EP1644429A1 - Resines de polyurethanne modifiees au fluor a un ou deux constituants, leur procede de production et leur utilisation - Google Patents

Resines de polyurethanne modifiees au fluor a un ou deux constituants, leur procede de production et leur utilisation

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Publication number
EP1644429A1
EP1644429A1 EP04740711A EP04740711A EP1644429A1 EP 1644429 A1 EP1644429 A1 EP 1644429A1 EP 04740711 A EP04740711 A EP 04740711A EP 04740711 A EP04740711 A EP 04740711A EP 1644429 A1 EP1644429 A1 EP 1644429A1
Authority
EP
European Patent Office
Prior art keywords
fluorine
component
modified polyurethane
modified
polyurethane resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04740711A
Other languages
German (de)
English (en)
Inventor
Alois Maier
Norbert Steidl
Stefan Ingrisch
Frank Weinelt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Construction Research and Technology GmbH
Original Assignee
Construction Research and Technology GmbH
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Filing date
Publication date
Application filed by Construction Research and Technology GmbH filed Critical Construction Research and Technology GmbH
Publication of EP1644429A1 publication Critical patent/EP1644429A1/fr
Withdrawn legal-status Critical Current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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • 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
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3812—Polyhydroxy compounds having fluorine atoms
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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

Definitions

  • Fluorine-modified one- or two-component polyurethane resins process for their preparation and their use
  • the present invention relates to fluorine-modified one- or two-component polyurethane resins with excellent permanent dirt and water-repellent surface properties and very good material and
  • High-performance coating materials based on polyurethane consisting of a polyisocyanate and an isocyanate-reactive component, e.g. a higher molecular weight polyol, are generally known. They do show very good ones
  • EP 0 405 534 A1 describes hydroxyl-functional (per) fluoropolyether-containing polyurethanes for the treatment of stone surfaces, but these do not form real films.
  • Hydrophilic polyurethane films coated with fluorine-modified polymers based on perfluoroalkyl acrylates or methacrylates with high vapor permeability rates for oleo- and hydrophobization are known from WO 97/36951 AI.
  • US 4,504,401 B1 discloses low molecular weight perfluoroalkyl group-containing urethanes for the dirt-proofing of fiber products such as. B. carpets.
  • Allophanate and isocyanurate group-containing polyisocyanates are described which, in compositions for 1K or 2K coating systems, have surface energies between 19.4 and 43.7 dynes / cm.
  • Fluorine-modified urethane systems consisting of a fluorine-containing polyol with one or more hydroxyl groups and polyisocyanates with allophanate and isocyanurate structures in a molecular weight ratio of 4: 1 to 1:10 are known from EP 0 566 037 A2. When used as a hardener component, these systems lead to clear films.
  • abrasion-resistant urethane coating compositions with reduced friction based on fluorinated alcohols, non-fluorinated polyols and blocked polyisocyanates and at least one amine crosslinker disclosed. Due to the blocked polyisocyanates, however, the coating composition must first be heated to above 120 ° C. before it can be crosslinked with polyamine components.
  • compositions for coatings based on (per) fluoropolyethers are described in EP 1 116 759 AI. In addition to solvents, they contain bi-functional (per) fluoropolyether diols in conjunction with IPDI trimers. The (per) fluoropolyethers are not incorporated laterally in this application.
  • Fluorinated branched oligourethanes prepared from monomers or macromonomers such as polyisocyanate in blocked form, a hydrophilic alcohol or thiol component, mono- and bifunctional hydroxyl (per) fluoropolyether alcohols and monofunctional (per) fluoroalkyl alcohols and chemically crosslinkable alcohol or thiol components are disclosed the application EP 1 059319 A2. Here too, the (per) fluoropolyether compounds are not pendant.
  • the present invention was therefore based on the object of developing fluorine-modified one- or two-component polyurethane resins with improved surface properties for permanent oil and water-repellent surface treatment or modification of mineral and non-mineral substrates for various fields of application which do not have the disadvantages of the prior art mentioned , but have good application properties and can also be manufactured taking ecological, economic and physiological aspects into account.
  • a 2 optionally the fluorine-modified polyurethane prepolymer or polyol mixture from stage ai) with an optionally fluorine-modified functionalization component (C) (i) with one or more amino and / or hydroxyl groups reactive towards isocyanate groups and / or one or more isocyanate groups reactive towards hydroxyl groups and a molecular mass of 50 to 2500 daltons, selected from the groups of the (cyclo) aliphatic and / or aromatic polyols and / or polyamines and / or polyamino alcohols and / or reactive polyhedral oligomers Polysilasesquioxane (POSS) of the general formula (RSiO ⁇ .
  • PPS polysilasesquioxane
  • the one- or two-component polyurethane resins have covalently bonded fluorinated side chains that can be introduced using suitable macromonomers.
  • the fluorine-modified one- or two-component polyurethane resins can also be produced without solvents or with a low solvent content.
  • the fluorine-modified one- or two-component polyurethane resins according to the invention with improved surface properties are defined by their multi-stage production process.
  • a fluorine-modified polyurethane prepolymer with free isocyanate groups and / or free amino and or hydroxyl groups or a fluorine-modified polyol mixture is prepared by using a fluorine-modified macromonomer (AI) together with a higher molecular weight polyol in step a_) -Component (A2) and a low molecular weight polyol component (A3) (i) either with a polyisocyanate component (B) (i) optionally in the presence of a solvent component (L) (i) and a catalyst for the reaction or the fluorine-modified Macromonomer (AI), the higher molecular weight polyol component (A2) and the lower molecular weight polyol component (A3) (i) optionally in the presence of a solvent component (L) (i) and a catalyst.
  • a fluorine-modified macromonomer AI
  • the fluorine-modified polyurethane prepolymer or polyol mixture from stage ai) can be reacted with an optionally fluorine-modified functionalization component (C) (i).
  • step a 3 ) below the fluorine-modified polyurethane prepolymer or polyol mixture from steps ai) or a 2 ) is mixed with a formulation component (F) (i).
  • the subsequent production of the fluorine-modified polyurethane resin in stage b) takes place in that the fluorine-modified polyurethane prepolymer from stage a 3 ) in the case of a one-component application with air humidity or the fluorine-modified polyurethane prepolymer or polyol mixture from stage a 3 ) (binder) in the case of a two-component application with a crosslinking component (D) (hardener), a formulation component (F) (ü) optionally in the presence of a solvent component (L) (üi) and a catalyst.
  • a polyisocyanate component (B) (üi) is used as the crosslinking component (D), while in the case of the polyurethane prepolymer a polyisocyanate component (B) (üi) or a low molecular weight polyol component (A3) (ii) and / or a low molecular weight polyamine component (E) is used.
  • a fluorine-modified macromonomer (AI) is used, which was prepared by
  • Ci a fluoroalcohol component (A4) consisting of a perfluoroalkyl alcohol with terminal methylene groups (hydrocarbon spacers) of the general formula
  • CF 3 CF 2 CF 2 O-CF (CF3) CF 2 O) z -CF (CF3) CH2-OH, with z 1-10 or mixtures thereof with a hydroxyl group reactive towards isocyanate groups and a molecular mass from 250 to 5000 Daltons with a polyisocyanate component (B) (ü), consisting of at least one diisocyanate, polyisocyanate, polyisocyanate derivative or polyisocyanate Brings homologs with two or more (cyclo) aliphatic or aromatic isocyanate groups of the same or different reactivity, if appropriate in the presence of a solvent component (L) (ü) and if appropriate in the presence of a catalyst,
  • a functionalization component (C) (ü) with two or more amino and / or hydroxyl groups reactive towards isocyanate groups and a molecular mass of 50 to 500 daltons from the group of (cyclo) aliphatic and or aromatic polyols and / or polyamines and / or polyamino alcohols.
  • the fluorine-modified macromonomer (AI) Preferably, the fluorine-modified macromonomer (AI)
  • Reaction products or macromonomers with monomodal molecular weight distribution from monofunctional perfluoroalkyl alcohols, isophorone diisocyanate or toluene diisocyanate and diethanolamine are used.
  • the higher molecular weight polyol component (A2) consists of a polymeric polyol with two or more hydroxyl groups reactive towards isocyanate groups and an average molecular weight (number average) of 500 to 6,000 daltons.
  • Suitable polymeric polyols which can be used are, for example, (hydrophobically modified) polyalkylene glycols, aliphatic or aromatic polyesters, polycaprolactones, polycarbonates, hydroxy-functional macromonomers and telechelics such as, ⁇ -
  • Polymethacrylate diols, ⁇ , ⁇ -dihydroxyalkylpolydimethylsiloxanes, hydroxy-functional epoxy resins, hydroxy-functional ketone resins, hydroxy-functional polysulfides, hydroxy-functional triglycerides, oxidatively drying alkyd resins based on bisepoxides and unsaturated fatty acids or suitable mixtures thereof can be used.
  • Linear or difunctional (hydrophobically modified) polyether and / or polyester and / or polycaprolactone and / or polycarbonate are preferred.
  • Polyols and / or ⁇ , ⁇ -polymethacrylate diols with a molecular mass of 500 to 3,000 daltons are used.
  • the low molecular weight polyol components (A3) (i) and (A3) (ii) consist of a polyol with two or more hydroxyl groups reactive towards polyisocyanates and an average molecular mass of 50 to 499 daltons.
  • Suitable low molecular weight polyols are, for example, 1,2-ethanediol or ethylene glycol, 1,2-propanediol or 1,2-propylene glycol, 1,3-propanediol or 1,3-propylene glycol, 1,4-butanediol or 1,4-butylene glycol 1,6-hexanediol or 1,6-hexamethylene glycol 2-methyl-l, 3-propanediob 2,2-dimethyl-l, 3-propanediol or neopentylglycob 1,4-bis (hydroxymethyl) cyclohexane or cyclohexanedimethanob 1 , 2,3-propanetriol or
  • the fluoroalcohol component (A4) consists of a perfluoroalkyl alcohol with terminal methylene groups (hydrocarbon spacers) of the general formula
  • Suitable perfluoroalkyl alcohols can also be 2,2-bis (trifluoromethyl) propanob 1H, 1H-2,5-di (trifluoromethyl) -3,6-dioxaundecafluorononanob 1H, 1H, 7H-dodecafluoroheptanob 2,2,3,3,4,4,5 , 5,6,6,7,7-dodecafluoro-l, 8-octanediob 1H, 1H-heptafluorobutanob lH, lH, 9H-hexadecafluorononanob 1H, 1H, 3H-hexafluorobutanob 2H-hexafluoro-2-propanob 2,2,3, 3,4,4,5,5-octafluoro-l, 6-hexanediob 1H, 1H, 5H-octafluoropentanob 1H, 1H-pentaflu
  • the polyisocyanate components (B) (i), (B) (ü) and / or (B) (üi) consist of at least one polyisocyanate, polyisocyanate derivative or polyisocyanate homologues with two or more aliphatic or aromatic isocyanate groups of the same or different reactivity.
  • the polyisocyanates or combinations thereof which are well known in polyurethane chemistry are particularly suitable.
  • Suitable aliphatic polyisocyanates include, for example, 1,6-diisocyanatohexane (HDI), l-isocyanato-5-isocyanatomethyl-3,3,5-trimethylcyclohexane or isophorone diisocyanate (IPDI), bis- (4-isocyanatocyclohexyl) - methane (H 1 2MDI), 1,3-bis- (l-isocyanato-l-methyl-ethyl) -benzene (m-TMXDI) or technical isomer mixtures of the individual aromatic polyisocyanates are used.
  • HDI 1,6-diisocyanatohexane
  • IPDI isophorone diisocyanate
  • H 1 2MDI bis- (4-isocyanatocyclohexyl) - methane
  • m-TMXDI 1,3-bis- (l-isocyanato-l-methyl-ethyl)
  • Suitable aromatic polyisocyanates include, for example, 2,4-diisocyanatotoluene or toluene diisocyanate (TDI), bis (4-isocyanatophenyl) methane (MDI) and, if appropriate, its higher homologs (Polymeric MDI) or technical isomer mixtures of the individual aromatic polyisocyanates be used.
  • TDI 2,4-diisocyanatotoluene or toluene diisocyanate
  • MDI bis (4-isocyanatophenyl) methane
  • Polymeric MDI polymeric MDI
  • technical isomer mixtures of the individual aromatic polyisocyanates be used.
  • the so-called "paint polyisocyanates” based on bis (4-isocyanatocyclo-hexyl) methane (H12MDI), 1,6-diisocyanatohexane (HDI), 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethyl -cyclohexane (IPDI) is basically suitable.
  • lacquer polyisocyanates denotes derivatives of these diisocyanates containing allophanate, biuret, carbodiimide, isocyanurate, uretdione, urethane groups, 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, which are accessible, for example, by hydrophilic modification of "paint polyisocyanates” based on 1,6-diisocyanate hexane (HDI).
  • Difunctional polyisocyanate derivatives or reaction products of at least trifunctional aliphatic or aromatic polyisocyanates and (optionally fluorine-modified) an )iofunctional polyhedral oligomeric polysilasesquixanes (POSS) of the general formula are also suitable
  • Silasesquioxanes are oligomeric or polymeric substances whose fully condensed representatives have the general formula (Si ⁇ 3 2 R) n, where n> 4 and the radical R can be a hydrogen atom, but usually represents an organic radical.
  • the smallest structure of a silasesquioxane is the tetrahedron. Voronkov and Lavrent'yev (Top. Curr. Chem.
  • Silasesquioxanes of the formula can be base-catalyzed to functionalized, incompletely condensed silasesquioxanes, such as R 7 Si 7 O 9 (OH) 3 or and R ⁇ Si ⁇ Oio OH) 4, (Chem. Commun. (1999), 2309-10; Polym. Mater. Sei. Eng. 82 (2000), 301-2; WO 01/10871) and thus as a parent compound for a large number various incompletely condensed and functionalized silasesquioxanes are used.
  • functionalized, incompletely condensed silasesquioxanes such as R 7 Si 7 O 9 (OH) 3 or and R ⁇ Si ⁇ Oio OH) 4, (Chem. Commun. (1999), 2309-10; Polym. Mater. Sei. Eng. 82 (2000), 301-2; WO 01/10871) and thus as a parent compound for a large number various incompletely condensed and functionalized silasesquioxanes are used.
  • silasesquioxanes (trisilanols) of the formula R 7 Si 7 O 9 (OH) 3 can be converted into appropriately modified oligomeric silasesquioxanes by reaction with functionalized, monomeric silanes (corner capping).
  • component (B) (i) 2,4-toluenediisocyanate or technical isomer mixtures of 2,4-toluenediocyanate and 2,6-toluenediocyanate or technical cis / trans isomer mixtures of isophorone diisocyanate (IPDI) are preferred.
  • IPDI isophorone diisocyanate
  • Polyisocyanates with isocyanate groups of different reactivity are particularly preferred.
  • Component (B) contains 2,4-toluene diisocyanate or technical isomer mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or bis- (4-isocyanatophenyl) methane (MDI) and possibly its higher homologues ( Polymeric MDI) or technical isomer mixtures or technical cis / tr - ns isomer mixtures of isophorone diisocyanate (IPDI) are preferred.
  • Component (B) (iii) contains 2,4-toluene diisocyanate or technical isomer mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or bis- (4-isocyanatophenyl) methane (MDI) and possibly its higher homologues ( Polymeric MDI) or technical isomer mixtures or technical cis / trans isomer mixtures of isophorone diisocyanate (IPDI) or "lacquer polyisocyanates" based on 1,6-diisocyanatohexane (HDI) are to be regarded as preferred.
  • MDI bis- (4-isocyanatophenyl) methane
  • Polymeric MDI or technical isomer mixtures or technical cis / trans isomer mixtures of isophorone diisocyanate (IPDI) or "lacquer polyisocyanates" based on 1,6-diisocyanatohe
  • PES polyhedral oligomeric polys
  • Suitable compounds which can be used are, for example, monoalcohols, monoamines, ethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, N- (2-aminoethyl) -2-arninoethanob trimethylolpropane, polyisocyanate components analogous to (B) (i), (B) (ü) and (B ) (iii) and reactive polyhedral oligomeric polysilasesquixanes (POSS) of the general formula (RSiO ⁇ .
  • R aminopropyl and / or isocyanatopropyl and optionally CHzCHzCFaCF ⁇ CFzCFzCFaCFs and / or H and / or alkyl and / or cycloalkyl and / or aryl and / or (CH) 3 (OCH 2 CH2) nOMe and / or and / or epoxypropyl and / or dimethoxysilyloxy and / or methacryloyloxypropyl and / or triethoxysilylpropyl.
  • the functionalization component (C) (i) can furthermore consist of compounds and having two or more amino and / or hydroxyl groups reactive towards isocyanate groups and having a molecular mass of 50 to 500 daltons, selected from the groups of (cyclo) aliphatic and / or aromatic polyols and or polyamines and / or polyamino alcohols.
  • Suitable compounds which can be used are, for example, ethanolamine, diethanolamine, ethylenediamine, diethylenetriarnine, N- (2-A-ammoethyl) -2-aminoethanol and trimethylolpropane.
  • Diethanolamine is preferably used.
  • the low molecular weight polyamine component (E) consists of a polyamine with two or more (cyclo) aliphatic or aromatic amino groups reactive towards polyisocyanates and a molecular mass of 50 to 500 daltons.
  • suitable (cyclo) aliphatic polyamines for example, adipic dihydrazide, ethylenediamine, Diethylentriarnin, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, hexamethylenediamine, hydrazine, isophoronediamine, N- (2-A-rninoethyl) -2-aminoethanob Jeffamine ® (polyoxyalkylenamines) from can.
  • Suitable aromatic polyamines include, for example, bis (4-amino-3-methylphenyl) methane, cumendiamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), diethyltoluenediamine, methylenedianiline (MDA), m-phenylenediamine (m- PDA) or any mixture thereof.
  • MOCA 3,3'-dichloro-4,4'-diaminodiphenylmethane
  • MDA methylenedianiline
  • m- PDA m-phenylenediamine
  • latent hardeners based on aldimines and / or ketimines and / or enamines can also be used, which release the polyamines again with or without the release of volatile cleavage products when water (for example atmospheric humidity) enters.
  • the solvent components (L) (i), (L) (ü) and (L) (üi) consist of low- or high-boiling organic solvents.
  • suitable solvents are N-methylpyrrolidone and glycol ethers
  • Dipropylene glycol dimethyl ether (Proglyde DMM ® ), cyclic alkylene carbonates, xylob ethylbenzob C3-alkylbenzene (cumene), ethyl acetate, butyl acetate, butylglycobl. Methoxypropyl acetate, methyl isobutyl ketone can be used.
  • Fluorine-modified one- or two-component polyurethane resins preferably contain less than 10% by weight of organic solvents in the overall system.
  • the formulation components (F) (i) and (F) (ü) are, for example, defoamers, deaerators, lubricants and leveling additives, dispersing additives, substrate wetting additives, hydrophobizing agents, rheology additives, coalescing agents, matting agents, bonding agents, antifreeze agents, antioxidants, UV and UV agents.
  • the formulation constituents can be introduced both during and after the preparation after the preparation of the fluorine-modified one- or two-component polyurethane resins.
  • the solids content of fluorine-modified polyurethane prepolymer or polyol mixture consisting of components (AI), (A2), (A3) (i), (B) (i) and (C) (i) in step a), is reduced to 25 to 100 wt .-%, preferably 50 to 75 wt .-% based on the total amount of the binder, consisting of the components (AI), (A2), (A3) (i), (B) (i), optionally (C) (i), (F) (i), optionally (L ) (i) and possibly (L) (iü).
  • the solids content of crosslinker component consisting of components (B) (iii) or (B) (iii) or (A3) (ü) and / or (E), in stage c) is from 25 to 100% by weight. -%, preferably 50 to 75 wt .-% based on the total amount of hardener (D), consisting of components (B) (iü) or (A4) (ü) and / or (E), (F) (ü ) and optionally (L) (iii).
  • the polyurethane polymer consisting of components (A), (B), (C) and (E), has a preferred number average molecular weight of 10,000 to 100,000 daltons.
  • the present invention further relates to a process for the preparation of fluorine-modified one- or two-component polyurethane resins by producing a fluorine-modified polyurethane prepolymer or a fluorine-modified polyol mixture (binder) in stage a) and the subsequent production of the fluorine-modified polyurethane resin in stage b).
  • a fluorine-modified polyurethane prepolymer or polyol mixture (binder) is prepared in the reaction stage in that components (AI), (A2) and (A3) (i) either with component (B) (i) if appropriate in the presence of a solvent component (L) (i) and if appropriate in the presence of a catalyst, the hydroxyl groups of the components (AI ), (A2), (A3) (i) are partially or completely reacted with the isocyanate groups of component (B) (i) or, if appropriate, in the presence of a solvent component (L) (i) and if appropriate in the presence a catalyst is mixed, optionally reacting the fluorine-modified polyurethane prepolymer or the polyol mixture from stage ai) in reaction stage a 2 ) with an optionally fluorine-modified functionalization component (C) (i) and the fluorine-modified polyurethane prepo ly
  • the fluorine-modified macromonomer (AI) is preferably prepared by reacting a fluoroalcohol component (A4) with the polyisocyanate component (B) (ii) in the reaction stage Ci), if appropriate in the presence of a solvent component (L) (ü) and optionally reacting in the presence of a catalyst, the reaction conditions and the selectivities of components (A4) and (B) (ü) being chosen so that only one isocyanate group of component (B) (ü) with component (A4 ) reacts, and if necessary subsequently in reaction step c 2 ) brings the uniform pre-add from step Ci) completely with the functionalization component (C) (ü), the reaction conditions and the selectivity of component (C) (ii) thus can be chosen so that only a reactive group of component (C) (ü) reacts with the free isocyanate group (s) of the preaduct.
  • the fluoroalcohol component (A4) is added to the polyisocyanate component (B) (ü) at a temperature between - 20 and 50 ° C, optionally with the addition of a suitable solvent (L) and optionally with the addition of a catalyst. added dropwise within a period of 30 to 60 minutes and reacted in such a way that only one isocyanate group is reacted.
  • the resulting product is dripped into the functionalization component (C) (ü) with cooling within a few minutes.
  • Suitable solvents (L) (ü) are e.g. B. N-methylpyrrolidone (NMP) or tetrahydrofuran.
  • a fluorine-modified polyurethane resin is finally produced by using the fluorine-modified polyurethane prepolymer from stage b 3 ) in the case of one-component application with atmospheric moisture or the fluorine-modified polyurethane prepolymer or polyol mixture from stage b 3 ) (binder ) ) in the case of a two-component application with a crosslinker component (D) (hardener), consisting of a polyisocyanate component (B) (üi) or a low molecular weight polyol component (A4) (ü) and / or one low molecular weight polyamine component (E), a formulation component (F) (ü) and optionally a solvent component (L) (iii), if appropriate in the presence of a catalyst, the formulation components individually or together, be added during or after the mixing of the individual components.
  • a crosslinker component D
  • hardener consisting of a polyisocyanate component (B) (üi) or
  • the NCO / OH equivalent ratio of components (AI), (A2), (A3) (i) and (B) (i) in step a) is preferably from 0.5 to 10.0, preferably 1.5 to 6.0.
  • the NCO / OH equivalent ratio of binder and hardener in stage b) is set to a preferred value of 1.0 to 2.0, preferably 1.0 to 1.5.
  • the NCO / OH equivalent ratio of components (A4) and (B) (ü) in stage Ci) is in particular from 1.9 to 2.1 and the NCO / OH + NH equivalent ratio of the components in the precursor from stage Ci) and (C) (ü) in step c 2 ) set to 0.95 to 1.05.
  • Reaction stages a), b) and c) are usually carried out in the presence of 0.01 to 1% by weight, based on components (A) and (B), of a catalyst which is customary for polyaddition reactions on polyisocyanates. Examples of common catalysts for polyaddition reactions on polyisocyanates.
  • DABCO 1,4-diaza-bicyclo [2,2,2] octane
  • DBU 1,4-diaza-bicyclo [3,2 ( 0] -5-nonen
  • DBU 1,5-diaza-bicyclo [5,4,0] -7-undecene
  • reaction stages ai) and a 2 ) are preferably carried out at a temperature of 40 to 120 ° C., in particular at 50 to 110 ° C.
  • the reaction stages Ci) and c 2 ) are preferably carried out at a temperature of from ⁇ 20 to 50 ° C., in particular at 0 to 30 ° C.
  • reaction stages a 3 ) and b) are preferably carried out at a temperature of 10 to 60 ° C., in particular at 20 to 50 ° C.
  • Another object of the present invention relates to the use of fluorine-modified one- or two-component polyurethane resins with improved surface properties in the construction or industrial sector for permanent oil- and water-repellent surface treatment or modification of mineral and non-mineral substrates, such as
  • Inorganic surfaces e.g. porous, absorbent, rough and polished building materials and building materials of all kinds (such as concrete, gypsum, silica and silicates, artificial stone, natural stone (such as granite, marble, sandstone, slate, serpentine), clay, cement, Brick) as well as enamel, fillers and pigments, glass, ceramics, metals and metal alloys,
  • Organic surfaces such as. B. wood and wood-based materials, wood veneer, glass fiber reinforced plastics (GRP), plastics, leather, natural fibers, polar organic polymers of all kinds, composite materials.
  • GRP glass fiber reinforced plastics
  • Construction such as B.
  • Non-construction and industry such as B. Automotive Coil Coatings stoving lacquers glass facades and glass surfaces ceramics and sanitary ware leather finishing surface-modified fillers and pigments paper coating rotors of wind turbines ship colors.
  • fluorine-modified one- or two-component polyurethane resins proposed according to the invention with improved surface properties in the construction sector are suitable for the mass hydrophobization / oleophobization of concrete, such as e.g.
  • the fluorine-modified one- or two-component polyurethane resins according to the invention can be used
  • the fluorine-modified one- or two-component polyurethane resins according to the invention are superior to aqueous binder systems with fluorine modification.
  • the fluorine-modified one- or two-component polyurethane resins according to the invention with improved surface properties can in principle be used both in formulated and in unformulated form for the respective fields of application.
  • the formulation is carried out in accordance with the methods and techniques known from paint and coating technology.
  • aqueous or non-aqueous binders denotes water-based polyurethanes, polymer dispersions, redispersible polymer powders or non-aqueous solvent-containing or solvent-free and possibly reactive polymers.
  • the fluoro-modified one- or two-component polyurethane resins according to the invention with improved surface properties are applied using the known methods, such as e.g. Flooding, pouring, knife coating, rolling, spraying, painting, dipping, rolling.
  • the drying and curing of the coatings produced from the fluorine-modified one- or two-component polyurethane resins according to the invention with improved surface properties is generally carried out at normal (outside and inside) temperatures in the range from 5 to 50 ° C., i.e. without special heating of the coatings, but depending on the application can also be carried out at higher temperatures in the range of 50 to 150 ° C.
  • T-Bone Fluorine-modified diol component 0.1 mol of 2,4-toluene diisocyanate (TDI) (Desmodur T 80, Bayer AG) was dissolved in a four-necked flask equipped with a dropping funnel, KPG stirrer, reflux condenser, internal thermometer and nitrogen blanket in 28.8 g of N-methylpyrrolidone (NMP), placed under a nitrogen blanket and cooled to about 15-20 ° C. On Crystallization of 2,4-tolylene diisocyanate (TDI) should be avoided.
  • NMP N-methylpyrrolidone
  • Fluorine-modified 2-component polyurethane floor coating self-leveling. low solvent content
  • Sovermol ® 805 (Cognis Deutschland GmbH) and 13.5 parts by weight of fluorine-modified diol component (see Example 1, contains 4.0 parts by weight of N-methylpyrrolidone (NMP)) slowly, with constant stirring, 4.4 parts by weight of zeolite Paste (Finma Chemie), 1.0 part by weight of Perenol E 8 (Cognis Deutschland GmbH), 0.5 part by weight of Perenol F 40 (Cognis Germany), 8.0 part by weight Parts of Micro Tale AT 1 (Norwegian-Talc), 17 parts by weight of Baryte C 14 (Sachtleben), 5.0 parts by weight of pigment powder (Heucosin types from Heubach) and 20.0 parts by weight. Parts of Millisil W12 (Fa. Quarzwerke) added. This mixture was then dispersed under vacuum at 1500 rpm for about 20 minutes.
  • NMP N-methylpyrrolidone
  • Desmodur VL R 10 polymeric MDI, Bayer AG, isocyanate
  • Fluorine content (based on the formulation): 3.6% by weight
  • Desmodur VL polymeric MDI, Bayer AG, isocyanate content 31.5% by weight
  • Fluorine content (based on the formulation): 3.4% by weight
  • Fluorine content (based on binder): 2.2% by weight

Abstract

L'invention concerne une résine de polyuréthanne modifiée au fluor à un ou deux constituants présentant des propriétés de surface améliorées. On obtient la résine de polyuréthanne selon l'invention a) par production d'un prépolymère de polyuréthanne modifié au fluor à groupes isocyanate libres ou à groupes amino et/ou hydroxyle libres ou par production d'un mélange de polyols modifié au fluor à groupes hydroxyle libres (liant), ainsi que b) par production d'une résine de polyuréthanne modifiée au fluor ayant une teneur en fluor lié au polymère comprise entre 1 et 4 % en poids dans le système total, en faisant réagir, dans le cas d'une application à un constituant, le prépolymère de polyuréthanne modifié au fluor de l'étape a3) avec l'humidité de l'air ou en faisant réagir, dans le cas d'une application à deux constituants, le prépolymère de polyuréthanne ou le mélange de polyols modifié au fluor (liant) avec un constituant réticulant (D) (durcisseur) et un constituant de formulation (F), (ii) éventuellement en présence d'un constituant solvant (L) (iii) ainsi que d'un catalyseur. Grâce à l'utilisation de macromonomères fluorés appropriés dans les résines de polyuréthanne à un ou deux constituants selon l'invention, il est possible de produire des systèmes de revêtement ou des surfaces durs, à tensions superficielles très faibles et à angles de contact très importants. Ces résines de polyuréthanne présentent en outre une tendance à la salissure significativement réduite par rapport à l'état de la technique.
EP04740711A 2003-07-11 2004-07-06 Resines de polyurethanne modifiees au fluor a un ou deux constituants, leur procede de production et leur utilisation Withdrawn EP1644429A1 (fr)

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DE10331483A DE10331483A1 (de) 2003-07-11 2003-07-11 Fluormodifizierte ein- oder zweikomponentige Polyurethanharze, Verfahren zu ihrer Herstellung und deren Verwendung
PCT/EP2004/007391 WO2005007722A1 (fr) 2003-07-11 2004-07-06 Resines de polyurethanne modifiees au fluor a un ou deux constituants, leur procede de production et leur utilisation

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