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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/34—Filling pastes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

• the present invention relates to the use of aqueous polyurethane dispersions in formulations for sports floor coverings.
• polyurethane liquid plastics are usually used to manufacture athletic tracks, school sports facilities, multi-purpose sports surfaces, tennis or ball games facilities, elastic layers under artificial turf, playgrounds, sidewalks, small play areas, sports halls, athletics halls and
• Multi-purpose sports halls used.
• water-permeable or water-impermeable coverings can be constructed.
• Interiors can be produced on various substrates such as asphalt, cement-bound substrates, wood and screed. Specifically, it is covering structures consisting of polyurethane prepolymers with free isocyanate groups, which either cure in one component with moisture or cure in one component with a formulation based on polyol and / or amine in a defined mixing ratio.
• Binder for elastic layers are usually polyurethane prepolymers made from higher-functional polyalcohols (e.g. polyethers and / or polyester alcohols) and higher-functional isocyanates (e.g. MDI, TDI, IPDI, HDI). You are i. a. moisture-curing, d. H. they harden with atmospheric moisture to form urea bridges to form more or less elastic films.
• binders for binding rubber granules are of particular interest. Black recycled granules or fibers are primarily used for base layers, and colored EPDM granules are preferably used for visible surfaces.
• SBR styrene-butadiene rubber
• EPDM ethylene-propylene-diene copolymer
• EVA Vinyl acetate copolymer
• These coverings are used as surfaces for e.g. B. ball games, school sports facilities, athletics tracks or tennis surfaces or as an invisible, built-up elastic layer for water-impermeable or impermeable sports surfaces or artificial turf surfaces.
• Rubber granulate grit toppings made of z. B. SBR, EPDM, EVA or recycled granules with a grain size of 0.5 to 50 mm or from fibers with a length of 0.1 to 50 mm and mineral additives with a grain size of 1 to 20 mm. These coatings are used as an elastic base layer, especially under artificial turf, but also as a pavement. • Coverings of other granulated materials such as cork, PVC, polyethylene, PU foam, composite foam or their fibers.
• an adhesion promoter or a primer is usually moisture-curing polyurethane prepolymers that generally contain considerable amounts of organic solvents for better penetration into the substrate.
• Two-component curing adhesives or primers are also used, polyisocyanates or
• Prepolymers are cured in a predetermined mixing ratio with a polyol-based formulation.
• Solvent-free adhesion promoters or primers are also known.
• Polyurethane coatings can be applied by spraying. In this way, generally water-permeable, but also water-impermeable structural coverings are obtained by previously filling the substrate. Both one- and two-component structural spray coatings are usually moisture-curing and contain considerable amounts of organic to ensure good sprayability Solvents. In addition to the reactive substances and solvents described, the polyurethane spray coatings on the market also contain fillers, pigments, catalysts and thixotropic agents.
• Elastic layer or other substrates e.g. asphalt, cement-bound substrates, wood
• an elastic granulate e.g. EPDM
• Rubber granulate mats can be applied.
• the surface can later be provided with a seal for protection or can be sprinkled with rubber granulate in excess (while still liquid).
• the prior art is two-component curing
• Polyurethane coatings in which a component usually consists of one or more higher-functionality polyalcohols (e.g. polyether and / or polyester alcohols), fillers, pigments, catalysts and additives to adjust the ventilation, flow and settling behavior.
• the isocyanate component is i. a. an aromatic polyurethane prepolymer.
• polyurethane leveling coatings are solvent-free, but occasionally formulated with plasticizers.
• the polyurethane coating can be applied to the previously defined elastic layer, which is closed with a filler material even after mixing with 5 to 80 wt .-% rubber granules with a grain size of 0.1 to 10 mm directly by z. B. rolls, syringes or doctor blades can be applied. Subsequent surface sealing is possible.
• Multi-layer applied leveling coatings with smooth, sealed or structured by a bedding granulate, u. U. also sealed surface. Each individual layer can, but need not, be sprinkled with a structural filler.
• Such systems are used for athletic tracks, multi-purpose sports facilities, but also for multi-purpose and athletic sports halls.
• Filler compounds allow a pore closure of prefabricated or locally installed rubber granulate coverings or other substrates for the subsequent application of a flow coating or for the construction of water-impermeable structural spray coatings.
• the leveling compounds on the market are formulated in two components.
• the A component consists i. a. from one or more higher functional polyalcohols (e.g. polyether and / or polyester alcohols), fillers, pigments, catalysts and thixotropic agents;
• the B component is a polyisocyanate or a polyurethane prepolymer based on an aromatic isocyanate.
• polyurethane fillers are formulated without solvents.
• Adhesives are used in the manufacture of sports flooring primarily for gluing elastic mats, e.g. B. prefabricated rubber granulate mats, on asphalt and cement-bound substrates.
• Adhesives can be formulated as one-component, moisture-curing or two-component.
• they also contain higher-functional polyalcohols (e.g. polyether and / or polyester alcohols) in the two-component case.
• the isocyanate is polyfunctional in nature and is often an aromatic polyurethane prepolymer.
• Plasticizers or solvents can also be formulation components.
• Seals are used in many systems in the manufacture of sports flooring in the last step to increase wear resistance, weather resistance,
• Seals are usually formulated in two components and contain in the A component, in addition to polyalcohols (e.g. polyether and / or polyester alcohols), matting agents, pigments, additives for adjusting the ventilation, flow and settling behavior, considerable amounts of organic solvents.
• the hardener component consists i. a. from modified aliphatic isocyanates.
• Solids content of> 30 wt .-% and a solvent content of ⁇ 10 wt .-% used in formulations for sports flooring It has surprisingly been shown that these polyurethane dispersions are not only more environmentally friendly and easier to process, but also partially improved product properties of the corresponding sports flooring, such as. B. mechanical properties (tensile strength, elongation), UV resistance and color stability. In addition, higher layer thicknesses can be applied during application compared to the isocyanate-containing moisture-curing systems, which was also not predictable.
• aqueous, isocyanate-free polyurethane dispersions proposed according to the invention have a solids content of
• the corresponding polyurethane dispersions are used in solvent-free form.
• isocyanate-free means that the isocyanate content of the solvent-free polyurethane dispersion is ⁇ 0.1%, preferably ⁇ 0.01%.
• the solvent-free polyurethane dispersion particularly preferably contains no isocyanate at all.
• the preferred average particle size of the polyurethane polymer is 100 to 500 nm, preferably 200 to 400 nm, the corresponding information relating to measurements using photon correlation spectroscopy (PCS).
• PCS photon correlation spectroscopy
• the corresponding polyurethane polymer generally has an average molecular weight of 25,000 to 100,000 daltons.
• the corresponding information relates to the number average M n and measurement using gel permeation chromatography (GPC).
• the prepolymer from stage b) with 0.25 to 2.5% by weight of a neutralization component (C) for complete or partial reaction of the carboxyl groups can react, subsequently or simultaneously d) the neutralized prepolymer from stage c) in 10 to 60% by weight of water, which may also consist of 10 to 70% by weight of a formulation component (F) contains from fillers, pigments, plasticizers, fiber materials and other conventional additives, dispersed, subsequently
• a chain extension component (D) consisting of at least one polyamine with one or more amino groups reactive towards polyisocyanates
• the dispersion from stage e) can react with 0.05 to 0.5% by weight of a chain stopper component (E) consisting of at least one monoamine with an amino group which is reactive towards polyisocyanates.
• a chain stopper component (E) consisting of at least one monoamine with an amino group which is reactive towards polyisocyanates.
• Component (A) (i) consists of at least one higher molecular weight polyol with two or more hydroxyl groups reactive towards polyisocyanates and an average molecular weight (number average M n ) of 250 to 20,000 daltons, in particular based on a polyether - And / or polyester polyols.
• These are preferably polymeric polyols such as polyalkylene glycols, aliphatic or aromatic polyesters, polycaprolactones, polycarbonates, macromonomers, telecheles or epoxy resins or mixtures thereof.
• Polyalkylene glycols are obtained from monomers such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran by polymerization in the presence of boron trifluoride or by polyaddition to starter compounds with reactive hydrogen atoms such as water, alcohols, amines or bisphenol A. Mixtures of the monomers can also be used simultaneously or in succession.
• Suitable polyalkylene glycols include, for example, polyethylene glycols, polypropylene glycols (for example Voranol types from Dow), mixed polyglycols based on ethylene oxide and propylene oxide and Polytetramethylene glycols or polytetrahydrofurans (eg PolyTHF 2000 from BASF) can be used.
• Linear or difunctional polypropylene glycols with an average molecular mass (number average M n ) of 3,000 to 4,000 daltons are to be regarded as preferred.
• Aliphatic or aromatic polyester polyols are obtained by polycondensation reaction and / or polyaddition reaction from di- or polyhydric alcohols and di- or polyhydric carboxylic acids, carboxylic acid anhydrides or carboxylic acid esters.
• Suitable aliphatic or aromatic polyesters are condensates based on 1,2-ethanediol or ethylene glycol, 1,4-butanediol or 1,4-butylene glycol, 1,6-hexanediol or 1,6-hexamethylene glycol and 2, 2-dimethyl-1,3-propanediol or neopentyl glycol and 1,6-hexanedioic acid or adipic acid and 1,3-benzenedicarboxylic acid or isophthalic acid (for example best types from Poliolchimica) are used.
• Linear or difunctional aliphatic or aromatic polyester polyols with an average molecular mass (number average M n ) of 1,000 to 3,000 daltons are preferred.
• Polycaprolactones eg Capa types from Solvay Interox
• polycarbonates eg Desmophen C 200 from Bayer
• the former are obtained by reacting phosgene or aliphatic or aromatic carbonates, such as, for example, diphenyl carbonate or diethyl carbonate, with dihydric or polyhydric alcohols.
• the latter are produced by polyaddition of lactones, such as, for example, ⁇ -caprolactone, onto starter compounds with reactive hydrogen atoms such as water, alcohols, amines or bisphenol A. Synthetic combinations of polyesters, polycaprolactones and polycarbonates are also conceivable. Macromonomers, telecheles or epoxy resins are also suitable. The macromonomers and telecheles are
• Polyhydroxyolefins such as, for example, ⁇ - ⁇ -dihydroxypolybutadienes, -ß-
• the epoxy resins are preferably derivatives of bisphenol A diglycidyl ether (BADGE).
• Component (A) (ii) consists of at least one low molecular weight polyol with two or more hydroxyl groups reactive towards polyisocyanates and a molecular mass of 60 to 250 daltons.
• suitable low-molecular polyols are 1, 2-ethanediol and ethylene glycol, 1,2-propanediol and 1,2-propylene glycol, 1,3-propanediol and 1,3-propylene glycol, 1,4-butanediol and 1 , 4-butylene glycol, 1,6-hexanediol or 1, 6-hexamethylene glycol, 2-methyl-l, 3-propanediol
• Component (B) consists of at least one aliphatic or aromatic polyisocyanate, polyisocyanate derivative or polyisocyanate homologue with two or more isocyanate groups. Particularly suitable are those in the
• Suitable aliphatic polyisocyanates include, for example, 1,6-diisocyanatohexane (HDI), l-isocyanato-5-isocyanatomethyl-3, 3,5-trimethylcyclohexane (IPDI), bis- (4-isocyanatocyclo-hexyl) methane (H 12 MDI), 1,3-bis- (1-isocyanato-1-methyl-ethyl) -benzene (m-TMXDI) or technical isomer mixtures of the individual aromatic polyisocyanates.
• HDI 1,6-diisocyanatohexane
• IPDI bis- (4-isocyanatocyclo-hexyl) methane
• H 12 MDI 1,3-bis- (1-isocyanato-1-methyl-ethyl) -benzene
• m-TMXDI 1,3-bis- (1-isocyanato-1-methyl-ethyl) -benzene
• Suitable aromatic polyisocyanates which can be used are, for example, 2,4-diisocyanatotoluene (TDI), bis (4-isocyanatophenyl) methane (MDI) and, if appropriate, its higher homologues (Polymeric MDI) or technical isomer mixtures of the individual aromatic polyisocyanates.
• TDI 2,4-diisocyanatotoluene
• MDI bis (4-isocyanatophenyl) methane
• Polymeric MDI Polymeric MDI
• lacquer polyisocyanates based on bis (4-isocyanatocyclo-hexyl) methane (H 12 MDI), 1, 6-diisocyanatohexane (HDI), 1-isocyanato-5-isocyanatomethyl-3, 3, 5 -trimethyl-cyclohexane (IPDI) is generally suitable.
• lacquer polyisocyanates denotes allophanate, biuret, carbodiimide, isocyanurate, uretdione, urethane groups derivatives of these diisocyanates in which the residual content of monomeric diisocyanates has been reduced to a minimum in accordance with the prior art.
• modified polyisocyanates can also be used, for example by hydrophilic modification of
• Lacquer polyisocyanates based on 1, 6-diisocyanatohexane (HDI) are accessible.
• the aliphatic polyisocyanates are preferred over the aromatic polyisocyanates.
• Polyisocyanates with isocyanate groups of different reactivity are also preferred.
• reaction step a) is relatively uncritical with regard to the reaction conditions.
• the formation of the polyurethane precursor takes place in such a way that component (B) is added or added to the mixture of components (A) (i) and optionally (A) (ii) within a period of a few minutes to a few hours is metered in or, alternatively, the mixture of component (A) (i) and optionally (A) (ii) is added or metered in to component (B) within a period of from a few minutes to a few hours.
• the preferred NCO / OH equivalent ratio of components (A) (polyols) and (B) (polyisocyanates) is set to a value of 1.5 to 2.5, but in particular 1.8 to 2.2.
• the reaction approach is taking advantage of the exothermic
• reaction stage a) The reaction of components (A) and (B) in reaction stage a) can take place in the presence of a catalyst system which is customary for polyaddition reactions on polyisocyanates. If required, these catalysts are added in amounts of 0.01 to 1% by weight, based on the reaction mixture.
• Common catalysts for polyaddition reactions on polyisocyanates are, for example, dibutyltin oxide, dibutyltin dilaurate (DBTL), triethylamine, tin (II) octoate, 1,4-diazabicyclo [2, 2, 2] octane (DABCO), 1, 4- Diaza-bicyclo [3, 2, 0] -5-nonen (DBN), 1, 5-diaza-bicyclo [5,4, 0] -7-undecene (DBU).
• the polyurethane pre-duke from stage a) is reacted with 0.5 to 5% by weight of component (A) (iii) to the corresponding prepolymer, the preferably finely ground polyol component (A) ( iii) with a particle size of ⁇ 150 ⁇ m is added or metered in to the polyurethane precursor from stage a) within a period of a few minutes to a few hours.
• Component (A) (iii) consists of at least one low molecular weight and anionically modifiable polyol with two or more hydroxyl groups reactive towards polyisocyanates and one or more carboxyl groups inert towards polyisocyanates, which in the presence of bases are wholly or partly in carboxylate groups can be transferred.
• low molecular weight and anionically modifiable polyols are 2-hydroxymethyl-3-hydroxypropanoic acid and dimethylolacetic acid, 2-hydroxymethyl-2-methyl-3-hydroxypropanoic acid and dimethylolpropionic acid, 2-hydroxymethyl-2-ethyl-3-hydroxypropanoic acid and
• Dimethylolbutyric acid, 2-hydroxymethyl-2-propyl-3-hydroxypropanoic acid or dimethylolvaleric acid, citric acid, tartaric acid are used.
• Bishydroxyalkanecarboxylic acids with a molecular mass of 100 to 200 daltons are preferably used, and preferably 2-hydroxymethyl-2-methyl-3-hydroxypropanoic acid or dimethylolpropionic acid
• polyisocyanates with isocyanate groups of different reactivity are preferably used to narrow Obtain molecular mass distributions with less inconsistency.
• polyurethane prepolymers with a linear structure are preferred, which are composed of difunctional polyol and polyisocyanate components.
• the prepolymers corresponding to reaction stage b) are preferably produced at temperatures from 60 to 120 ° C., in particular at 80 to 100 ° C.
• the viscosity of the polyurethane prepolymers is relatively low and largely independent of the structure of the polyol and polyisocyanate components used. It is therefore not necessary to add solvents to reduce the viscosity or to improve the dispersing properties of the polyurethane prepolymers.
• the special structure of the prepolymers enables the production of products with extremely high solids contents.
• due to the uniform distribution of the carboxyl or carboxylate groups over the polyurethane polymer only low charge densities are required for the stabilization of the corresponding polyurethane dispersions.
• the polyurethane prepolymer from stage b) is reacted in the subsequent reaction stage c) with 0.25 to 2.5% by weight of a neutralization component (C) for the complete or partial neutralization of the carboxyl groups
• the neutralization component (C) is preferably present in an amount such that the degree of neutralization, based on the free carboxyl groups of the polyurethane prepolymer, is 70 to 100 equivalent%, preferably 80 to 90 equivalent%.
• Neutralization is formed from the carboxyl groups carboxylate groups, which serve for the anionic modification or stabilization of the polyurethane dispersion.
• the reaction stage c) is carried out at a temperature of 40 to 60 ° C, preferably at about 50 ° C.
• the neutralization component (C) can also be introduced into the dispersing medium in accordance with stage d).
• the neutralization component (C) consists of one or more bases which are used for the complete or partial neutralization of the carboxyl groups.
• Suitable bases can be tertiary amines such as N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, N, N-dimethylisopropanolamine, N-methyldiisopropanolamine, triisopropylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, ammonia or alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide can be used.
• Tertiary amines and in particular triethylamine are preferably used.
• the neutralized polyurethane prepolymer from stage c) is in the subsequent reaction stage d) in 10 to 60% by weight of water, which may also contain 10 to 70% by weight of a formulation component (F) consisting of fillers, Pigments,
• Plasticizers, fiber materials, dispersion aids, rheology aids, defoamers, adhesion promoters, antifreezes, flame retardants, bactericides, fungicides, preservatives or other polymers or polymer dispersions are dissolved in the dispersing medium.
• dispersing and dispersing medium mean that, in addition to dispersed components with a micellar structure, solvated and / or suspended components can also be present.
• the polyurethane prepolymer can be stirred into the dispersing medium or the dispersing medium into the polyurethane prepolymer.
• the reaction stage d) is carried out at a temperature of 30 to 50 ° C, preferably at about 40 ° C. There are other alternatives to the procedure described.
• Steps c) and d) can be combined in such a way that the neutralization component (C) is added to the water in which the non-neutralized polyurethane prepolymer is dispersed in accordance with reaction step d) (indirect neutralization).
• the formulation component (F) can be wholly or partly stirred into the polyurethane prepolymer before the dispersion in reaction step d) if the production process is not impaired thereby.
• the polyurethane prepolymer dispersion from stage d) is in the subsequent reaction stage e) with 0.25 to 2.5% by weight of a chain extension component (D) and optionally in reaction stage f) with 0.05 to 0 , 5 wt .-% of a chain stopper component (E) implemented.
• the chain extension component (D) consists of at least one polyamine with two or more amino groups reactive towards polyisocyanates.
• Suitable polyamines are, for example, adipic acid dihydrazide, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, hexamethylenediamine, hydrazine, isophoronediamine, N- (2-aminoethyl) -2-aminoethanol, adducts from salts of 2-acrylamido-2-acrylamido-2-acrylamido sulfonic acid (AMPS) and ethylenediamine or any combination of these polyamines.
• Difunctional primary amines and in particular 1, 2-diaminoethane or ethylenediamine are preferably used.
• the chain stopper component (E) consists of at least one monoamine with an amino group reactive towards polyisocyanates.
• Suitable monoamines are, for example, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, ethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, morpholine, piperidine, pyrrolidine or any combination of these polyamines .
• Monofunctional primary amines and in particular 2-aminopropane or isopropylamine are preferably used.
• the chain extension component (D) is used in such an amount that the degree of chain extension, based on the free isocyanate groups of the polyurethane prepolymer, is 50 to 100 equivalent%, preferably 70 to 80 equivalent% , lies.
• the chain stopper component (E) is optionally used in such an amount that the degree of chain stop, based on the free isocyanate groups of the polyurethane prepolymer, is 1 to 20 equivalent%, preferably 5 to 10 equivalent% .
• the components can be used either in succession or simultaneously or as a mixture of the
• Polyurethane prepolymer dispersion from stage d) are added.
• the chain extension of the polyurethane prepolymer dispersion leads to the build-up of the molecular mass within the micelles and to the formation of a polyurethane-polyurea dispersion of high molecular mass.
• Component (D) reacts with reactive isocyanate groups much faster than water.
• the chain stop of the polyurethane prepolymer dispersion leads to the breakdown of the molecular mass build-up within the micelles and to the formation of a polyurethane-polyurea dispersion with a lower molecular mass.
• the chain stopper component (E) reacts with reactive isocyanate groups much faster than water. Following reaction stages e) and f), any free isocyanate groups still present can be completely chain-extended with water.
• Products can be made from the polyurethane dispersions by dispersing fillers or pigments or mixing them with liquid components.
• you can an "in situ formulation" can be carried out directly in the preparation of the polyurethane dispersion, ie first fillers and pigments and then the polyurethane polymer are dispersed into distilled water. In this way, the fillers can be incorporated into the polyurethane particles and particularly high-quality products with low settling behavior are obtained.
• the polyurethane dispersions formulated in situ extraordinarily high solids contents are achieved with comparatively low viscosities, which would not be possible with a conventional formulation of the pure polyurethane dispersions.
• aqueous polyurethane dispersions proposed according to the invention are particularly suitable as
• elastic layers consisting of rubber granules or fibers, which are made in particular from SBR, EPDM, EVA or recycled granules with a grain size of 0.5 to 50 mm or from fibers with a length of 0.1 to 50 mm. Possibly.
• These elastic layers can also contain mineral aggregates with a grain size of 1 to 20 mm.
• fillers for the pore closure of substrates for example, prefabricated or locally installed rubber granulate coverings
• substrates for example, prefabricated or locally installed rubber granulate coverings
• sports floor coverings for the subsequent application of a flow coating or for the construction of water-impermeable structural spray coatings.
• UV stabilizers of the sterically hindered amine type in concentrations of 0.1 to 1.0% by weight, based on the total mass of the formulation, the
• HALS-I hindered amine light stabilizer
• UV absorbers such as substituted hydroxyphenylbenzotriazoles, hydroxybenzophenones, hydroxyphenyl-s-triazines, and antioxidants, such as substituted 2,6-di-tert-butylphenols.
• the polyurethane dispersions formulated according to the invention can be applied in layers with a total thickness of 0.1 to 50 mm to the elastic or rigid substrates. This usually requires 0.1 to 10.0 kg of the formulated polyurethane dispersion per m2 of the surface to be coated and per work step.
• the formulated polyurethane dispersions proposed according to the invention can be used in one- or two-component form, the one-component form is to be regarded as preferred because of the better manageability.
• polyurethane dispersions are aqueous emulsion polymers based on ethylenically unsaturated monomers, such as e.g. (Meth) acrylates, styrene, vinyl acetate.
• aqueous polyurethane dispersions proposed according to the invention also enable the following advantageous product properties with regard to the corresponding sports floor coverings:
• Solvent-free polyurethane dispersion with high solids content based on Polvpropylenglvkol 1000
• the prepolymer was neutralized directly with 90 equivalent% of triethylamine. 160.00 g of the prepolymer were then dispersed with vigorous stirring in 110.77 g of demineralized water and then chain-extended with 80 equivalent% of ethylenediamine to build up the polyurethane dispersion.
• Hydroxyl number of 56.1 mg KOH-g "1 (trade name Voranol P2000 from Dow) and 35.49 g of isophorone diisocyanate (trade name Vestanat IPDI from Hüls) were stirred at 80-90 ° C. for 2 hours under a nitrogen blanket .
• the percentages relate to% by weight
• Typical values of a conventional IC binder e.g.
• this formulation can also be ready to use, i.e. H. can already be formulated in a mixture with the spray granulate that is otherwise added on site, which considerably simplifies handling at the construction site. All that is required here is a brief homogenization of the mixture before application.
• Example B.5 Gradient coating
• liquid components (1) to (4) are introduced and homogenized for 5 minutes. (5), (6) and (7) are added with stirring. The mixture is dispersed for 20 min, the temperature must not exceed 40 ° C.
• Typical values for a conventional 2-component gradient coating e.g. Conipur 210): 3,600 mPas (mixture); 2 N / mm 2 , 150%
• liquid components (1) to (3) are introduced and homogenized for 5 minutes. Then (5) and 10 minutes later (6) and (7) are dispersed in at high shear rate until the system has reached its final viscosity. The temperature of the formulation must not exceed 40 ° C.
• Typical values of a conventional 2K filler material e.g. Conipur 203: thixotropic; 3.5 N / mm 2 , 80%
• the liquid components (1) to (3) are introduced and homogenized for 5 min at a low shear rate. Then (4) is added and dispersed for 10 min at high shear rate. After adding (5), the mixture is dispersed until the final viscosity is reached. The temperature of the formulation must not exceed 40 ° C.
• Formulation components (1) to (5) are initially introduced and dispersed for 20 minutes at high shear rate.
• the post-crosslinking component is mixed in with moderate stirring immediately before application (mixing ratio 100: 2).
• the processing time of the system is approx. 40 min at 20 ° C.
• Example C.2 Use as a binder for rubber granulate chippings
• Example B.2 5.9 kg / m 2 SBR granules, 1 to 4 mm 1.9 kg / m 2 binder based on PU dispersion
• Example B1 6.0 kg / m 2 EPDM granules, 1 to 3 mm 1.9 kg / m 2 binder based on PU dispersion
• a mixture of spray coating and EPDM granules of small grain size is sprayed onto an installed and walkable rubber granulate ceiling in two work steps.
• Example B.2 6.9 kg / m 2 SBR granules, 1 to 4 mm
• Example B.3 0.8 kg / m 2 EPDM granules, 0.5 to 1.5 mm
• Example B.4 0.8 kg / m 2 EPDM granules, 0.5 to 1.5 mm
• the pores of a rubber granulate cover are closed with a spatula before the spray coating is applied.
• Example B.3 0.8 kg / m 2 EPDM granules, 0.5 to 1.5 mm
• Example B.2 6.9 kg / m 2 SBR granules, 1 to 4 mm 2.3 kg / m binder based on PU dispersion
• Example B.6 1.2 kg / m spray coating based on PU dispersion acc.
• Example B.3 1.2 kg / m spray coating based on PU dispersion acc.
• Conipur 322 1.5 kg / m 2 filler material (conventional), e.g. B. Conipur
• a spatula material is applied to an installed and walkable rubber granulate ceiling. After hardening, a leveling coating is applied, which, while still liquid, is sprinkled in excess with EPDM granules. The amount of EPDM granules that is not bound is reversed after the coating has hardened and can be used again.
• a sports floor covering manufactured in the same way as in example C.9 is sealed in two spray passes after the excess EPDM granules have been swept away. 2
• Example B.7 prefabricated rubber granulate mat, 10 mm 0.5 kg / m filler material based on PU dispersion according to Example B.6
• a prefabricated rubber granulate mat is glued to it, a pore seal is made with a spatula material and the flow coating applied, which is sprinkled with EPDM granules, is applied in the manner described above.
• the gradient coating is applied in three work steps and sealed in two spray passes after complete hardening.
• the gradient coating is applied in three work steps, each layer being sprinkled and brushed off after curing.
• a fourth layer of gradient coating is sprinkled with EPDM granules, the excess is absorbed after curing and the surface is sealed in two spray passes.
• Example B.6 pore closure 0.6 kg / m of filler material on PU dispersion material according to Example B.6 (scraping; then
• Example B.6 (scraping; then structuring by means of a structural roller)

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• 1998
  • 1998-07-28 DE DE19833819A patent/DE19833819B4/de not_active Revoked
• 1999
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