WO2012013681A1 - Polyisocyanates présentant des groupes uréthane hautement fonctionnels - Google Patents

Polyisocyanates présentant des groupes uréthane hautement fonctionnels Download PDF

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Publication number
WO2012013681A1
WO2012013681A1 PCT/EP2011/062836 EP2011062836W WO2012013681A1 WO 2012013681 A1 WO2012013681 A1 WO 2012013681A1 EP 2011062836 W EP2011062836 W EP 2011062836W WO 2012013681 A1 WO2012013681 A1 WO 2012013681A1
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Prior art keywords
urethane
groups
polyisocyanates
group
containing polyisocyanates
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PCT/EP2011/062836
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German (de)
English (en)
Inventor
Oihana Elizalde
Frederic Lucas
Angelika Maria Steinbrecher
Lydie Tuchbreiter
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Basf Se
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Priority to EP11735668.3A priority Critical patent/EP2598549A1/fr
Priority to JP2013522201A priority patent/JP5871924B2/ja
Priority to CN2011800477000A priority patent/CN103140530A/zh
Publication of WO2012013681A1 publication Critical patent/WO2012013681A1/fr

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    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three 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
    • C08G18/40—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • 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
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

  • the present invention relates to novel urethane group-containing polyisocyanates based on aliphatic and / or cycloaliphatic diisocyanates and their use.
  • EP1091991 B1 describes two-component polyurethane mixtures with a highly functional, preferably at least four-functional, polyisocyanate as the A component and a polyol as the B component.
  • the B component may also contain low molecular weight di- to penta-alcohols.
  • Polyisocyanate and polyol are used only in an NCO: OH ratio of 0.6 to 1.4: 1, since the mixtures are coating compositions for coatings in which substantially all reactive groups are to be reacted after curing.
  • EP 1497351 B1 describes the preparation of highly functional polyisocyanates by trimerization of a mixture comprising aliphatic diisocyanates and uretdiones. Alcohols are not present.
  • EP 1061091 A describes at least difunctional polyisocyanates with allophanate groups by reaction of polyisocyanates with a monoalcohol and optionally higher-functional diols or polyols.
  • the disadvantage of this is that no more than two polyisocyanates can be linked together by means of an allophanate bond and thereby you limited functionality of the resulting products.
  • EP 620237 A2 describes prepolymers of diisocyanates and polyols. Reaction with higher-functional polyisocyanates is not disclosed.
  • DE-OS 2305695 describes prepolymers of diisocyanates and low molecular weight polyols having 2 to 4 hydroxyl groups.
  • the object of the present invention was to provide novel polyisocyanates having a high functionality for paints, especially for clearcoats, which have a high hardness and / or scratch resistance, in particular already when cured at low temperatures and / or in bicomponent.
  • Component polyurethane coatings show accelerated drying and / or improved sulfuric acid resistance.
  • the object is achieved by highly functional urethane-containing polyisocyanates obtainable by
  • the molar ratio of NCO groups to OH groups between (B) and (A) is at least 3: 1.
  • the compound (A) may be a tertiary dialkanolamine or a trialkanolamine.
  • a trialkanolamine is understood to mean the reaction product of ammonia with propylene oxide and / or ethylene oxide, preferably propylene oxide or ethylene oxide, particularly preferably ethylene oxide.
  • Preferred trialkanolamines (A) are those of the formula
  • the trialkanolamine (A) is 5- [bis (2'-hydroxyethyl) amino] -3-oxa-pentane-1-ol, triethanolamine or tripropanolamine, more preferably triethanolamine.
  • a tertiary dialkanolamine is understood to mean the reaction product of a primary amine with propylene oxide and / or ethylene oxide, preferably propylene oxide or ethylene oxide, particularly preferably ethylene oxide.
  • Preferred tertiary dialkanolamines are
  • R 1 is a straight or branched Ci to C 20 alkyl group, an optionally substituted C 5 to C 12 cycloalkyl group, an optionally substituted C 7 - to Cio-aralkyl group, or an optionally substituted C6-Ci2-aryl group
  • a straight-chain or branched C 1 - to C 20 -alkyl group mean, for example, methyl,
  • R 1 is preferably a C 5 - to C 12 -cycloalkyl or C 1 - to C 20 -alkyl, more preferably C 5 - to C 6 -cycloalkyl or C 1 - to C 10 -alkyl, very particularly preferably C 1 - to C 12 -alkyl and in particular C 1 - to C 4 -alkyl.
  • R 1 Preferred for R 1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, phenyl, ⁇ - or ß-naphthyl, benzyl , Cyclopentyl or cyclohexyl.
  • radicals R 1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, cyclopentyl or cyclohexyl. Very particular preference is given to methyl, ethyl, n-propyl, isopropyl and n-butyl.
  • tertiary dialkanolamines N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N-cyclopentyldiethanolamine, N-cyclohexyldiethanolamine, N-ethyldipropanolamine, N-methyldipropanolamine and N-butyldipropanolamine.
  • N-ethyldiethanolamine, N-methyldiethanolamine and N-butyldiethanolamine Preference is given to N-ethyldiethanolamine, N-methyldiethanolamine and N-butyldiethanolamine, particularly preferably N-ethyldiethanolamine and N-methyldiethanolamine.
  • Polyols (A2) have a functionality of at least 3, for example 3 to 6, preferably 3 to 4, particularly preferably 3 or 4 and very particularly preferably 3.
  • polyols (A2) are trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), Maltitol and isomalt.
  • polyols (A2) are trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (
  • Preferred polyols are trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane and dipentaerythritol, particular preference is given to trimethylolpropane, pentaerythritol and glycerol, very particular preference to trimethylolpropane and glycerol.
  • diols (A1) are aliphatic diols which have from 2 to 20, preferably 2 to 12, carbon atoms, more preferably 1, 2-ethanediol, 2,2-dimethyl-1,2-ethanediol, 1,2-propanediol, 1, 3-propanediol, 2,2-dimethyl-1, 3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentan-1, 5-diol, 1, 6-hexanediol, 2- Ethyl 1,3-hexanediol, 2-propyl-1,3-heptane
  • the aliphatic diols are preferred, preferably 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,6 Hexanediol, 2-ethyl-1,3-hexanediol and 2-propyl-1,3-heptanediol, more preferably 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2 Ethyl-1, 3-hexanediol and 2-propyl-1, 3-heptanediol, most preferably 1, 4-butanediol and 1, 6-hexanediol.
  • alkoxylated polyol is understood to mean a polyol which is formally reacted with one or more identical or different alkylene oxides on at least one hydroxy group.
  • Suitable alkylene oxides for such an alkoxylation are, for example, ethylene oxide, propylene oxide, n-butylene oxide, isobutylene oxide, vinyl oxirane and / or styrene oxide.
  • the alkylene oxide chain may preferably be composed of ethylene oxide, propylene oxide and / or butylene oxide units. Such a chain may be composed of a species of alkylene oxide or a mixture of alkylene oxides. When a mixture is used, the different alkylene oxide units may be random or block or blocks of individual species.
  • Preferred as the alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof, particularly preferably either ethylene oxide or propylene oxide and most preferably ethylene oxide.
  • the number of alkylene oxide units in the chain is, for example, 1 to 10, preferably 1 to 5, particularly preferably 1 to 4 and in particular 1 to 3, based on the particular hydroxyl groups of the polyol.
  • R 2 is hydrogen or C 1 -C 6 -alkyl
  • These are preferably one to five times, more preferably one to four times and very particularly preferably one to three times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated or especially unalkoxylated glycerol, trimethylolpropane, trimethylolethane or pentaerythritol.
  • the ratio of diols (A1) to polyols (A2) is preferably from 10:90 to 90:10 (based on the molar amounts of diol and polyol), particularly preferably from 20:80 to 80:20, very particularly preferably from 30 : 70 to 70:30 and especially from 40:60 to 60:40.
  • the polyisocyanate (B) has a functionality of more than 2, preferably at least 2.2, particularly preferably at least 2.4, very particularly preferably at least 2.8 and in particular at least 3.
  • the polyisocyanates (B) are composed of aliphatic and / or or cycloaliphatic, preferably either aliphatic or cycloaliphatic diisocyanates.
  • the diisocyanates are preferably isocyanates having 4 to 20 C atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4-, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'- Di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclo
  • Preferred diisocyanates are 1,6-hexamethylene diisocyanate, isophorone diisocyanate and / or 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, particular preference is given to 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate and very particular preference to 1,6 -Hexamethylendiisocyanat.
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane and / or allophanate groups of linear or branched C 4 -C 20 -alkylene diisocyanates or cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or mixtures thereof ,
  • hexamethylene diisocyanate 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane or its polyisocyanates, very particularly preferably isophorone diisocyanate and hexamethylene diisocyanate or their polyisocyanates, particularly preferably hexamethylene diisocyanate or its polyisocyanates.
  • isocyanurate-containing polyisocyanates of aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and / or isophorone diisocyanate.
  • the isocyanurates present are, in particular, tris-isocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 4.5.
  • uretdione diisocyanates having aliphatically and / or cycloaliphatically bonded isocyanate groups and in particular those of hexamethylene diisocyanate or isophorone diisocyanate naturally derived.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used as polyisocyanates (B) in admixture with other polyisocyanates, in particular those mentioned under 1).
  • biuret polyisocyanates having cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs.
  • These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO
  • polyisocyanates containing urethane and / or allophanate groups with aliphatically or cycloaliphatically bonded isocyanate groups as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with monohydric or polyhydric alcohols, e.g.
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.
  • the polyisocyanates can be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • polyisocyanate (B) and compound (A) are reacted with or without solvent under urethanization conditions.
  • “Urethanization conditions” means that the reaction conditions are selected so that at least partially urethane groups are formed by reaction of the isocyanate group-containing component (B) and the hydroxyl-containing component (A).
  • the temperature in this reaction is generally up to 150 ° C., preferably up to 120 ° C., more preferably below 100 ° C. and very particularly preferably below 90 ° C., and is usually carried out in the presence of at least one catalyst which contains the urethanization catalyzed reaction.
  • the reaction can also be carried out in the absence of a catalyst.
  • the temperature of the reaction should be at least 20 ° C, preferably at least 30, more preferably at least 40 and most preferably at least 50 ° C.
  • Catalysts are in this case those compounds which, owing to their presence in a starting material mixture, lead to a higher proportion of urethane group-containing reaction products than the same starting material mixture in their absence under the same reaction conditions.
  • Lewis acidic organic metal compounds are e.g. Tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) diacetate, stannous (II) dioctoate, stannous (II) bis (ethylhexanoate) and stannous (II) dilaurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • zinc (II) salts can be used, such as zinc (II) dioctoate.
  • Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel, zinc and cobalt are also possible. Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, Vol. 35, pages 19-29.
  • Preferred Lewis-acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium-2, 2,6,6-tetramethyl-3,5-heptanedionate. Also bismuth and cobalt catalysts and cesium salts can be used as catalysts.
  • Suitable cesium salts are those compounds in which the following anions are used: F - C, CIO " , CIO 3 -, CI0 4 -, Br, J, J0 3 -, CN, OCN, N0 2 -, N0 3 -, HC0 3 -, C0 3 2-, S 2 -, SH-, HSO 3 -, S0 3 2 " , HS0 4 -, S0 4 2” , S 2 0 2 2 -, S 2 0 4 2 -, S 2 0 5 2 -, S 2 0 6 2 -, S 2 0 7 2 " , S 2 0 8 2 -, H 2 P0 2 -, H 2 P0 4 -, HP0 4 2 -, P0 4 3 " , P 2 0 7 4" , (OC n H 2n + i) -, (C n H 2n -i0 2 ) -, (C n H 2n - 3 0 2
  • A is a hydroxyl group or a hydrogen atom, n is a number from 1 to 3,
  • R is a polyfunctional linear or branched, aliphatic or aromatic hydrocarbon radical
  • M ® in cation for example an alkali metal cation or a quaternary ammonium cation, such as tetraalkylammonium, and
  • Quaternary ammonium salts are particularly suitable as catalysts for the process
  • the radical Y.sup.- is preferably a carboxylate, carbonate or hydroxide and particularly preferably a carboxylate or hydroxide.
  • R 13 is hydrogen, C 1 to C 20 alkyl, CQ to C 12 -Al 1 or C 7 to C 20 arylalkyl, each of which may optionally be substituted.
  • R 13 is hydrogen or C 1 to C 6 alkyl.
  • Preferred quaternary ammonium salts are those in which the radicals R 9 to R 12 represent identical or different alkyl groups having 1 to 20, preferably 1 to 4, carbon atoms, which are optionally substituted by hydroxyl or phenyl groups. Two of the radicals R 9 to R 12 may also together with the nitrogen atom and optionally a further nitrogen or oxygen atom form a heterocyclic, five-, six- or seven-membered ring.
  • the radicals R 9 to R 11 may in any case also represent ethylene radicals which together with the quaternary nitrogen atom and another tertiary nitrogen atom form a bicyclic triethylenediamine structure, provided that the radical R 12 then represents a hydroxyalkyl group having 2 to 4 carbon atoms, in which the hydro xyl group is preferably located in the 2-position to the quaternary nitrogen atom.
  • the hydroxy-substituted radical or the hydroxy-substituted radicals may also contain other substituents, for example C 1 -C 4 -alkyloxy substituents.
  • ammonium ions may also be part of a mono- or poly-ring system, for example derived from piperazine, morpholine, piperidine, pyrrolidine, quinuclidine or di-azabicyclo [2.2.2] octane.
  • R 9 to R 12 examples are independently of one another methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl , 2,4,4-trimethylpentyl, nonyl, isononyl, decyl, dodecyl, tetradecyl, heptadyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl , 1 - phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl
  • R 9 to R 12 Ci to C4-alkyl are independently of one another the radicals R 9 to R 12 Ci to C4-alkyl.
  • R 12 may additionally be benzyl or a remainder of the formula
  • R 14 and R 15 independently of one another may be hydrogen or C 1 to C 4 -alkyl.
  • R 9 to R 12 are independently methyl, ethyl and n-butyl and for R 12 additionally benzyl, 2-hydroxyethyl and 2-hydroxypropyl.
  • the following catalysts may preferably be used for the process according to the invention:
  • Quaternary ammonium hydroxides preferably N, N, N-trimethyl-N-benzylammonium hydroxide and N, N, N-trimethyl-N- (2-hydroxypropyl) -ammonium hydroxide, according to DE-A-38 06 276.
  • Organic metal salts of the formula No. 3,817,939 in which A, a hydroxyl group or a hydrogen atom, n is a number from 1 to 3, R is a polyfunctional linear or branched, aliphatic or aromatic hydrocarbon radical and M is a cation of a strong base, for example an alkali metal cation or a quaternary ammonium cation, such as tetraalkylammonium.
  • Preferred catalysts are zinc (II) salts, among them especially zinc acetylacetonate.
  • dibutyltin dilaurate is also preferred.
  • the catalyst is normally used in amounts of from 0.001 to 10 mol% with respect to isocyanate groups used, preferably from 0.5 to 8, more preferably from 1 to 7 and very particularly preferably from 2 to 5 mol%.
  • the polyisocyanate (B) is used in at least a threefold excess of the NCO groups based on the hydroxy groups in the compound (A), preferably in an at least 4-fold excess, more preferably at least 5 and most preferably at least 6-fold Excess.
  • the unreacted portion of polyisocyanate (B) can either be separated or preferably remain in the reaction mixture.
  • reaction is preferably carried out without solvent, but can also be carried out in the presence of at least one solvent.
  • reaction mixture obtained can be formulated in a solvent after completion of the reaction.
  • Suitable solvents are those which have no isocyanate-reactive groups and in which the polyisocyanates at least 10% by weight, preferably at least 25, more preferably at least 50, most preferably at least 75, in particular at least 90 and especially are soluble to at least 95% by weight.
  • examples of such solvents are aromatic (including alkylated benzenes and naphthalenes) and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated Alkanklarealkylester, ethers, respectively mixtures of solvents.
  • Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 4 -hydrocarbons and may have a boiling range of from 10 to 300 ° C., particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® grades from ExxonMobil Chemical, in particular Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio-aromatics, boiling range about 154-178 ° C.), 150 (boiling range approx 182-207 ° C) and 200
  • Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also known under the designations crystal oil (for example crystal oil 30, boiling range about 158-198 ° C. or crystal oil 60: CAS No. 64742-82-1), white spirit (for example likewise CAS No. 64742). 82-1) or solvent naphtha (light: boiling range about 155-180 ° C, heavy: boiling range about 225-300 ° C) commercially available.
  • the aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • (Cyclo) aliphatic hydrocarbons are, for example, decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • the content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.
  • esters are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.
  • Ethers are, for example, tetrahydrofuran (THF), dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • THF tetrahydrofuran
  • dioxane dioxane
  • dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • ketones are acetone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, methyl amyl ketone and tert-butyl methyl ketone. It is a preferred embodiment of the present invention to formulate the high-functionality polyisocyanates according to the invention with a solvent.
  • a preferred solvent is n-butyl acetate.
  • the concentration of the polyisocyanate according to the invention in the solution should be at least 50% by weight, preferably at least 60% by weight and more preferably at least 70% by weight.
  • the urethane-containing high-functionality polyisocyanates according to the invention generally have an NCO functionality of more than 2, preferably at least 3, more preferably at least 4, very preferably at least 5 and in particular more than 6.
  • the urethane-containing high-functionality polyisocyanate according to the invention generally have a number-average molecular weight Mn of from 1,000 to 20,000, preferably from 1,200 to 10,000 and more preferably from 1,500 to 5,000 g / mol and a weight-average molecular weight Mw of from 1,000 to 50,000 and preferably from 1,500 to 30,000.
  • the molecular weights can be determined by gel permeation chromatography with a suitable polymer standard and tetrahydrofuran or dimethylformamide as eluent.
  • the high-functionality urethane group-containing polyisocyanates according to the invention are used, for example, in two-component polyurethane coatings containing at least one component which contain at least two isocyanate-reactive groups (binders).
  • the high-functionality urethane group-containing polyisocyanates according to the invention can be used alone or in admixture with other polyisocyanates (C) as crosslinking component.
  • Such other polyisocyanates (C) are obtainable by oligomerization of monomeric isocyanates.
  • the monomeric isocyanates used for this purpose can be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which in this document is referred to briefly as (cyclo) aliphatic, particularly preferred are aliphatic isocyanates.
  • Aromatic isocyanates are those which contain at least one aromatic ring system, ie both purely aromatic and also araliphatic compounds.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system. Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • the monomeric isocyanates are preferably diisocyanates which carry exactly two isocyanate groups. In principle, however, it may also be monoisocyanates with an isocyanate group. In principle, higher isocyanates having an average of more than 2 isocyanate groups are also considered.
  • Triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, tri- and higher polyisocyanates suitable for example by phosgenation of corresponding aniline / formaldehyde are suitable for this purpose Condensates are obtained and represent methylene bridged polyphenyl polyisocyanates.
  • the monomeric isocyanates have no significant reaction products of the isocyanate groups with itself.
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 carbon atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetra methylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2
  • Isophorone diisocyanate is usually present as a mixture, namely of the cis and trans isomers, generally in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75 : 25 and most preferably in the ratio of about 75:25.
  • Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.
  • (cyclo) aliphatic diisocyanates eg such as 1, 6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-3-isocyanato-methyl-3,5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to give (cyclo) aliphatic biscarbamic esters and their thermal cleavage into the corresponding diisocyanates and alcohols.
  • HDI 1, 6-hexamethylene diisocyanate
  • IPDI isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical
  • diisocyanates generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
  • the isocyanates used have a total content of hydrolyzable chlorine of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, in particular less than 15 ppm and especially less than 10 ppm. This can be measured, for example, by ASTM D4663-98.
  • monomeric isocyanates having a higher chlorine content, for example up to 500 ppm.
  • mixtures of such monomeric isocyanates which have been obtained by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the resulting (cyclo) aliphatic biscarbamic acid esters, with such diisocyanates, which have been obtained by phosgenation of the corresponding amines, be used.
  • the polyisocyanates (C) to which the monomeric isocyanates can be oligomerized are generally characterized as follows:
  • the average NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably 2 to 5 and more preferably 2.4 to 4.
  • the polyisocyanates (C) are preferably the following compounds: Isocyanurate group-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs containing more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.
  • Uretdione group-containing polyisocyanates having aromatically, aliphatically and / or cyclo-aliphatically bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or first the uretdione groups formed and these are then reacted to the other polyisocyanates or the diisocyanates first to the other polyisocyanates and these then to uretdione groups-containing Products are implemented.
  • These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6 on.
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.5 to 4.5.
  • Such urethane and / or allophanate groups containing polyisocyanates can uncatalyzed or preferably in the presence of catalysts such as ammonium carboxylates or Hydroxides, or Allophanatleiterskatalysatoren, eg Zn (II) compounds, each in the presence of mono-, di- or polyhydric, preferably monohydric alcohols produced.
  • catalysts such as ammonium carboxylates or Hydroxides, or Allophanatleiterskatalysatoren, eg Zn (II) compounds, each in the presence of mono-, di- or polyhydric, preferably monohydric alcohols produced.
  • Oxadiazintrion phenomenon containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
  • Iminooxadiazindion phenomenon containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
  • Hyperbranched polyisocyanates as are known, for example, from DE-A1 10013186 or DE-A1 10013187.
  • the polyisocyanates 1) -1 1), preferably 1), 3), 4) and 6) may after their preparation in biuret or urethane / allophanate groups having polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably (cyclo ) aliphatically bound isocyanate groups.
  • the formation of biuret groups takes place, for example, by addition of water or reaction with amines.
  • the formation of urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts.
  • These biuret or urethane / allophanate groups containing polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6 on.
  • Hydrophilically modified polyisocyanates ie polyisocyanates which, in addition to the groups described under 1 -12, contain those which formally arise by adding molecules having NCO-reactive groups and hydrophilizing groups to the isocyanate groups of the above molecules.
  • the latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.
  • Modified polyisocyanates for dual-cure applications ie polyisocyanates which contain, in addition to the groups described under 1-12, those which formally form by addition of molecules with NCO-reactive groups and UV- or actinic radiation-crosslinkable groups to the isocyanate groups of the above molecules , These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxyl groups.
  • the diisocyanates or polyisocyanates listed above may also be present at least partially in blocked form.
  • classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.
  • the polyisocyanate (C) is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably from the group consisting of isocyanurates and allophanates, in particular is an isocyanurate group-containing polyisocyanate.
  • the polyisocyanate (C) is isocyanurate group-containing polyisocyanates of 1,6-hexamethylene diisocyanate.
  • the polyisocyanate is a mixture of isocyanurate-containing polyisocyanates of 1,6-hexamethylene diisocyanate and of isophorone diisocyanate.
  • the polyisocyanate (C) is a mixture comprising low-viscosity polyisocyanates, preferably polyisocyanates containing isocyanurate groups, having a viscosity of 600-1500 mPa * s, in particular less than 1200 mPa * s, low-viscosity urethanes and / or allophanates having a viscosity of 200-1600 mPa * s, in particular 600-1500 mPa * s, and / or iminooxadiazinedione-containing polyisocyanates.
  • low-viscosity polyisocyanates preferably polyisocyanates containing isocyanurate groups, having a viscosity of 600-1500 mPa * s, in particular less than 1200 mPa * s, low-viscosity urethanes and / or allophanates having a viscosity of 200-1600 mPa * s, in particular 600-1
  • the viscosity at 23 ° C according to DIN EN ISO 3219 / A.3 is given in a cone-plate system with a rate gradient of 1000 s 1 , unless otherwise noted.
  • the high-functionality urethane group-containing polyisocyanates according to the invention may optionally be used in admixture with other polyisocyanates (C) as crosslinker components with at least one binder in polyurethane coatings.
  • C polyisocyanates
  • the highly functional urethane group-containing polyisocyanates according to the invention preferably 50 to 90% by weight and more preferably 60 to 80% by weight, and 0 to 50% by weight of other polyisocyanates (C), preferably 10 to 50, particularly preferably 20 to 40% by weight %, with the proviso that the sum is always 100% by weight.
  • the binders may be, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea; Polyesterpolyacrylatpolyole; Polyester polyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers, graft polymers of the substance groups mentioned with e.g. different Glasübergangstempera- ren, and mixtures of said binders act. Preference is given to polyacrylate polyols, polyester polyols and polyether polyols.
  • Preferred OH numbers measured according to DIN 53240-2, are 40-350 mg KOH / g solid resin for polyester, preferably 80-180 mg KOH / g solid resin, and 15-250 mg KOH / g solid resin for polyacrylate, preferably 80 -160 mg KOH / g.
  • the binders may have an acid number according to DIN EN ISO 3682 up to 200 mg KOH / g, preferably up to 150 and particularly preferably up to 100 mg KOH / g.
  • Polyacrylate polyols preferably have a molecular weight M n of at least 1000, particularly preferably at least 2000 and very particularly preferably at least 5000 g / mol.
  • the molecular weight M n may in principle be unlimited upwards, preferably up to 200,000, particularly preferably up to 100,000, very particularly preferably up to 80,000 and in particular up to 50,000 g / mol.
  • the latter can be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid”), with di- or polyols, which preferably have 2 to 20 C atoms and have at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1 - dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 4-butanediol, 1,5-pentanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-e
  • the hydroxyl-containing monomers are used in the copolymerization in admixture with other polymerizable, preferably free-radically polymerizable monomers, preferably those which contain more than 50% by weight of C 1 -C 20, preferably C 1 -C 4 -alkyl (meth) acrylate , (Meth) acrylic acid, vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof , Particular preference is given to the polymers which consist of more than 60% by weight of C 1 -C 10 -alkyl (meth) acrylates, styrene and derivatives thereof, vinylimidazole or mixtures thereof.
  • the polymers may contain hydroxy-functional monomers corresponding to the above hydroxy group content and optionally further monomers, e.g.
  • polyesterols as obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols.
  • polycarboxylic acids in particular dicarboxylic acids
  • polyols in particular diols.
  • triols, tetrols, etc., as well as triacids, etc. are also used in some cases.
  • Polyesterpolyols are known, for example, from Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products as well as ves resterable derivatives such as anhydrides or dialkyl esters, for example Ci-C4-alkyl esters, preferably methyl, ethyl or n-buty
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molecular weight between 134 and 1 178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, Neopentyl glycol,
  • Alcohols of the general formula HO- (CH 2) x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred.
  • Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol.
  • Further preferred is neopentyl glycol.
  • polycarbonate diols as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
  • lactone-based polyesterdiols which are homopolymers or mixed polymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also denoted by a d- to C 4 - Alkyl radical may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone, and mixtures thereof.
  • Suitable starter components are, for example, those mentioned above as constituent components for the polyesterpolyols. dermolekularen dihydric alcohols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components.
  • polycondensates of butanediol are suitable.
  • hydroxy-functional carboxylic acids for example dimethylolpropionic acid or dimethylolbutanoic acid.
  • the polymers may of course also be compounds with primary secondary amino groups.
  • Polyisocyanate composition and binder are prepared in a molar ratio of isocyanate groups to isocyanate-reactive groups of 0.1: 1 to 10: 1, preferably 0.2: 1 to 5: 1, particularly preferably 0.3: 1 to 3, for the preparation of the polyurethane coatings. 1, very particularly preferably 0.5: 1 to 2: 1, in particular 0.8: 1 to 1, 2: 1 and especially 0.9: 1 to 1, 1: 1 mixed together, where appropriate, further typical of the paint Components can be mixed and applied to the substrate.
  • the paint mixture is cured under suitable conditions. Depending on the application, this can be done, for example, at 100 to 140 ° C, for example, in paints in OEM applications, or in a lower temperature range of, for example, 20 to 80 ° C.
  • coating compositions may contain 0 to 10% by weight of at least one UV stabilizer.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter being available as Tinuvin® grades from Ciba Specialty Chemicals) and benzophenones. These may additionally 0 to 5% by weight of suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, for. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate included. Furthermore, coating compositions may furthermore contain 0 to 10% by weight of further typical coatings additives.
  • suitable radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, for. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) se
  • antioxidants for example, antioxidants, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.
  • Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
  • chelating agents e.g. Ethylenediamine and their salts and ß-diketones are used.
  • Suitable fillers include silicates, e.g. For example, by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • the substrates are coated by conventional methods known in the art, wherein at least one coating composition on the substrate to be coated in the desired strength and the optional volatile constituents of the coating composition, optionally with heating, removed. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. Example by spraying, filling, doctoring, brushing, rolling, rolling, pouring, laminating, injection molding or coextrusion.
  • the thickness of such a layer to be hardened may be from 0.1 ⁇ m to several mm, preferably from 1 to 2000 ⁇ m, more preferably from 5 to 200 ⁇ m, very particularly preferably from 5 to 60 ⁇ m (based on the paint in the state in which Solvent is removed from the paint).
  • substrates coated with a lacquer containing the urethane-containing polyisocyanates according to the invention are also an object of the present invention.
  • the resulting two-component coating compositions and paint formulations are suitable in principle for coating substrates such as wood, wood veneer, paper, cardboard, textile, film, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as ment-shaped blocks and fiber cement boards or metals, which may be optionally pre-coated or pretreated.
  • substrates such as wood, wood veneer, paper, cardboard, textile, film, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as ment-shaped blocks and fiber cement boards or metals, which may be optionally pre-coated or pretreated.
  • they are particularly preferably suitable for coating plastic surfaces and metallic substrates.
  • These coating compositions are preferably used as clearcoats, basecoats and topcoats, primers and fillers; they are particularly suitable as a topcoat, preferably as a clearcoat, owing to their high scratch resistance, in particular in coatings on (large) vehicles and aircraft and in automotive coatings as an OEM and refinish application. It is an advantage of the urethane group-containing polyisocyanates according to the invention that they give high scratch resistance and clear elasticity in clearcoats. In addition, the products of the invention usually give a lower viscosity.
  • Basonat® HI 100 from BASF SE Basonat® HI 100 from BASF SE, HDI isocyanurate with an NCO content of 22.2% and a viscosity of 3500 mPa * s at 23 ° C, functionality of about 3.4.
  • Basonat® Hl 100 from BASF SE HDI isocyanurate with an NCO content of 22.2% and a viscosity of 2800 mPa * s at 23 ° C.
  • Desmodur® N3790 from Bayer AG HDI isocyanurate (90% in butyl acetate) with an NCO content of 17.8% and a viscosity of 2150 mPa * s at 23 ° C.
  • the clearcoats thus contained were cured after 10 minutes of aeration time at room temperature or for the determination of scratch resistance and acid resistance at 60 ° C. over a period of 30 minutes. Before the tests, the paint films were stored for 24 h at 23 ⁇ 2 ° C and 50 ⁇ 10% humidity.
  • the gel time is considered to be the time between paint formulation and complete gelation of the paint.
  • the paint was touched after application at regular intervals with a cotton ball. The test is terminated as soon as cotton fibers no longer adhere to the paint surface.
  • the pendulum hardness was determined to König (EN ISO 1522).
  • the cross hatch was determined according to EN ISO 2409. The marks are between 0 (very good adhesion) and 5 (very bad adhesion).
  • the surface is scratched with a corundum particle-containing abrasive fleece under a weight of 500 g.
  • the damage is determined by the gloss value of the paint.
  • the reflow is determined by annealing at the temperature indicated in the table for the period specified in the table after scratching over 50 double strokes.
  • a 25 ⁇ drop of 1% sulfuric acid was added to a cured coating at a given temperature (30 minutes at 80 or 130 ° C) on a gradient oven tray and heated in the gradient oven at 35-75 ° C for 30 minutes. The sheet was then washed off with water and dried. Indicated is the lowest temperature at which it was apparent that there was an etching on the paint.
  • nb stands for non-specific measured values.

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Abstract

La présente invention concerne des polyisocyanates contenant des groupes uréthane à base de diisocyanates aliphatiques et/ou cycloaliphatiques et leur utilisation.
PCT/EP2011/062836 2010-07-30 2011-07-26 Polyisocyanates présentant des groupes uréthane hautement fonctionnels WO2012013681A1 (fr)

Priority Applications (3)

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EP11735668.3A EP2598549A1 (fr) 2010-07-30 2011-07-26 Polyisocyanates présentant des groupes uréthane hautement fonctionnels
JP2013522201A JP5871924B2 (ja) 2010-07-30 2011-07-26 ウレタン基を有する高官能性ポリイソシアナート
CN2011800477000A CN103140530A (zh) 2010-07-30 2011-07-26 包含氨基甲酸酯基的高官能度多异氰酸酯

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WO2016169810A1 (fr) * 2015-04-20 2016-10-27 Basf Se Matières de revêtement à deux composants
WO2019062383A1 (fr) * 2017-09-26 2019-04-04 Covestro Deutschland Ag Système à deux constituants pour revêtements élastiques

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EP3774970A1 (fr) * 2018-04-02 2021-02-17 DDP Specialty Electronic Materials US, Inc. Compositions adhésives de polyuréthane à deux composants
CN110293616A (zh) * 2019-06-18 2019-10-01 广州厚邦木业制造有限公司 一种桉木指接地板的制备工艺
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Publication number Priority date Publication date Assignee Title
EP2910586A1 (fr) * 2014-02-21 2015-08-26 Bayer MaterialScience AG Polyuréthanes transparents à température de transition vitreuse Tg élevée
WO2016169810A1 (fr) * 2015-04-20 2016-10-27 Basf Se Matières de revêtement à deux composants
US10358576B2 (en) 2015-04-20 2019-07-23 Basf Se Two-component coating compounds
WO2019062383A1 (fr) * 2017-09-26 2019-04-04 Covestro Deutschland Ag Système à deux constituants pour revêtements élastiques
US11760828B2 (en) 2017-09-26 2023-09-19 Covestro Deutschland Ag Two-component system for elastic coatings

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