mixed.

The physical properties of the elastic sheet-like structures according to the invention, such as elasticity, hardness, density and water permeability, can be determined by varying the size, shape and nature of the plastic granules, binder content, average NCO functionality of the binder, content of the binder Isocyanate groups, degree of densification and curing conditions can be varied within wide limits.

The shaping of the laminate according to the invention is usually carried out by pouring, distributing and compacting the mixture of polyurethane binders and plastic granules by means of machines and tools known per se for the production of floor and road coverings onto the respective substrate to be coated, e.g. Concrete, screed or asphalt, in the desired layer thickness, which is generally 2 to 30 mm in the above applications. However, the shaping can also take place in optionally heated molds or presses, wherein the sheets are obtained after curing in the form of plates, which in turn are then laid in a conventional manner for the production of said coverings. Preferably, in the shaping and curing in heated molds or presses for accelerated curing water, particularly preferably in the form of water vapor added.

The laminates according to the invention are preferably not foamed and have a density of 0.2 to 2.0 g / cm ³ . Furthermore, laminates of the invention have increased durability and resilience, which is particularly noticeable by increased tensile strength. Therefore laminates according to the invention are particularly suitable as a covering for playgrounds, athletics tracks, sports fields and sports halls.

In the following the invention will be explained by means of examples.

Examples 1 to 3, Comparative Examples 1 and 2

The laminates were prepared according to Table 1. For this purpose, in a first step in a container made of polypropylene rubber granules with hyperbranched polyol, if present, at room temperature with a Vollrath stirrer (stirrer diameter: 8.5 cm, stirring speed: 750 revolutions / min. , Stirring time: 2 minutes) until the rubber particles were evenly wetted. Thereafter, in a second step, the addition of the Isocyanatprepolymers and again was mixed until a uniform coverage of the rubber particles was achieved with the binder. Subsequently, the mixture was filled in a wooden frame of dimensions 20 x 20 x 1, 5 cm and compressed to about 1, 5 cm thickness. The resulting laminates were cured for 7 days at room temperature and 50% relative humidity and then measured. For this purpose, the tensile strength and elongation at break according to DIN 53 504 were determined. Table 1: Starting materials for the production of laminates

The following starting materials were used:

Binder: isocyanate prepolymer of 36 parts by weight of Lupranat® Ml from Elastogran GmbH, a diphenylmethane diisocyanate having an NCO content of 33.2%, 2 parts by weight of Lupranat® MM 103 from Elastogran GmbH, a modified diphenylmethane diisocyanate having an NCO content of 29.5% and 62 parts by weight of Lupranol® 1000, a propylene oxide based polyetherol having an OH number of 56 mg KOH / g. The isocyanate prepolymer had an NCO content of 10%.

Rubber 1: rubber granulate from Krause (Dortmund), technical recycling rubber based on SBR / EPDM

Rubber 2: rubber granulate from RTW (Bindlach), scrap tire granules (15% car, 85% truck tires)

HP 1: hyperbranched polyester containing hydroxyl groups, carboxyl groups, polyether groups and branched alkyl radicals as functional elements prepared according to the following procedure:

250 g of a polyisobutylene adduct having a molecular weight of about 550 g / mol and maleic anhydride (PIBSA 550), 304 g of a trimethylolpropane-based polyetherol randomly grafted with 12 ethylene oxide units and 0.02 g of dibutyltin dilaurate were added to a 2L -Glaskolben equipped with stirrer, internal thermometer and descending condenser weighed with vacuum connection and heated to 160 ⁰ C with stirring at a pressure of 4 mbar. Within about one hour, the temperature was slowly increased to 180 ⁰ C. The water formed in the reaction was distilled off, whereby the experiment foamed somewhat by the resulting gas bubbles. The decrease in the acid number was checked regularly until a value of less than 10 mg KOH / g was reached. Thereafter, the product was cooled and analyzed. analytics:

Acid value: 6 mg KOH / g OH number: 87 mg KOH / g GPC: M _n = 990 g / mol, M _w = 8 900 g / mol (eluent: THF)

HP 2: hyperbranched polyester containing hydroxyl groups, carboxyl groups, polyether groups and branched alkyl radicals as functional elements prepared according to the following procedure:

593.3 g of an alkenylsuccinic acid (Pentasize 8), 459 g of a trimethylolpropane-based polyetherol, which was randomly grafted with 3 ethylene oxide units, and 0.06 g of dibutyltin dilaurate were placed in a 4 L glass flask equipped with stirrer, internal thermometer and weighed descending condenser with vacuum connection and slowly heated to 180 ⁰ C with stirring. In this case, a vacuum of 40 mbar was applied slowly, the experiment foamed somewhat by the resulting gas bubbles. The reaction mixture was stirred for 0.5 h at 180 ⁰ C, wherein the water formed in the reaction distilled off. The decrease in the acid number was checked regularly until a value of about 75.1 mg KOH / g was reached. Thereafter, the product was cooled and analyzed.

analytics:

Acid value: 75.1 mg KOH / g OH number: 80.8 mg KOH / g GPC: Mn = 1700, Mw = 4700 (eluent: DMAC)

Analysis of hyperbranched polymers:

The polymers were analyzed by gel permeation chromatography with a refractometer as detector. Tetrahydrofuran (THF) or dimethylacetamide (DMAc) was used as the mobile phase; polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.

The determination of the glass transition temperature Tg was carried out by means of differential scanning calorimetry (DSC), the second heating curve was evaluated.

The determination of the acid number and the OH number was carried out according to DIN 53240, part 2.

The mechanical properties of the resulting laminates are given in Table 2. Table 2

Table 2 shows that addition of hyperbranched polymer increases tensile strength and elongation.

Claims

claims

1. Polyurethane binder for the production of elastic, plastic granulate-containing laminates, characterized in that the polyurethane binder contains an isocyanate group-containing prepolymer obtainable by reacting or mixing polyisocyanates (a) with isocyanate-reactive compounds (b), hyperbranched polymer ( c) and optionally chain extenders and / or crosslinking agents (d), wherein the polyisocyanate (a) is used in excess and the binder has a viscosity at 25 ⁰ C of 500 to 4000 mPa.

2. polyurethane binder according to claim 1, characterized in that the hyperbranched polymer (c) and the prepolymer having isocyanate groups in the form of a physical mixture or the hyperbranched polymer (c) is bound by covalent bonding to the polymer matrix of the isocyanate group-containing prepolymer.

3. Polyurethane binder according to claim 1 or 2, characterized in that the isocyanate prepolymer has an NCO content in the range of 1, 0 to 20, based on the total weight of the Isocyanatprepolymers having.

4. polyurethane binder according to any one of claims 1 to 3, characterized in that the hyperbranched polymer (c) to 0.001 to 50 wt .-%, based on the total weight of the binder, is contained in the polyurethane binder.

5. polyurethane binder according to one of claims 1 to 4, characterized in that the hyperbranched polymer (c) has a weight-average molecular weight of greater than 500 g / mol and a degree of branching of greater than or equal to 0.05.

6. polyurethane binder according to one of claims 1 to 5, characterized in that the hyperbranched polymer (c) is a hyperbranched polymer based on ethers, amines, esters, carbonates, amides, urethanes or ureas and their mixed forms, such as ester amides, amidoamines, esters - Carbonates and urea urethanes is.

7. Polyurethane binder according to one of claims 1 to 6, characterized in that the hyperbranched polymer (c) hydrophob interactions gene generating molecule regions and / or free-radical polymerization reactive groups.

8. polyurethane binder according to one of claims 1 to 7, characterized in that the hyperbranched polymer is a hyperbranched polyester d1), which is obtained by esterification of α-ß unsaturated carboxylic acids or their derivatives with polyhydric alcohols

9. Polyurethane binder according to one of claims 1 to 8, characterized in that the hyperbranched polymer (c) is a hyperbranched polymer containing hydrophobic units having more than 6 carbon atoms.

10. polyurethane binder according to claim 9, characterized in that the hydrophobic unit is a fatty acid residue or a fatty alcohol residue.

1 1. polyurethane binder according to one of claims 1 to 9, characterized in that the hyperbranched polymer (c) is a hyperbranched polyester (c2), by esterification of α-ß unsaturated carboxylic acids or their

Derivatives with polyhydric alcohols is obtained, wherein the α-ß unsaturated carboxylic acids or their derivatives before or after the esterification with a hydrophobizing agent containing at least one C-C double bond, is hydrophobized.

12. polyurethane binder according to claim 1 1, characterized in that the hydrophobizing agent is linear or branched polyisobutylene.

13. polyurethane binder according to one of claims 1 to 12, characterized in that the compound containing at least two reactive hydrogen atoms (b) to at least 50 wt .-%, based on the total weight of component (b) contains a polyesterol and that hyperbranched polymer (c) to at least 5 wt .-%, based on the total weight of component (c) contains a hyperbranched polyester (d).

14. Polyurethane binder according to one of claims 1 to 12, characterized in that the at least one compound having at least two reactive hydrogen atoms (b) at least 50 wt .-%, based on the total weight of component (b) contains a polyetherol and that hyperbranched polymer (c) to at least 10 wt .-%, based on the total weight of component (c) contains a hyperbranched polyester (c2).

15. polyurethane binder according to one of claims 1 to 14, characterized in that the content of isocyanates having a molecular weight of less 249 g / mol in the binder is less than 1 wt .-%, based on the total weight of the polyurethane binder.

16. Polyurethane binder according to one of claims 1 to 15, characterized in that the content of NCO in Isocyanatprepolymer 2-18 wt .-%, based on the weight of the prepolymer containing isocyanate groups.

17. A process for producing an elastic laminate, characterized in that one mixes a binder according to one of claims 1 to 16 with plastic granules and optionally catalyst and other additives and cures to the laminate.

18. A process for producing an elastic laminate by mixing plastic granules with polyisocyanates (a), isocyanate-reactive compounds (b), hyperbranched polymer (c), optionally chain extender and / or crosslinking agents (d) and optionally further additives, characterized characterized in that in a first step

Plastic granules with at least part of the hyperbranched polymer c) is mixed and added to this mixture in a second step, the isocyanate prepolymer a) and mixed.

19. The method according to claim 18, characterized in that in the first

Step in addition to the hyperbranched polymer c) at least a portion of the isocyanate-reactive compounds b) and / or Kettenverlän- tion and / or crosslinking agent d) and optionally further additives are mixed with the plastic granules.

20. The method according to claim 18 or 19, characterized in that in the second step isocyanate prepolymer a), at least a portion of the isocyanate-reactive compounds b) and / or chain extenders and / or crosslinking agents d) in the form of an isocyanate prepolymer.

21. A method for producing an elastic laminate according to any one of claims 17 to 20, characterized in that the curing takes place under the action of water.

22. A process for producing an elastic laminate according to one of

Claims 17 to 21, characterized in that the plastic granulate is a rubber granulate based on butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), styrene-isoprene-butadiene rubber (SIBR), Acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), isobutene-isoprene rubber (NR), EPDM and natural rubber (NR) or mixtures thereof vulcanized with vulcanization accelerators and / or crosslinking agents based on sulfur or peroxide is, is used.

A flexible laminate obtainable by a method according to any one of claims 17 to 22.

24. Use of a laminate according to claim 23 as a floor covering for sports surface coverings for playing fields, athletics careers and sports halls, for children's playgrounds and sidewalks.