WO2007115752A1 - Zweikomponentiges (wässriges) hybridreaktivharzsystem, verfahren zu seiner herstellung sowie dessen verwendung - Google Patents

Zweikomponentiges (wässriges) hybridreaktivharzsystem, verfahren zu seiner herstellung sowie dessen verwendung Download PDF

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Publication number
WO2007115752A1
WO2007115752A1 PCT/EP2007/003009 EP2007003009W WO2007115752A1 WO 2007115752 A1 WO2007115752 A1 WO 2007115752A1 EP 2007003009 W EP2007003009 W EP 2007003009W WO 2007115752 A1 WO2007115752 A1 WO 2007115752A1
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WIPO (PCT)
Prior art keywords
component
weight
functional
epoxy
reactive
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Ceased
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PCT/EP2007/003009
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German (de)
English (en)
French (fr)
Inventor
Norbert Steidl
Alois Maier
Michael Schroers
Roswitha Haindl
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Construction Research and Technology GmbH
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Construction Research and Technology GmbH
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Priority to MX2008012776A priority Critical patent/MX2008012776A/es
Priority to BRPI0710585-1A priority patent/BRPI0710585A2/pt
Priority to US12/279,081 priority patent/US20100285311A1/en
Priority to EP07723950A priority patent/EP2001920A1/de
Priority to AU2007236222A priority patent/AU2007236222A1/en
Priority to CA 2648153 priority patent/CA2648153A1/en
Priority to JP2009503482A priority patent/JP2009532541A/ja
Publication of WO2007115752A1 publication Critical patent/WO2007115752A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/2845—Monohydroxy epoxy compounds
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31525—Next to glass or quartz
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal

Definitions

  • the present invention relates to a two-component (aqueous) hybrid reactive resin system having improved processing properties and properties profile, processes for its preparation and its use in the construction or industrial sector.
  • epoxy-modified polyurethanes are mainly used in the field of adhesives and sealants, pottings and coatings.
  • Epoxy-modified polyurethanes are characterized not only by an improved property profile compared to conventional polyurethanes, they also lead to improved properties in mixtures with epoxy resins. Both the synthesis of epoxy-modified polyurethanes and their properties in blends with epoxy resins in terms of adhesion, impact resistance and fracture behavior is described in Journal of Applied Polymer Science (1994), 52 (8), 1137-51. Pre-reaction of the synthesized polyurethanes with various hardeners results in systems which are characterized by a lower degree of phase separation and improved mechanical properties.
  • an epoxy-functional (aqueous) binder component (I) having an epoxide equivalent of 100 to 12500 g / eq, an average molecular weight of 200 to 25,000 daltons and a
  • a functionalized low molecular weight polyol component (A) (i), consisting of a hydroxy-functional epoxy alcohol and / or glycidyl ether with a or more isocyanate-reactive hydroxyl group (s) and one or more isocyanate groups substantially inert epoxide group (s), an epoxy equivalent of 100 to 500 g / eq and a molecular mass of 50 to 1000 daltons,
  • a polyisocyanate component (B) consisting of at least one diisocyanate, polyisocyanate, polyisocyanate derivative or polyisocyanate homologs having two or more (cyclo) aliphatic and / or aromatic isocyanate groups and a molecular mass of 100 to 2500 daltons , If necessary, in the presence of 0.01 to 0.5 parts by weight of a customary for polyaddition reactions on polyisocyanates catalyst component (K) (i) reacting, wherein the mixture of the components (A) (i) and (B) either simultaneously or stepwise with the component (A) (U) is reacted and optionally the reaction mixture
  • a low molecular weight polyol component (A) (Ui) having one or more isocyanate-reactive hydroxyl group (s) and a molecular mass of 50 to 500 daltons,
  • a functionalized low molecular weight polyol component (A) (iv) with one or more opposite Isocyanate groups reactive hydroxyl group (s) and one or more isocyanate-inert carboxyl and / or phosphonate and / or sulfonate group (s) and / or polyalkylene oxide group (s) and / or perfluoroalkyl group (n) and a molecular mass of 50 to 2500 daltons as well
  • a high molecular weight (polymeric) polyol component (A) (v) having one or more isocyanate-reactive hydroxyl groups and a molecular mass of 500 to 5000 daltons,
  • a Reactiwertechnischner component (C) 1 consisting of at least one (aqueous) epoxy resin with one or more isocyanate groups substantially inert epoxy group (s), an epoxy equivalent of 130 to 400 g / eq and a Molecular mass of 50 to 1000 daltons as well
  • a formulation component (F) (i) consisting of reactive and / or inert fillers, pigments, support materials, nanomaterials, nanocomposites, other additives, plasticizers, solvents and water
  • a 2 optionally emulsifying or dispersing the prepolymer from step ai) in 0 to 900 parts by weight of water and optionally adding the formulation component (F) (i), and by b) the preparation of a (latent) amino-functional hardener component (II), wherein
  • a (polymeric) polyamine component (E) consisting of one or more (polymeric) polyamines having one or more epoxy groups reactive (cyclo) aliphatic and / or aromatic primary and / or secondary amino group ( n) and optionally one or more hydroxyl group (s) and a molecular mass of 60 to 5000 daltons in the form of pure (polymeric) polyamines, polyaspartic esters, latent hardeners or reactive diluents based on aldimines and / or ketimines and / or enamines and or oxazolidines, cleavage product-free latent hardeners based on acetothines and / or diazepines and / or ammonium salts, commercially available liquid amine hardener formulations or suitable combinations thereof,
  • a formulation component (F) (U) consisting of reactive and / or inert fillers, pigments, support materials, nanomaterials, other additives, plasticizers, solvents and water, and
  • the use of calcium oxide and / or calcium hydroxide in the formulation component can be dispensed with in comparison with the prior art.
  • the hardener component can also be immobilized within the formulation component.
  • suitable functionalized low molecular weight polyol component (A) are glycidol, glycerol diglycidyl ether, (cyclo) aliphatic and / or aromatic polyols such as butane-1, 4-diol, p-tert-butylphenol, 1,4 -Cyclohexanedimethanol, ethylene glycol, n-dodecanol, 2-ethylhexanol, glycerol and polyglycerol, hexane-1, 6-diol, hydrogenated bisphenol-A, hydrogenated bisphenol-F, 2-methylpropane-1,3-diol, o-cresol, neopentyl glycol , Pentaerythritol, polyethylene glycols, polypropylene glycols, polyalkylene glycols, propane-1, 2 (3) -diol, n-tetradecanol, trimethylolpropane or
  • Suitable functionalized higher molecular weight (polymeric) polyol component (A) (U) for example, epoxidised and (partial) ring-opened (un) saturated triglycerides, dimer fatty acid diols, oleochemical polyols, the commercial products Sovermol ® 45, 100, 320, 650, NS 750, 760, 805, 810, 815, 818, 819, 820, 850, 860, 908, 912 Pearls, 920, 1005, 1012, 1014, 1052, 1055, 1058, 1059, 1066, 1068, 1080, 1083, 1090, 1095 , 1102, 1106, 1111, 9155 and Speziol ® C 10-2 C 18-2 C 36-2.
  • Suitable low molecular weight polyol component (A) (Ui) for example, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 2,2-dimethyl-1, 3-propanediol, 1, 2-Dihydroxyalkandiole with 5- 50 carbon atoms of the general formula (I)
  • Suitable higher molecular weight (polymeric) polyol component (A) (v) may be, for example, (hydrophobically modified) polyalkylene glycols, (un) saturated aliphatic and / or aromatic polyesters, polycaprolactones, polycarbonates, ⁇ , ⁇ -polybutadiene polyols, ⁇ , ⁇ -polymethacrylate diols, ⁇ , ⁇ -
  • polyisocyanate component (B) for example, polyisocyanates, polyisocyanate derivatives or polyisocyanate homologs having two or more aliphatic and / or aromatic isocyanate groups of the same or different reactivity or suitable combinations thereof can be used. Particularly suitable are the polyisocyanates or combinations thereof which are well known in polyurethane chemistry.
  • aliphatic polyisocyanates for example, 1, 6-diisocyanatohexane (HDI), 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethyl-cyclohexane or isophorone diisocyanate (IPDI, commercial product VESTANAT ® IPDI from Degussa AG), bis- (4-isocyanatocyclohexyl) - methane (MDI Hi 2, commercial product VESTANAT H12MDI ® from Degussa AG.), 1, 3-bis (1-isocyanato-1-methyl-ethyl) benzene (m-TMXDI ).
  • HDI 1, 6-diisocyanatohexane
  • IPDI 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethyl-cyclohexane or isophorone diisocyanate
  • MDI Hi commercial product VESTANAT H12MDI ® from Degussa AG
  • TMDI Diisocyanatohexane 6-2,2,4-trimethyl-1, or 2,4,4-trimethyl-1, 6-diisocyanatohexane
  • TMDI commercial product VESTANAT TMDI ®. From Degussa AG
  • suitable aromatic polyisocyanates include 2,4-diisocyanatotoluene or toluene diisocyanate (TDI), bis (4-isocyanatophenyl) -methane (MDI) and optionally its higher homologs (polymer MDI) or technical isomer mixtures of the individual aromatic polyisocyanates or suitable combinations thereof are used.
  • lacquer polyisocyanates denotes allophanate, biuret, carbodiimide, isocyanurate, oxadiazinetrione, uretdione, Urethane-containing derivatives of these diisocyanates, in which the residual content of monomeric diisocyanates was reduced according to the prior art to a minimum.
  • modified polyisocyanates which are obtainable, for example, by hydrophilic modification of "lacquer polyisocyanates” with monohydroxy-functional polyethylene glycols or aminosulfonic acids.
  • VESTANAT ® T 1890 E VESTANAT ® T 1890 L 1 VESTANAT ® T 1890 M, VESTANAT ® T 1890 SV, VESTANAT ® T 1890/100 (polyisocyanates based on IPDI trimer), VESTANAT ® HB 2640 MX, VESTANAT HB ® 2640/100, VESTANAT ® HB 2640 / LV (polyisocyanates based on HDI biuret), VESTANAT ® HT 2500 L, VESTANAT HB ® 2500/100, VESTANAT ® HB 2500 / LV (polyisocyanates based on HDI Isocyanurate) from Degussa AG or suitable combinations thereof.
  • VESTANAT ® T 1890 E VESTANAT ® T 1890 L 1 VESTANAT ® T 1890 M, VESTANAT ® T 1890 SV, VESTANAT ® T 1890/100
  • a suitable reactive diluent component (C) for example, fully etherified (cyclo) aliphatic and / or aromatic polyols such as butane-1, 4-diol, p-tert-butylphenol, 1, 4-cyclohexanedimethanol, ethylene glycol, n-dodecanol, with epichlorohydrin, 2-ethylhexanol, glycerol and polyglycerol, hexane-1, 6-diol, hydrogenated bisphenol-A, hydrogenated bisphenol-F, 2-methylpropane-1, 3-diol, o-cresol, neopentyl glycol, pentaerythritol, polyethylene glycols, polypropylene glycols, polyalkylene glycols, Propane 1, 2 (3) - diol, n-tetradecanol, trimethylolpropane or mono- and polyfunctional glycidyl ethers, bisphenol
  • epichlorohydrin which has been fully etherified (cyclo) aliphatic and / or aromatic polyols or hydroxy-functional mono- and polyfunctional glycidyl ethers.
  • suitable extenders for example, alcohols such. B. benzyl alcohol or a suitable combination thereof.
  • suitable coalescing aid component (D) are low-boiling, aprotic solvents, such as acetone or propanone, butanone, 4-methyl-2-pentanone, ethyl acetate, n-butyl acetate or high-boiling, aprotic solvents, such as N-methyl-2-pyrrolidone, N Ethyl-2-pyrrolidone, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dialkyl adipates, cyclic alkylene carbonates, or suitable combinations thereof.
  • aprotic solvents such as acetone or propanone, butanone, 4-methyl-2-pentanone, ethyl acetate, n-butyl acetate or high-boiling
  • aprotic solvents such as N-methyl-2-pyrrolidone
  • high-boiling solvents such as N-ethylpyrrolidone and / or N-methylpyrrolidone and / or dipropylene glycol dimethyl ether and / or dialkyl adipate and / or cyclic alkylene carbonates.
  • Suitable (polymeric) polyamine component (E) for example, polyamines having two or more aliphatic and / or aromatic, primary and / or secondary amino groups of the same or different reactivity or suitable combinations thereof.
  • Suitable aliphatic polyamines may be, for example, 1,3-pentanediamine (DAMP), 2-methylpentamethylenediamine (MPMDA), benzylaminopropylamine (BAPA), bisaminomethylcyclohexane or 1,3-bis (aminomethyl) cyclohexane (1,3-BAC), cyclohexylaminopropylamine ( NAPCHA), diaminocyclohexane or 1,2-diaminocyclohexane (DAC or DCH), diethylaminopropylamine (DE ⁇ APA), diethylenetriamine or 1, 4,7-triazaheptane (DETA), dimethyl-PACM or bis- (4.4 l ).
  • DAMP 1,3-pentanediamine
  • D-PACM dipropylenetriamine or 1, 5,9-triazanonan, ethylenediamine or 1,2-diaminoethane (EDA), hexamethylenediamine or 1,8-diaazaoctane (HMDA) , Isophoronediamine or 3-methylamino-3,5,5-trimethylaminocyclohexane (IPD or IPDA), methylpentamethylenediamine or 2-methyl-1, 7-diaazaheptane, N3-amine or 1, 4,8-triazaoctane, N4-amine or 1,5,8,12-tetraazadodecane, n-aminomethylpiperazine or 1- (2-aminoethyl) -1,4-diazacyclohexane (NAEP), N-aminopropylcyclohexylamine (NAPCHA), p-aminocyclohex
  • aromatic polyamines examples include diaminodiphenylmethane or bis (4,4'-aminophenyl) methane (DDM), diaminodiphenylsulfone or bis (4,4'-aminophenyl) sulfone (DDS), diethylaminodiphenylmethane (DEDDM), diethyltoluenediamine (DETDA ), m-xylylenediamine or 1, 3-bis (aminomethyl) benzene (mXDA) or suitable combinations thereof.
  • DDM diaminodiphenylmethane or bis (4,4'-aminophenyl) methane
  • DEDDM diethylaminodiphenylmethane
  • DETDA diethyltoluenediamine
  • mXDA 1, 3-bis (aminomethyl) benzene
  • aromatic polyoxyalkylene amines examples include polyoxyethylene polyamines, polyoxypropylene polyamines, Polytetrahydrofuranpolyamine, other polyoxyalkylenepolyamines based on any alkylene oxide or mixtures thereof (co, block, random), Butandioletherdiamin or 1, 14-diaza-5,10-dioxotetradecan (BDA) or suitable combinations thereof can be used.
  • BDA Butandioletherdiamin or 1, 14-diaza-5,10-dioxotetradecan
  • polyaminoamides, Mannich bases, epoxy adducts such as EDA adduct DETA adduct, Type 100, Type 115, Type 125, Type 140, Type 250 can (Genamid), PAA adduct, the commercial products Polypox IH ® 7001, 7002 IH, IH 7003 , IH 7004, H 013, H 014, H 015, H 016, H 030, H 038, H 043, H 043 S 1 H 043 L, H 051, H 060, H 100, H 129, H 147, H 160 , H 205, H 206, H 229, H 244, H 262, H 269, H 276/90, H 300, H 300 S, H 300 SL, H 310, H 333, H 354, H 354 L 1 H 415 , H 445, H 445 L, H 480, H 483, H 488, H 488 L, H 489, H 490, H 497, H 501, H 503, H
  • the component (E) can be present in coated and / or microencapsulated and / or carrier-fixed and / or hydrophilicized and / or solvent-containing form and, if appropriate, released in a sustained release.
  • suitable formulation components (F) (i) and (F) (U) it is possible, for example, to use reactive inorganic fillers selected from the group consisting of cement, calcium oxide, calcium hydroxide or calcium sulfate or suitable combinations thereof.
  • suitable formulation components (F) (i) and (F) (U) include (functionalized) inorganic and / or organic, water-inert fillers and / or light fillers, (Functionalized) inorganic and / or organic pigments, (functionalized) inorganic and / or organic support materials, (functionalized) inorganic and / or organic nanomaterials, (functionalized) inorganic and / or organic nanocomposites, inorganic and / or organic fibers, graphite, carbon black , Carbon fibers, carbon nanotubes, metal fibers and powders, conductive organic polymers, redispersible polymer powders or superabsorbents and suitable combinations thereof.
  • suitable formulation components (F) (i) or (F) (U) it is also possible to use, for example, other additives selected from the group of defoamers, deaerators, lubricants and flow additives, substrate wetting additives, wetting and dispersing additives, water repellents, rheology additives, coalescing aids, Matting agents, adhesion promoters antifreeze, antioxidants, UV stabilizers, biocides or suitable combinations thereof may be used.
  • other additives selected from the group of defoamers, deaerators, lubricants and flow additives, substrate wetting additives, wetting and dispersing additives, water repellents, rheology additives, coalescing aids, Matting agents, adhesion promoters antifreeze, antioxidants, UV stabilizers, biocides or suitable combinations thereof may be used.
  • plasticizers selected from the group of dialkyl phthalates, dialkyl adipates, biodiesel, rapeseed oil methyl ester, fatty acid derivatives, triglyceride derivatives or suitable combinations thereof.
  • Suitable catalyst component (K) (i) may, for example, dibutyltin oxide, dibutyltin dilaurate (DBTL), triethylamine, tin (II) octoate, 1, 4-diaza-bicyclo [2,2,2] octane (DABCO) 1 1, 4-diaza-bicyclo [3,2,0] -5-nonene (DBN), 1, 5-diazabicyclo [5,4,0] -7-undecene (DBU), morpholine derivatives such as e.g. B. JEFFCAT ® Amine Catalysts or suitable combinations thereof may be used.
  • DBU 4-diaza-bicyclo [2,2,2] octane
  • DBU 4-diaza-bicyclo [3,2,0] -5-nonene
  • DBU 5-diazabicyclo [5,4,0] -7-undecene
  • morpholine derivatives such as e
  • Suitable accelerator component (K) (U) may be, for example, benzyldimethylamine, 4-N, N-dimethylaminophenol, 2,4,6-tris- (N, N-) dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, other suitable tertiary amines or suitable combinations thereof.
  • Another object of the present invention relates to a process for the preparation of the novel two-component (aqueous) hybrid reactive resin system, characterized in that
  • Stage ai) is carried out while avoiding epoxide / isocyanate side reactions (eg cycloaddition to form cyclic urethanes).
  • the dosage of the components (A), (B), (C), (D), (F) (i), (K) (i) used in stages a) and b) can be carried out in any desired manner.
  • the NCO / OH equivalent ratio of components (A) and (B) in step a) is preferably adjusted to 1.2 to 2.5, in particular to 1.3 to 2.0.
  • the stage ai) is carried out at a preferred temperature of 40 to 90 0 C, in particular at 65 to 85 0 C.
  • the stage a 2 is carried out at a preferred temperature of 30 to 60 0 C, in particular at 40 to 50 0 C.
  • the step b) is carried out at a preferred temperature of 10 to 40 ° C, in particular at 20 to 30 0 C.
  • an epoxy-functional binder component (I) which is self-emulsifying without additional anionic and / or nonionic hydrophilicization.
  • the solids content of the epoxy-functional aqueous binder component (I) consisting of components (A), (B) and (C) in stage a) is preferably from 10 to 100% by weight, in particular from 25 to 75% by weight, set.
  • the solids content of the two-component coating system consisting of the components (I) and (II) is preferably adjusted to 10 to 100 wt .-%, in particular to 25 to 75 wt .-%.
  • a further subject matter of the present invention relates to the use of the two-component (aqueous) hybrid reactive resin system according to the invention for the production of chemical-resistant, heat-resistant, abrasion-resistant, mechanically highly stressable and easy-to-clean coating systems for mineral and non-mineral surfaces based on concrete, cement, lime, gypsum, Anhydrite, geopolymers, glass, wood and wood-based materials, composite materials, artificial and natural stone, plastic and glass fiber reinforced plastic (GRP), metal, polymers.
  • aqueous hybrid reactive resin system for the production of chemical-resistant, heat-resistant, abrasion-resistant, mechanically highly stressable and easy-to-clean coating systems for mineral and non-mineral surfaces based on concrete, cement, lime, gypsum, Anhydrite, geopolymers, glass, wood and wood-based materials, composite materials, artificial and natural stone, plastic and glass fiber reinforced plastic (GRP), metal, polymers.
  • GRP plastic and glass fiber reinforced plastic
  • novel two-component (aqueous) hybrid reactive resin system is suitable in the construction and industrial sectors for the production of chemical-resistant, heat-resistant, abrasion-resistant, mechanically highly stressable and easy-to-clean coating systems for the applications
  • the novel two-component (aqueous) hybrid reactive resin system is suitable in the construction and industrial sectors for the production of chemical-resistant, heat-resistant, abrasion-resistant, mechanically highly stressable and easy-to-clean coating systems for the fields of application
  • Clean room areas e.g., chip and wafer fabrication
  • the two-component (aqueous) hybrid reactive resin system according to the invention is suitable in the construction and industrial sector for system construction of chemical-resistant, heat-resistant, abrasion-resistant, mechanically highly stressable and easy-to-clean coating systems, consisting of optionally a primer and at least one base layer, which is not lightfast and possibly sanded or are as well as from possibly a cover layer that is light-fast and, if necessary, fluorine-modified and possibly sanded.
  • the two-component (aqueous) hybrid reactive resin system according to the invention may be in any combination with conventional three-component PCC coating systems (Ucrete ®) and / or aqueous and / or reactive polyurethane coating systems and / or aqueous and / or reactive Epoxidharzbe Anlagenllssystemen in the applications
  • the two-component (aqueous) hybrid reactive resin system according to the invention can be used in applications
  • Concrete products precast concrete products, concrete products, concrete blocks
  • the epoxy-functional (aqueous) binder component (I) and the (latently) amino-functional hardener component (II) are used in the preferred epoxide / amino equivalent ratio of 0.8 to 1.2, in particular 0.9 to 1.1 mixed into a two-component coating system.
  • the coating system is preferably applied in layers with a total thickness of 0.1 to 50 mm on elastic or rigid substrates applied, wherein it is used in particular in an amount of 0.1 to 10.0 kg per m 2 of the surface to be coated and per operation.
  • the coating system can be applied horizontally, vertically and without primer (and without blistering) to (wet) fresh concrete.
  • the hybrid reactive resin system according to the invention can be used in particular for crack-bridging and cavity-filling coatings.
  • the application of the coating system is carried out by the methods known from lacquer and coating technology, such as e.g. Flooding, pouring, knife-coating, rolling, spraying, brushing, dipping, rolling.
  • lacquer and coating technology such as e.g. Flooding, pouring, knife-coating, rolling, spraying, brushing, dipping, rolling.
  • the product obtained was a homogeneous, slightly yellow-colored resin having an epoxide value of 3.03 mol / kg.
  • the product obtained was a homogeneous, slightly yellow-colored resin having an epoxide value of 276.73 g / eq.
  • the product obtained was a homogeneous, slightly yellow resin with an epoxy value of 390.69 g / eq.
  • the product obtained was a homogeneous, slightly yellow-colored resin having an epoxide value of 426.37 g / eq and a viscosity of 50,000 mPa.s.
  • the total proportion of active ingredient is 26.95% by weight.
  • Pos. 1-5 were placed in a mixing cup and homogenized. Posings 6-9 were then weighed into another beaker and added to the mixture of 1-5. The resulting total mixture was dispersed in the speed mixer until a temperature of 50 0 C. was reached (temperature control). For deaeration, the color thus obtained was allowed to stand overnight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
PCT/EP2007/003009 2006-04-04 2007-04-03 Zweikomponentiges (wässriges) hybridreaktivharzsystem, verfahren zu seiner herstellung sowie dessen verwendung Ceased WO2007115752A1 (de)

Priority Applications (7)

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MX2008012776A MX2008012776A (es) 2006-04-04 2007-04-03 Sistema de resina reactivo hibrido (acuoso) de dos componentes, metodo para la produccion y uso del mismo.
BRPI0710585-1A BRPI0710585A2 (pt) 2006-04-04 2007-04-03 sistema de resina reativa hìbrida de componente duplo (aquoso), processo para sua produção e uso do mesmo
US12/279,081 US20100285311A1 (en) 2006-04-04 2007-04-03 Dual component (aqueous) hybrid reactive resin system, method for production and use thereof
EP07723950A EP2001920A1 (de) 2006-04-04 2007-04-03 Zweikomponentiges (wässriges) hybridreaktivharzsystem, verfahren zu seiner herstellung sowie dessen verwendung
AU2007236222A AU2007236222A1 (en) 2006-04-04 2007-04-03 Dual component (aqueous) hybrid reactive resin system, method for production and use thereof
CA 2648153 CA2648153A1 (en) 2006-04-04 2007-04-03 Dual component (aqueous) hybrid reactive resin system, method for production and use thereof
JP2009503482A JP2009532541A (ja) 2006-04-04 2007-04-03 ２成分（水性）ハイブリッド反応性樹脂系、その製造方法および使用

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DE200610015774 DE102006015774A1 (de) 2006-04-04 2006-04-04 Zweikomponentiges (wässriges) Hybridreaktivharzsystem, Verfahren zu seiner Herstellung sowie dessen Verwendung
DE102006015774.5 2006-04-04

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WO2007115752A1 true WO2007115752A1 (de) 2007-10-18

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AR (1) AR060293A1 (https=)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2716680A1 (de) 2012-10-04 2014-04-09 Basf Se Fluorierte polymerisierbare Verbindung
CN105086897A (zh) * 2014-10-31 2015-11-25 上海优金复合新材料有限公司 双组分水基型亮彩瓷砖美缝剂
US9574089B2 (en) 2012-10-04 2017-02-21 Basf Coatings Gmbh Fluorine-containing nonaqueous coating material composition, coating methods, and the use of the coating material composition

Families Citing this family (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9676895B2 (en) * 2006-08-04 2017-06-13 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
DE102010039318A1 (de) * 2010-08-13 2012-02-16 Sgl Carbon Se Stabilisierung nanopartikulärer Füllstoffe in Harzformulierungen
BR112014003329A2 (pt) * 2011-08-19 2017-03-14 Ppg Europe Bv composição de revestimento, uso da composição e substrato
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US9611175B2 (en) 2012-11-15 2017-04-04 Kalkfabrik Nestal AG Surface-modified calcium oxide
JP6465891B2 (ja) * 2013-09-06 2019-02-06 ダウ グローバル テクノロジーズ エルエルシー コーティング組成物
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WO2016153818A1 (en) * 2015-03-20 2016-09-29 Lubrizol Advanced Materials, Inc. Blends of water dispersible polymer with dispersions of polymers from epoxidized triglycerides
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3814578A (en) * 1972-01-14 1974-06-04 Us Agriculture Treatment of textiles with glycidol-modified polyurethanes
DE3205733A1 (de) * 1982-02-18 1983-08-25 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von verklebungen sowie von verbundfolien
DE3520763A1 (de) * 1984-06-08 1985-12-19 The Yokohama Rubber Co., Ltd., Tokio/Tokyo Harzzusammensetzung fuer korrosionsschutz

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424766A (en) * 1966-08-03 1969-01-28 Celanese Coatings Co Epoxidized urethane oils
US4542165A (en) * 1983-09-08 1985-09-17 Sanyo Chemical Industries, Ltd. Polyurethane based on epoxy-containing polymer polyol and process for making the same
DE4218449A1 (de) * 1992-03-25 1993-09-30 Hoechst Ag Wasserverdünnbare Zweikomponenten-Überzugsmasse, ein Verfahren zu deren Herstellung und deren Verwendung
US5354808A (en) * 1992-12-08 1994-10-11 Minnesota Mining And Manufacturing Company Polyurethanes including pendant hindered amines and compositions incorporating same
US6258875B1 (en) * 2000-03-17 2001-07-10 E. I. Du Pont De Nemours And Company Aqueous dispersions of epoxy resins
US7163984B2 (en) * 2000-12-19 2007-01-16 Basf Corporation Waterborne coating compositions containing monomeric difunctional compounds
DE10208567A1 (de) * 2002-02-27 2003-09-11 Degussa Construction Chem Gmbh Wässriges fluormodifiziertes Polyurethansystem für Anti-Graffiti- und Anti-Soiling-Beschichtungen
CA2529737C (en) * 2003-07-07 2013-05-07 Dow Global Technologies Inc. Adhesive epoxy composition and process for applying it

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3814578A (en) * 1972-01-14 1974-06-04 Us Agriculture Treatment of textiles with glycidol-modified polyurethanes
DE3205733A1 (de) * 1982-02-18 1983-08-25 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von verklebungen sowie von verbundfolien
DE3520763A1 (de) * 1984-06-08 1985-12-19 The Yokohama Rubber Co., Ltd., Tokio/Tokyo Harzzusammensetzung fuer korrosionsschutz

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2716680A1 (de) 2012-10-04 2014-04-09 Basf Se Fluorierte polymerisierbare Verbindung
WO2014053636A1 (en) 2012-10-04 2014-04-10 Basf Se Fluorinated polymerizable compound
US9574089B2 (en) 2012-10-04 2017-02-21 Basf Coatings Gmbh Fluorine-containing nonaqueous coating material composition, coating methods, and the use of the coating material composition
CN105086897A (zh) * 2014-10-31 2015-11-25 上海优金复合新材料有限公司 双组分水基型亮彩瓷砖美缝剂

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DE102006015774A1 (de) 2007-10-11
BRPI0710585A2 (pt) 2011-08-16
US20100285311A1 (en) 2010-11-11
AU2007236222A1 (en) 2007-10-18
CN101410428A (zh) 2009-04-15
EP2001920A1 (de) 2008-12-17
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CA2648153A1 (en) 2007-10-18
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