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WO2019068529A1 - Polyisocyanates dispersibles dans l'eau - Google Patents

Polyisocyanates dispersibles dans l'eau Download PDF

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Publication number
WO2019068529A1
WO2019068529A1 PCT/EP2018/076072 EP2018076072W WO2019068529A1 WO 2019068529 A1 WO2019068529 A1 WO 2019068529A1 EP 2018076072 W EP2018076072 W EP 2018076072W WO 2019068529 A1 WO2019068529 A1 WO 2019068529A1
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Prior art keywords
water
polyisocyanate
groups
polyisocyanates
component
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Inventor
Frederic Lucas
Sebastian Roller
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/3885—Phosphate compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • 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
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • 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
    • C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
    • 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

Definitions

  • the present invention relates to improved water-dispersible polyisocyanates for coatings with enhanced drying behaviour, more particularly for two-component polyurethane coating materials.
  • Water-dispersible polyisocyanates have already been known for a long time and are frequently used as a crosslinker component together with aqueous polyol dispersions in aqueous coating systems. A large number of constituents with a water-dispersing effect have become established for such polyisocyanates.
  • Polyisocyanates containing such carboxylate groups as actively dispersing groups exhibit inadequate stability on storage and an insufficient dispersibility.
  • EP 198343 A2 describes polyisocyanates which contain carbodiimide groups and which are rendered water-dispersible by means of sulfonate groups and, if appropriate, polyether groups. Disclosed explicitly as synthesis components carrying sulfonate groups are alkoxylated sulfonates, and sulfonated diisocyanates, which have to be prepared specially.
  • WO 2009/010469 discloses water-dispersible polyisocyanates bearing sulfonate groups bound to an aromatic ring and polyether groups.
  • the polyisocyanates are easily emulsifyable and coatings obtained with such water-dispersible polyisocyanates exhibit high gloss.
  • WO 98/56843 and WO 09/71784 disclose water-dispersible polyisocyanates with phosphate compounds as emulgators.
  • WO 2014/048634 discloses water-dispersible polyisocyanates which contain not only phosphate groups but also monofunctional polyalkylene glycol and exhibit not only high hardness but also good gloss and good drying properties.
  • R 1 and R 2 independently of one another are Cio - C20 alkyl
  • mixture of compounds of formulae (I) and (II) being characterised in that the molar ra- tio between compound (II), i.e. the monoester-type compound, and compound (I), i.e. the diester-type compound, is from 5:95 to 95:5,
  • Such polyisocyanates (A) of the invention feature not only high ease of incorporation into aqueous polyol dispersions but also good drying properties. Moreover, they give coatings featuring good hardness, and high gloss.
  • Synthesis component (a) is at least one, one to three for example, one to two for preference, and more preferably precisely one diisocyanate or polyisocyanate.
  • the monomeric isocyanates used may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which is referred to for short in this text as (cyclo)aliphatic. Aliphatic isocyanates are particularly preferred.
  • Aromatic isocyanates are those which comprise at least one aromatic ring system, in other words not only purely aromatic compounds but also araliphatic compounds.
  • Cycloaliphatic isocyanates are those which comprise at least one cycloaliphatic ring system.
  • Aliphatic isocyanates are those which comprise exclusively linear or branched chains, i.e., acyclic compounds.
  • the monomeric isocyanates are preferably diisocyanates, which carry precisely two isocyanate groups. They can, however, in principle also be monoisocyanates having an isocyanate group.
  • isocyanates having on average more than 2 isocyanate groups are also possible.
  • Suitability is possessed for example by triisocyanates, such as triisocyanatononane, 2,6-diisocyanato-1 -hexanoic acid 2'-isocyanatoethyl ester, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether, or the mixtures of diisocyanates, triisocyanates, and higher polyisocyanates that are obtained, for example, by phosgenation of corresponding aniline/formaldehyde condensates and represent methylene- bridged polyphenyl polyisocyanates and the corresponding ring-hydrogenated isocyanates.
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 carbon atoms.
  • typical diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, pen- tamethylene 1 ,5-diisocyanate, hexamethylene diisocyanate (1 ,6-diisocyanatohexane), octa- methylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradec- amethylene diisocyanate, derivatives of lysine diisocyanate (e.g.
  • lysine methyl ester diisocyanate lysine ethyl ester diisocyanate
  • trimethylhexane diisocyanate or tetramethylhexane diiso- cyanate cycloaliphatic diisocyanates such as 1 ,4-, 1 ,3- or 1 ,2-diisocyanatocyclo-hexane, 4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, 1 -isocyanato-3,3,5-trimethyl-5-(iso-cyanatomethyl)cy- clohexane (isophorone diisocyanate), 1 ,3- or 1 ,4-bis(isocyanatomethyl)cyclohexane or 2,4-, or 2,6-diisocyanato-1 -methylcyclohexane, and also 3 (or 4), 8 (or 9)-bis(isocy-anatomethyl
  • hexamethylene 1 ,6-diisocyanate Particular preference is given to hexamethylene 1 ,6-diisocyanate, 1 ,3-bis(isocyanatomethyl)cy- clohexane, isophorone diisocyanate, and 4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, very particular preference to isophorone diisocyanate and hexamethylene 1 ,6-diisocyanate, and especial preference to hexamethylene 1 ,6-diisocyanate.
  • Mixtures of said isocyanates may also be present.
  • Isophorone diisocyanate is usually in the form of a mixture, specifically a mixture of the cis and trans isomers, generally in a proportion of about 60:40 to 80:20 (w/w), preferably in a proportion of about 70:30 to 75:25, and more preferably in a proportion of approximately 75:25.
  • Dicyclohexylmethane 4,4'-diisocyanate may likewise be in the form of a mixture of the different cis and trans isomers.
  • EP-A-0 126 299 US 4 596 678
  • (cyclo)aliphatic diisocyanates such as hexamethylene 1 ,6-diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, and 1 -iso- cyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), for example, can be prepared by reacting the (cyclo)aliphatic diamines with, for example, urea and alcohols to give (cyclo)aliphatic biscarbamic esters and subjecting said esters to thermal cleavage into the corresponding diisocyanates and alcohols.
  • HDI hexamethylene 1 ,6-diisocyanate
  • IPDI isophorone diisocyanate
  • Diisocyanates obtained in this way generally contain a very low or even unmeasurable fraction of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
  • the isocyanates used have a total hydrolyzable chlorine content of less than 200 ppm, preferably of less than 120 ppm, more preferably less than 80 ppm, very preferably less than 50 ppm, in particular less than 15 ppm, and especially less than 10 ppm. This can be measured by means, for example, of ASTM specification D4663- 98. Of course, though, monomeric isocyanates having a higher chlorine content can also be used, of up to 500 ppm, for example.
  • diisocyanates which have been obtained by phosgenating the corresponding amines.
  • the polyisocyanates (a) to which the monomeric isocyanates can be oligomerized are generally characterized as follows:
  • the average NCO functionality of such compounds is in general at least 1.8 and can be up to 8, preferably 2 to 5, and more preferably 2.4 to 4.
  • the polyisocyanates (a) are preferably compounds as follows:
  • Polyisocyanates containing isocyanurate groups and derived from aromatic, aliphatic and/or cycloaliphatic diisocyanates Particular preference is given in this context to the corresponding aliphatic and/or cycloaliphatic isocyanatoisocyanurates and in particular to those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanu- rates present are, in particular, tris-isocyanatoalkyl and/or trisisocyanatocycloalkyl isocy- anurates, which constitute cyclic trimers of the diisocyanates, or are mixtures with their higher homologs containing more than one isocyanurate ring.
  • the isocyanatoisocyanurates generally have an NCO content of 10% to 30% by weight, in particular 15% to 25% by weight, and an average NCO functionality of 2.6 to 8.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the polyisocyanates containing uretdione groups are obtained in the context of this invention as a mixture with other polyisocyanates, more particularly those specified under 1 ).
  • the diisocyanates can be reacted under reaction conditions under which not only uretdione groups but also the other polyisocyanates are formed, or the uretdione groups are formed first of all and are subsequently reacted to give the other polyisocyanates, or the diisocyanates are first reacted to give the other polyisocyanates, which are subsequently reacted to give products containing uretdione groups.
  • These polyisocyanates containing biuret groups generally have an NCO content of 18% to 22% by weight and an average NCO functionality of 2.8 to 6.
  • diisocyanate such as of hexamethylene diisocyanate or of isophorone diisocyanate
  • mono- or polyhydric alcohols a
  • These polyisocyanates containing urethane and/or allophanate groups generally have an NCO content of 12% to 24% by weight and an average NCO functionality of 2.1 to 4.5.
  • Polyisocyanates of this kind containing urethane and/or allophanate groups may be prepared without catalyst or, preferably, in the presence of catalysts, such as ammonium carboxylates or ammonium hydroxides, for example, or allophanatization catalysts, such as Zn(ll) compounds, for example, in each case in the presence of monohydric, dihydric or polyhydric, preferably monohydric, alcohols.
  • catalysts such as ammonium carboxylates or ammonium hydroxides, for example, or allophanatization catalysts, such as Zn(ll) compounds, for example, in each case in the presence of monohydric, dihydric or polyhydric, preferably monohydric, alcohols.
  • the polyisocyanates containing urethane and/or allophanate groups can also be prepared in a mixture with other polyisocyanates, more particularly those specified under 1 ).
  • Polyisocyanates comprising oxadiazinetrione groups, derived preferably from hexameth- ylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this kind comprising oxadiazinetrione groups are accessible from diisocyanate and carbon dioxide.
  • Polyisocyanates comprising iminooxadiazinedione groups, derived preferably from hexa- methylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this kind compris- ing iminooxadiazinedione groups are preparable from diisocyanates by means of specific catalysts.
  • Hyperbranched polyisocyanates of the kind known for example from DE-A1 10013186 or DE-A1 10013187.
  • Polyurethane-polyisocyanate prepolymers from di- and/or polyisocyanates with alcohols.
  • the polyisocyanates 1 )-1 1 ), preferably 1 ), 3), 4) and 6), can be converted, following their preparation, into polyisocyanates containing biuret groups or urethane/allophanate groups and having aromatically, cycloaliphatically or aliphatically attached, preferably (cyclo)ali- phatically attached, isocyanate groups.
  • the formation of biuret groups for example, is accomplished by addition of water, water donor compounds (e.g., tert-butanol), or by reaction with amines.
  • urethane and/or allophanate groups are accom- plished by reaction with monohydric, dihydric or polyhydric, preferably monohydric, alcohols, in the presence if appropriate of suitable catalysts.
  • These polyisocyanates containing biuret or urethane/allophanate groups generally have an NCO content of 18% to 22% by weight and an average NCO functionality of 2.8 to 6. 13) Hydrophilically modified polyisocyanates, i.e., polyisocyanates which as well as the
  • groups described under 1 -12 also comprise groups which result formally from addition of molecules containing NCO-reactive groups and hydrophilizing groups to the isocyanate groups of above molecules.
  • the latter groups are nonionic groups such as alkylpoly- ethylene oxide and/or ionic groups derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, and/or their salts.
  • Modified polyisocyanates for dual care applications i.e., polyisocyanates which as well as the groups described under 1 -12 also comprise groups resulting formally from addition of molecules containing NCO-reactive groups and UV-crosslinkable or actinic-radiation- crosslinkable groups to the isocyanate groups of above molecules.
  • These molecules are, for example, hydroxyalkyl (meth)acrylates and other hydroxyl-vinyl compounds.
  • diisocyanates or polyisocyanates recited above may also be present at least partly in blocked form.
  • Classes of compounds used for blocking are described in D.A. Wicks, Z.W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41 , 1 -83 (2001 ) and also 43, 131 -140 (2001 ).
  • Examples of classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxyl benzoic esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.
  • the polyisocyanate (a) is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, more preferably from the group consisting of isocyanurates and allophanates; in particular it is a polyisocyanate containing isocyanurate groups.
  • the polyisocyanate (a) encompasses polyisocyanates comprising isocyanurate groups and obtained from hexamethylene 1 ,6-diisocyanate.
  • the polyisocyanate (a) encompasses polyisocyanates comprising isocyanurate groups having a viscosity of 500 - 4000 mPa * s, more particularly 2000 - 3500 mPa * s.
  • composition according to the invention particularly advantageously contains a mixture of compounds based on the following formulae (I) and (II):
  • R 1 and R 2 being as defined above for formulae (I) and (II).
  • R 1 and R 2 independently of one another are Cio - C20 alkyl, preferably C13 - C17 alkyl Definitions therein are as follows:
  • C10 - C20 alkyl is for example n-Decyl, 2-Propylheptyl, n-Undecyl, iso-Undecyl, n-Dodecyl, n- Tridecyl, iso-Tridecyl, Ethylundecyl, Methyldodecyl, 3,3,5,5,7-Pentamethyloctyl, n-Tetradecyl, n- Pentadecyl, n-Hexadecyl, n-Heptadecyl, iso-Heptadecyl, 3,3,5,5,7,7,9-Heptamethyldecyl, n- Octadecyl und n-Eicosyl.
  • C10 - C20 alkyl can be branched or linear.
  • R 1 and R 2 independently of one another are branched C10 - C20 alkyl with a degree of branching according to Iso-lndex from 1 ,2 to 3, preferably from 1 ,7 to 2,5.
  • R 1 and R 2 independently of one another are unsubstituted C10 - C20 alkyl, more preferably unsubstituted C13 - C17 alkyl, in particular n-Tridecyl, iso-Tridecyl, n-Heptadecyl and iso-Heptadecyl, very preferably n-Tridecyl and iso-Tridecyl.
  • Unsubstituted means for each of the stated radicals not to be substituted by aryl, aryloxy, alkyloxy, heteroatoms, heterocycles and or any other group other than alkyl.
  • the compounds of component (b) are preferably mono iso-tridecyl phosphate, di iso-tridecyl phosphate, mono n-tridecyl phosphate, di n-tridecyl phosphate, mono iso-heptadecyl phosphate, di iso-heptadecyl phosphate, mono n-heptadecyl phosphate, di n-heptadecyl phosphate, and mixtures thereof.
  • the mixture of compounds of formulae (I) and (II) is characterised in that the molar ratio between compound (II), i.e. the monoester-type compound, and compound (I), i.e. the diester-type compound, is from 5:95 to 95:5, preferably 1 :20 to 20:1 , more preferably from 1 :5 to 15:1 , particularly preferably from 1 :1 to 10:1 and especially preferably from 1 ,05:1 to 5:1.
  • Component (c) encompasses monofunctional polyalkylene oxide polyether alcohols, which are reaction products of suitable starter molecules with polyalkylene oxides.
  • Suitable starter molecules for preparing monohydric polyalkylene oxide polyether alcohols are thiol compounds, monohydroxy compounds of the general formula R 5 -0-H or secondary monoamines of the general formula
  • R 5 , R 6 and R 7 each independently of one another are Ci - C20 alkyl, C2 - C20 alkyl uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or by one or more substituted or unsubstituted imino groups, or C6 - C12 aryl, C5 - C12 cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and/or sulfur atoms, or R 6 and R 7 together form an unsaturated, saturated or aromatic ring which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or by one or more substituted or unsubstituted imino groups, it being possible for the stated radicals to be substituted in each case by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles.
  • R 5 , R 6 , and R 7 independently of one another are Ci- to C 4 alkyl, i.e., methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl; more preferably R 5 , R 6 , and R 7 are methyl.
  • Suitable monovalent starter molecules are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols, and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, cyclopentanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxy-methyloxetane, or tetrahydrofurfuryl alcohol; unsaturated alcohols such as allyl alcohol, 1 ,1 -dimethylallyl alcohol or oleyl alcohol, aromatic alcohols such as
  • polyethers prepared starting from amines are the Jeffamine® M series, which represent methyl-capped polyalkylene oxides with an amino function, such as M-600 (XTJ-505), having a propylene oxide (PO)/ethylene oxide (EO) ratio of approximately 9:1 and a molar mass of approximately 600, M-1000 (XTJ-506): PO/EO ratio 3:19, molar mass approximately 1000, M-2005 (XTJ-507): PO/EO ratio 29:6, molar mass approximately 2000, or M-2070: PO/EO ratio 10:31 , molar mass approximately 2000.
  • M-600 XTJ-505
  • PO propylene oxide
  • EO ethylene oxide
  • M-1000 PO/EO ratio 3:19
  • M-2005 XTJ-507
  • M-2070 PO/EO ratio 10:31 , molar mass approximately 2000.
  • Alkylene oxides suitable for the alkoxylation reaction are ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane and/or styrene oxide, which may be used in any order or else in a mixture in the alkoxylation reaction.
  • alkylene oxides are ethylene oxide, propylene oxide, and their mixtures; ethylene oxide is particularly preferred.
  • Preferred polyether alcohols are those which are based on polyalkylene oxide polyether alcohols in whose preparation saturated aliphatic or cycloaliphatic alcohols of the
  • the monohydric polyalkylene oxide polyether alcohols have on average in general at least two alkylene oxide units, preferably at least 5 alkylene oxide units, per molecule, more preferably at least 7, and very preferably at least 8 alkylene oxide units, more particularly ethylene oxide units.
  • the monohydric polyalkylene oxide polyether alcohols have on average in general up to 50 al- kylene oxide units per molecule, preferably up to 30, more preferably up to 13, and very preferably up to 1 1 alkylene oxide units, more particularly ethylene oxide units.
  • the molar weight of the monohydric polyalkylene oxide polyether alcohols is preferably up to 4000, more preferably not above 2000 g/mol, very preferably not below 250 and more particularly 500 ⁇ 200 g/mol.
  • Preferred polyether alcohols are therefore compounds of the formula
  • R 5 is as defined above
  • k is an integer from 5 to 30, preferably 7 to 13, and more preferably 8 to 1 1 , and
  • the polyalkylene oxide polyether alcohols are generally prepared by alkoxylating the starter compounds in the presence of a catalyst, such as of an alkali metal or alkaline earth metal hydroxide, oxide, carbonate or hydrogencarbonate, for example.
  • a catalyst such as of an alkali metal or alkaline earth metal hydroxide, oxide, carbonate or hydrogencarbonate, for example.
  • the polyalkylene oxide polyether alcohols can also be prepared with the aid of multimetal cyanide compounds, frequently also referred to as DMC catalysts, which have been known for a long time and have been widely described in the literature, as for example in US 3,278,457 and in US 5,783,513.
  • the DMC catalysts are typically prepared by reacting a metal salt with a cyanometalate compound. To enhance the properties of the DMC catalysts it is customary to add organic ligands during and/or after the reaction. A description of the preparation of DMC catalysts is found, for example, in US-A 3,278,457.
  • Typical DMC catalysts have the following general formula: M a[M 2 (CN)b]d*fM jX k 'h(H 2 0) eL » zP in which
  • M 1 is a metal ion selected from the group comprising Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Al 3+ , Sr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 4+ , Ag + , Rh 2+ , Ru 2+ , Ru 3+ , Pd 2+ ,
  • M 2 is a metal ion selected from the group comprising Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , Ni 2+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , lr 3+ ,
  • M 1 and M 2 are alike or different
  • X is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO2 " ) or a mixture of two or more of the aforementioned anions, or a mixture of one or more of the aforementioned anions with one of the uncharged species selected from CO, H 2 0, and NO,
  • L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides or mixtures thereof,
  • P is an organic additive selected from the group comprising polyethers, polyesters, and
  • polycarbonates polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylamide-co- maleic acid), polyacrylnitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxylethylcellulose, polyacetates, ionic surface- and interface-active compounds, bile acid or salts, esters or amides thereof
  • e, f, h and z are integral or fractional numbers greater than or equal to zero, with a, b, d, g, n, j, k, and r, and also s and t, being selected so as to ensure electroneutrality.
  • M 1 is Zn 2+ and M 2 is Co 3+ or Co 2+ .
  • the metals M 1 and M 2 are alike particularly when they are cobalt, manganese or iron.
  • the residues of the catalyst may remain in the product obtained or may be neutralized using an acid, preferably hydrochloric acid, sulfuric acid or acetic acid, with the salts being subsequently removable preferably by means, for example, of washing or of ion exchangers. If appropriate, a partial neutralization may take place, and the product may be used further without further removal of the salts.
  • an acid preferably hydrochloric acid, sulfuric acid or acetic acid
  • the optional synthesis component (d) encompasses high molecular mass diols or polyols, by which is meant a number-average molecular weight of at least 400, preferably 400 to 6000.
  • the compounds in question are more particularly dihydric or polyhydric polyester polyols and polyether polyols, the dihydric polyols being preferred.
  • Suitable polyester polyols include, in particular, the conventional reaction products of polyhydric alcohols with polybasic carboxylic acids, with the alcoholic component being employed in excess.
  • the polybasic carboxylic acids may be aliphatic, cycloaliphatic, aromatic, heterocyclic or ethylenically unsaturated in nature and may also, if appropriate, carry halogen atom substituents.
  • the polybasic carboxylic acids it is also possible for their anhydrides to be esterified.
  • Suitable polybasic starting carboxylic acids include the following: succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride or fumaric acid.
  • Polyhydric alcohols for use in excess include the following: ethane-1 ,2-diol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 ,2-diol, butane-1 ,3-diol, butane-1 ,4-diol, butene-1 ,4-diol, butyne-1 ,4- diol, pentane-1 ,5-diol and its positional isomers, hexane-1 ,6-diol, octane-1 ,8-diol, 1 ,4-bishydro- xymethylcyclohexane, 2,2-bis4-hydroxycyclohexyl)propane, 2-methyl-1 ,3-propanediol, glycerol, trimethylolpropane, trimethylolethane, hexane-1 ,2,6-triol, butane-1
  • polyester polyols formed from diols and dicarboxylic acids.
  • polyester polyols are the adducts of lactones or lactone mixtures with dihydric alcohols used as starter molecules.
  • lactones are ⁇ -caprolactone, ⁇ -pro- piolactone, ⁇ -butyrolactone or methyl-e-caprolactone.
  • Suitable starter molecules are more particularly the low molecular mass dihydric alcohols already specified as synthesis components for the polyester polyols. Also suitable, of course, are polyesters formed from hydroxycarboxylic acids as synthesis components. Synthesis components (d) suitable as polyesters are, furthermore, also polycarbonates, of the kind obtainable, for example, from phosgene or diphenyl carbonate and, in excess, the low molecular mass dihydric alcohols specified as synthesis components for the polyester polyols.
  • Suitable synthesis components (d) with polyether polyol suitability include, preferably, polyether diols, of the kind obtainable, for example, by boron trifluoride-catalyzed linking of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin to itself or to one another, or by addition reaction of these compounds, individually or in a mixture, with starter components containing reactive hydrogen atoms, such as water, polyfunctional alcohols or amines such as ethane-1 ,2-diol, propane-1 ,3-diol, 1 ,2- or 2,2-bis(4-hydroxyphenyl)- propane, or aniline.
  • polyether diols of the kind obtainable, for example, by boron trifluoride-catalyzed linking of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
  • polyether-1 ,3-diols examples being trimethylolpropane which is alkoxylated on one OH group and whose alkylene oxide chain is capped with an alkyl radical comprising 1 to 18 C atoms, are synthesis components (d) employed with preference.
  • Optional synthesis components (e) may be low molecular mass dihydric or polyhydric alcohols, among which the dihydric alcohols are preferred.
  • Low molecular mass here denotes a number- average molecular weight from 62 to 399.
  • Suitable synthesis components (e) include ethane-1 ,2-diol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 ,2-diol, butane-1 ,3-diol, butane-1 ,4-diol, butene-1 ,4-diol, butyne-1 ,4-diol, pentane-1 ,5- diol and its positional isomers, hexane-1 ,6-diol, octane-1 ,8-diol, 1 ,4-bishydroxymethylcyclo- hexane, 2,2-bis(4-hydroxycyclohexyl
  • the polyisocyanates (A) generally have the following construction, based on isocyanate groups (calculated as NCO with a molecular weight of 42 g/mol) in synthesis component (a):
  • the NCO content of the polyisocyanates (A) of the invention is generally 13% by weight or more, preferably 14% by weight or more, more preferably 15% by weight or more, and very preferably 16% by weight or more, in conjunction with very good water-dispersibility. Normally 22% by weight is not exceeded.
  • component (b) is incorporated into the polyisocyanate or not is not relevant for the present invention. Without wishing to be bound to a theory it is assumed that at least a part of compound (b) of formula (II) is incorporated into polyisocyanate (A) by reaction of at least one free anionic oxygen group or hydroxy group. It is further assumed that the compounds of formula (II) remain in the water phase. For the sake of simplicity the component (b) is referred to as "incorporated" into polyisocyanate (A) throughout the description, regardless of their actual state of binding.
  • the viscosity of the water-emulsifiable polyisocyanates of the invention is below 10 000 mPa * s, preferably below 9000 mPa * s, more preferably below 8000 mPa * s, very preferably below 7000 mPa * s, and more particularly between 800 and 6000 mPa * s.
  • the component (b) in the polyisocyanates (A) of the invention are preferably at least partly neutralized with at least one base (B).
  • the bases in question may be basic alkali metal, alkaline earth metal or ammonium salts, more particularly the sodium, potassium, cesium, magnesium, calcium and barium salts, especially sodium, potassium, and calcium salts, in the form of hydroxides, oxides, hydrogen carbonates or carbonates, preferably in the form of the hydroxides.
  • Preferred base (B) is ammonia or amine, preferably amine, very preferably tertiary amine.
  • the tertiary amines in question are preferably those which are exclusively alkyl- substituted and/or cycloalkyl-substituted.
  • amines examples include trimethylamine, triethylamine, tri-n-butylamine, ethyldiisopropyl- amine, dimethylbenzylamine, dimethylphenylamine, triethanolamine, cyclopentyldimethylamine, cyclopentyldiethylamine, cyclohexyldimethylamine, and cyclohexyldiethylamine.
  • base (B) is N,N-dimethylcyclohexylamine.
  • the base (B) is used to neutralize 10 to 100 mol% of the acid groups present in (A), preferably 20 to 100 mol%, more preferably 40 to 100 mol%, very preferably 50 to 100 mol%, and more particularly 70 to 100 mol%.
  • the at least partial neutralization of component (b) in the polyisocyanate (A) can take place before, during or after the preparation of the polyisocyanate (A), preferably before the preparation.
  • An advantageous composition according to the present invention comprises as base (B) an amine of the following formula (IV): in which R 8 , R 9 and R 10 represent a hydrocarbon chain, advantageously selected from cycloalkyl or alkyl, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,
  • R 8 , R 9 and R 10 groups form cyclic structures.
  • R 8 and R 9 or R 9 and R 10 or R 8 and R 10 may thus together form a cyclic structure formed preferably of three to six carbon atoms and optionally containing at least one heteroatom preferably selected from oxygen or sulphur.
  • N-ethyl morpholine, N-methyl morpholine and 1 ,2,2,6, 6-pentamethylpiperidine are exam- pies of cyclic structures of this type.
  • R 8 , R 9 and R 10 represent, independently, a Ci - Ci8 alkyl substituted if appropriate by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles or C6 - Ci2 aryl substituted if appropriate by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles.
  • ⁇ , ⁇ -dimethylcyclohexylamine, ethyldiisopropylamine, dimethylbutylamine, dimethylbenzyla- mine, etc. are examples of amines which may be suitable within the scope of the invention.
  • N,N- dimethylcyclohexylamine is especially preferred.
  • the polyisocyanates (A) are generally prepared by mixing and reacting the synthesis components in any order. Preference is given to introducing the diisocyanate or polyisocyanate (a) initially, adding the synthesis components (b) and/or (c) together or in succession, and allowing reaction to take place until the reactive groups in (b) and (c) have been converted. Subsequently, if desired, the compounds (d) and/or (e) can be added.
  • reaction regime in which monomeric diisocyanates are reacted with one another as components (a) in the presence of the compounds (b) and/or (c).
  • a reaction regime of this kind is described in WO 2008/1 16764, hereby fully incorporated by reference as part of the present disclosure content.
  • the reaction is carried out in general at a temperature of between 40°C and 170°C, preferably between 45°C and 160°C, more preferably between 50 and 150°C, and very preferably between 60 and 140°C.
  • the reaction can be accelerated by adding the typical catalysts (C) which catalyze the reaction of isocyanate groups with isocyanate-reactive groups.
  • C catalysts
  • Suitable for this purpose in principle are all of the catalysts that are typically used in polyurethane chemistry.
  • These catalysts are, for example, organic amines, more particularly tertiary aliphatic, cycloali- phatic or aromatic amines, and/or Lewis-acidic organometallic compounds.
  • suitable Lewis-acidic organometallic compounds include tin compounds, such as tin(ll) compounds of organic carboxylic acids, for example, such as tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexoate, and tin(ll) laurate, for example, and the dialkyltin(IV) compounds of organic carboxylic acids, examples being dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate, and dioctylt
  • metal complexes such as acetylacetonates of iron, of titanium, of aluminum, of zirconium, of manganese, of nickel, and of cobalt. Further metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, vol. 35, pages 19- 29.
  • Dialkyltin(IV) compounds of organic carboxylic acids are, for example, dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate, and dioctyltin diacetate. Preference is given to dibutyltin diacetate and dibutyltin dilaurate. For toxicological reasons, tin compounds are less preferred, but are still frequently used in practice.
  • Lewis-acidic organometallic compounds are zinc(ll) dioctoate,
  • acetylacetonate and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate.
  • Bismuth and cobalt catalysts cerium salts such as cerium octoates, and cesium salts can also be used as catalysts.
  • Bismuth catalysts are more particularly bismuth carboxylates, especially bismuth octoates, ethylhexanoates, neodecanoates or pivalates; examples are K-KAT 348 and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from Shepherd Lausanne, and also catalyst mixtures of, for example, bismuth organyls and zinc organyls.
  • Preferred Lewis-acidic organometallic compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zirconium acetylacetonate, and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate. Additionally, bismuth catalysts and cobalt catalysts, and cesium salts too, can be used as catalysts.
  • Suitable cesium salts are those compounds in which the following anions are used: F- , CI- CIO- CIOs “ , CIO4-, Br, I-, IO3-, CN-, OCN-, ⁇ 0 2 " , ⁇ 0 3 " , HCOs " , COs 2" , S 2" , Shr, HSO3-, SO3 2 -, HSO4-, S0 4 2 -, S2O2 2 -, S2O4 2 -, S 2 0 5 2 -, S 2 0 6 2 -, S2O7 2 -, S 2 0 8 2 -, H2PO2-, H2PO4-, HPO4 2 -, PO4 3 -, P2O7 4 -, (OCnH 2n+ i)-, (C n H 2 n-i0 2 )-, and (C n+ i H 2 n-20 4 ) 2 -, where n stands for the numbers 1 to
  • cesium and bismuth carboxylates in which the anion conforms to the formulae and also (Cn+i with n being 1 to 20.
  • Particularly preferred cesium salts contain monocarboxylate anions of the general formula (C n H2n-i02) _ , where n stands for the numbers 1 to 20.
  • Particularly deserving of mention in this context are formate, acetate, propionate, hexanoate, and 2-ethylhexanoate.
  • reaction mixtures comprising polyisocyanates (A) thus obtained are generally used further as they are.
  • the reaction can be carried out optionally in an inert solvent or solvent mixture (E). After the reaction this solvent or solvent mixture is preferably not removed, but instead the
  • polyisocyanate with solvent is used directly.
  • polar, nonprotic solvents such as esters, ethers, glycol ethers and glycol esters, preferably propylene glycol ethers and esters, more preferably ethylene glycol ethers and esters, and also carbonates.
  • Esters are, for example, n-butyl acetate, ethyl acetate, 1 -methoxyprop-2-yl acetate, and 2-me- thoxyethyl acetate, gamma-butyrolactone, and also the monoacetyl and diacetyl esters of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, examples being butylglycol acetate and butyldiglycol acetate. Additionally conceivable are poly(C2 to C3)alkylene glycol (Ci to C4)monoalkyl ether acetates such as, for example, acetic esters of mono- or dipropylene glycol monomethyl ether.
  • esters are based on the following formula (I I I),
  • R 3 and R 4 independently of one another are alkyl, cycloalkyl, or aryl, it being possible for each of the stated radicals to be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles.
  • R 3 is alkyl, alkyloxy or alkoxyalkyl and R 4 is alkyl or alkoxyalkyl.
  • carbonates preferably 1 ,2-ethylene carbonate, more preferably 1 ,2-pro- pylene carbonate or 1 ,3-propylene carbonate.
  • Ethers are, for example, tetrahydrofuran (THF), dioxane, and the dimethyl, diethyl or di-n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, preferably dipropylene glycol dimethyl ether, which is available as an isomer mixture under the trade name Proglyde® DMM from Dow Chemical Company, for example.
  • THF tetrahydrofuran
  • dioxane dioxane
  • dimethyl, diethyl or di-n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, preferably dipropylene glycol dimethyl ether, which is available as an isomer mixture under the trade name Proglyde® DMM from Dow Chemical Company, for example.
  • a solvent (E) can also be added to the reaction mixture after the end of the reaction and prior to dispersion in the binder.
  • the mixture may further be admixed optionally with a further diisocyanate or, preferably, polyisocyanate (F), which can in principle be the same diisocyanates or polyisocyanates as set out above under (a), but which may also be different than said component (a).
  • component (F) can be used in an amount from 0 to twenty times the amount of the polyisocyanate (A), preferably from 0 to ten times the amount.
  • the present invention provides for an aqueous coating composition
  • an aqueous coating composition comprising at least one water-dispersible polyisocyanate (A) and at least one aqueous polyol component (D) as binder and the preparation of two-component polyurethane coating materials or aqueous dispersion- based adhesives.
  • the polyisocyanates (A) are mixed with an aqueous polyol component (D), preferably by being introduced into it. This is generally done with gentle to vigorous stirring, in order to disperse the polyisocyanates. It is an advantage of the polyisocyanates of the invention that they are readily dispersible in such aqueous solutions or dispersions of polyols as binders.
  • the process for preparing the aqueous coating composition comprises mixing a polyisocanate (A) with at least an aqueous polyol component (D) with an energy input of 0 to not more than 10 8 W/m 3 ' preferably at a maximum shear rate of 10 to 1000 s _1 , more preferably 10 to 500 s _1 , very preferably 10 to 250 s _1 .
  • the mixing of the a polyisocanate (A) with at least an aqueous polyol component (D) is preferably performed by hand-incorporation, for example by hand-stirring using a spatula or spoon, or by gentle agitation up to vigourous shaking by hand.”
  • the dispersible polyisocyanates (A) of the invention may optionally further be blended with additional polyisocyanates that have not been modified for dispersibility, examples being those polyisocyanates as listed under (a), and, after blending, can be reacted with the binders.
  • additional polyisocyanates that have not been modified for dispersibility
  • examples being those polyisocyanates as listed under (a)
  • the polyisocyanates (A) of the invention must be equipped with the actively dispersing components (b) and (c) in such a way that they are sufficiently dispersible in order to disperse the polyisocyanates in their entirety (polyisocyanate (A) and polyisocyanates which have not been modified for dispersibility).
  • the preparation of coating compositions from the water-emulsifiable polyisocyanates containing isocyanurate groups and prepared in accordance with the invention is accomplished by reaction with aqueous solutions, emulsions or dispersions of polyols: polyacrylate-ol, polyester-ol, poly- urethane-ol, polyether-ol, and polycarbonate-ol dispersions, and also their hybrids and/or mixtures of the stated polyols.
  • Hybrids means graft copolymers and other chemical reaction products which include chemically attached molecular moieties having different (or else like) groups from among those stated.
  • polyacrylate-polyol dispersions Preference is given to polyacrylate-polyol dispersions, polyester-polyol dispersions, polyether-polyol dispersions, polyurethane-polyol dispersions, polycarbonate-polyol dispersions, and their hybrids.
  • Polyacrylate-ols can be prepared as primary or secondary dispersions, emulsions, and solutions. They are prepared from olefinically unsaturated monomers. These are, firstly, comonomers containing acid groups, having for example carboxylic, sulfonic acid and/or phosphonic acid groups or their salts, such as (meth)acrylic acid, vinylsulfonic acid or vinylphosphonic acid, for example. These are, secondly, comonomers containing hydroxyl groups, such as hydroxyalkyi esters or amides of (meth)acrylic acid, such as 2-hydroxyethyl and 2 or 3-hydroxypropyl (meth)acrylate, for example.
  • acid groups having for example carboxylic, sulfonic acid and/or phosphonic acid groups or their salts, such as (meth)acrylic acid, vinylsulfonic acid or vinylphosphonic acid, for example.
  • comonomers containing hydroxyl groups such as hydroxyalkyi esters or
  • unsaturated comonomers which contain neither acidic groups nor hydroxyl groups, such as alkyl esters of (meth)acrylic acid, styrene and derivatives, (meth)acrylonitrile, vinyl esters, vinyl halides, vinyl imidazole, etc.
  • the properties can be influenced, for example, via the composition of the polymer, and/or, for example, via the glass transition temperatures of the comonomers (with different hardness).
  • One example of a commercially available secondary polyacrylate emulsion is Bayhydrol® A 145 (a product of Covestro).
  • Examples of a primary polyacrylate emulsion are Bayhydrol® VP LS 2318 (a product of Covestro) and Luhydran® products from BASF AG.
  • Macrynal® VSM 6299w/42WA from Cytec
  • Setalux® AQ products from Nuplex Resins such as Setalux® 6510 AQ-42, Setalux® 651 1 AQ-47, Setalux® 6520 AQ-45, Setalux® 6801 AQ-24, Setalux® 6802 AQ-24, and Joncryl® from BASF Resins.
  • Polyacrylate-ols may also have a heterogeneous structure, as is the case for core-shell structures.
  • Polyester-ols for aqueous applications are described for example in EP 537568 (US 5344873), EP 610450 (US 6319981 , polycondensation resin), and EP 751 197 (US 5741849, polyester- polyurethane mixture).
  • Polyester-ols for aqueous applications are, for example, WorleePol products from Worlee-Chemie GmbH, Necowel® products from Ashland-Sudchemie-Kernfest GmbH, and Setalux® 6306 SS-60 from Nuplex Resins.
  • Polyurethane-polyol dispersions for aqueous applications are described for example in
  • EP 469389 (US 559805). They are marketed, for example, under the brand name Daotan® from DSM NV.
  • EP 417998 EP 496205 (US 5387642), EP 542085 (5308912, polyacrylate/polyether mixture), EP 542105 (US 5331039), EP 543228 (US 533671 1 , polyester/polyacrylate hybrids),
  • EP 578940 (US 5349041 , polyester/urethane/carbonate), EP 758007 (US 5750613,
  • EP 751 197 (US 5741849)
  • EP 1 141065 (US 6590028).
  • Polyesters/polyacrylates are described for example in EP 678536 (US 5654391 ).
  • One example of a secondary polyester/polyacrylate emulsion is Bayhydrol® VP LS 2139/2 (a product of Bayer MaterialScience).
  • water-emulsifiable polyisocyanates of the invention it is generally enough to distribute the inventively obtained polyisocyanate in the aqueous dispersion of the polyol.
  • Generating the emulsion generally requires an energy input of 0 to not more than 10 8 W/m 3 .
  • generating the emulsion generally requires a maximum shear rate of 10 to 1000 s _1 , more preferably 10 to 500 s _1 , very preferably 10 to 250 s _1 .
  • the shear rate is defined according to DIN 1342-1 .
  • the water-emulsifiable polyisocyanates of the invention preferably comprising said at least one solvent (E) can be mixed advantageously at low shear rates, for example by hand-incorporation, with the aqueous dispersion of the polyol. Additionally, the optical properties of the coatings obtained with these coating materials are improved, when mixed at low shear rates, for example by hand-incorporation.
  • the dispersions generally have a solids content of 10% to 85%, preferably of 20% to 70% by weight and a viscosity of 10 to 1500 mPa * s.
  • polyisocyanate (A) and also, optionally, (F) and binders are mixed with one another 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 , more preferably 0.3:1 to 3:1 , and very preferably 0.5:1 to 2.5:1 , it also being possible, if appropriate, for further, typical coatings constituents to be mixed in, and the final composition is applied to the substrate.
  • the ratio of NCO to NCO-reactive groups when using a primary (polyacrylate) dispersion, is from 5:1 to 1 :5, preferably from 2:1 to 1 :2, and more preferably about 1 :1 . In another embodiment of the invention, when using a secondary (polyacrylate) dispersion, the ratio of NCO to NCO-reactive groups is from 0.8:1 to 2:1 , more particularly from 1 .2:1 to 1.7:1.
  • Curing typically takes place until the cured materials can be handled further.
  • the properties associated with this are, for example, dust drying, through-drying, blocking resistance or packability.
  • the curing takes place at room temperature within not more than 12 hours, preferably up to 8 hours, more preferably up to 6 hours and very preferably up to 4 hours.
  • the curing takes place, for example, for half an hour at
  • the coating of the substrates takes place in accordance with typical methods known to the skilled worker, which involve applying at least one coating composition in the desired thickness to the substrate that is to be coated, and removing any volatile constituents that may be present in the coating composition, if appropriate with heating. This operation can if desired be repeated one or more times.
  • Application to the substrate may take place in a known way, as for example by spraying, troweling, knifecoating, brushing, rolling, roller coating, pouring, laminating, injection backmolding or coextruding.
  • the thickness of a film of this kind to be cured can be from 0.1 ⁇ up to several mm, preferably from 1 to 2000 ⁇ , more preferably 5 to 200 ⁇ , very preferably from 10 to 60 ⁇ (based on the coating material in the state in which the solvent has been removed from the coating material). Also provided by the present invention are substrates coated with a multicoat paint system of the invention.
  • Polyurethane coating materials of this kind are especially suitable for applications requiring a particularly high level of application reliability, external weathering resistance, optical qualities, solvent resistance, chemical resistance, and water resistance.
  • the resulting coating compositions and coating formulations are suitable for coating substrates such as wood, wood veneer, paper, paperboard, cardboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as cement moldings, fiber- cement slabs or metals, each of which may optionally have been precoated and/or pretreated, more particularly for plastics surfaces.
  • substrates such as wood, wood veneer, paper, paperboard, cardboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as cement moldings, fiber- cement slabs or metals, each of which may optionally have been precoated and/or pretreated, more particularly for plastics surfaces.
  • Coating compositions of this kind are suitable as or in interior or exterior coatings, i.e., applications of this kind involving exposure to daylight, preferably of parts of buildings, coatings on (large) vehicles, trains and aircraft, and industrial applications, decorative coatings, bridges, buildings, power masts, tanks, containers, pipelines, power stations, chemical plants, ships, cranes, posts, sheet piling, valves, pipes, fittings, flanges, couplings, halls, roofs, and structural steel, furniture, windows, doors, woodblock flooring, can coating and coil coating, for floor coverings, as in the case of parking levels, or in hospitals, wood coatings for furniture and flooring application, and in automobile finishes as OEM and refinish application.
  • Coating compositions of this kind are preferably used at temperatures between ambient temperature to 80°C, preferably to 60°C, more preferably to 40°C.
  • the articles in question here are preferably those which cannot be cured at high temperatures, such as large machines, aircraft, large-volume vehicles, and refinish applications.
  • the resulting coating compositions and coating formulations are used for coatings of agricultural, construction and earthmoving equipment, for example agricultural machinery, tractors, excavators, cranes, for wood coatings for furniture, preferably kitchen parts, and flooring, preferably for on-side parquet coatings, beton coatings and plastic coatings, and for coatings in automotive and transportation application.
  • the coating compositions of the invention are employed more particularly as clearcoat, basecoat, and topcoat materials, primers, and surfacers.
  • Polyisocyanate compositions of this kind can be used as curing agents for producing coating materials, adhesives, and sealants.
  • coating materials, adhesives, and sealants comprising at least one polyisocyanate composition of the invention, and also substrates which are coated, bonded or sealed using them.
  • Figures in ppm or percent that are used in this specification relate, unless otherwise indicated, to weight percentages and ppm by weight.
  • water dispersible polyisocyanates (A) of the invention are miscible with aqueous polyol dispersions under low shear rates at high concentrations of components (a), (b) and (c), which results in a reduced VOC in the resulting coating compositions.
  • Polyisocyanate was prepared by trimerizing some of the isocyanate groups of
  • HDI 1,6-diisocyanatohexane
  • said polyisocyanate being composed substantially of tris(6- isocyanatohexyl) isocyanurate and its higher homologs, with an NCO content of 22.2% and a viscosity at 23°C of 2800 mPa * s (commercially available as BASONAT® HI100 at BASF SE, Ludwigshafen, Germany)
  • Monofunctional polyethylene oxide was prepared starting from methanol and with potassium hydroxide catalysis, with an average OH number of 1 12 mg KOH/g, measured to DIN 53 240, corresponding to a molecular weight of 500 g/mol.
  • the residues of catalyst still present were subsequently neutralized with acetic acid and the product was desalinated. In the course of this procedure, potassium acetate formed was also removed.
  • Pluriol® A500E at BASF SE, Ludwigshafen, Germany
  • the polyisocyanate from the above example was diluted to a solids content of 70% or 85% respectively with Butoxyl ® (3-Methoxy-butyl acetate from Celanese). Mixing was performed at 1200-1300 rpm with a lab stirrer for 5 min. After degassing with nitrogen, the diluted isocyanate was let standing without stirring for 1 d, to give the polyisocyanate (A). Usage of Bayhydrol ® A 145 as binder component (D)
  • the mixture was stirred for 45 min., and let stand without stirring for 1 d, to give 700 g of formulated dispersion component with a solids content of 35,0%.
  • the dispersion component (D) and the polyisocyanate (A) component were mixed at an index of 150, i.e. such, that in the lacquer, hydroxy and isocyanate groups have a stoichiometric ratio of 1 :1 ,5.
  • NeoCryl ® XK-101 Usage of NeoCryl ® XK-101 as binder component (D)
  • NeoCryl ® XK-101 from DSM NeoResins, solids content: 40%, OH value: 33,4 mgKOH/g emulsion
  • 4,5 g Byk-340 wetting agent from Byk
  • 40,8 g deionized water was stirred for 45 min., and let stand without stirring for 1 d, to give 600 g of formulated dispersion component with a solids content of 36,8%.
  • the dispersion component and the polyisocyanate component were mixed at an index of 100, i.e. such, that in the lacquer hydroxy and isocyanate groups have a stoichiometric ratio of 1 :1 .
  • dispersion component (D) 54,35 g of the dispersion component (D) were stirred at 500 rpm using a Dispermat ® lab stirrer. 6,80 g of the polyisocyanate component (100%, i.e., non-diluted) were added under stirring during 2-3 min. The mixture was then stirred at 1000 rpm for 5 min. to give the water-based two- component coating system.
  • sand trickles out of the funnel on the applied lacquer film.
  • the film is still tacky and the sand will stick on the coating, whereas, when surface cure has occurred, the sand will can be wiped away with a brush.
  • the distance, during which sand sticks on the surface represents the time the coating needs to surface-cure or to be sand dry.
  • through-cure can be measured.
  • Pendulum hardness was tested according DIN EN ISO 1522 using films prepared on glass via draw down bar (180 ⁇ wet layer thickness).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des polyisocyanates dispersibles dans l'eau améliorés destinés à des revêtements à comportement de séchage amélioré, plus particulièrement pour des matériaux de revêtement en polyuréthane à deux constituant.
PCT/EP2018/076072 2017-10-06 2018-09-26 Polyisocyanates dispersibles dans l'eau Ceased WO2019068529A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021151774A1 (fr) * 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
EP3929230A1 (fr) * 2020-06-24 2021-12-29 Evonik Operations GmbH Utilisation d'esters d'acide phosphorique à longue chaîne dans des dispersions aqueuses de polyuréthane
WO2024059451A1 (fr) * 2022-09-16 2024-03-21 Ppg Industries Ohio, Inc. Compositions de revêtement à base de solvant comprenant un polyisocyanate dispersible dans l'eau
EP4357382A1 (fr) * 2022-10-19 2024-04-24 Covestro Deutschland AG Mélange de polyisocyanates modifié ioniquement
WO2024112978A1 (fr) * 2022-11-24 2024-05-30 Michael Windsor Symons Compositions d'imprégnation de bois

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021151774A1 (fr) * 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
CN115427473A (zh) * 2020-01-30 2022-12-02 巴斯夫欧洲公司 包含水分散性聚异氰酸酯的颜色稳定的固化剂组合物
EP3929230A1 (fr) * 2020-06-24 2021-12-29 Evonik Operations GmbH Utilisation d'esters d'acide phosphorique à longue chaîne dans des dispersions aqueuses de polyuréthane
WO2024059451A1 (fr) * 2022-09-16 2024-03-21 Ppg Industries Ohio, Inc. Compositions de revêtement à base de solvant comprenant un polyisocyanate dispersible dans l'eau
EP4357382A1 (fr) * 2022-10-19 2024-04-24 Covestro Deutschland AG Mélange de polyisocyanates modifié ioniquement
WO2024112978A1 (fr) * 2022-11-24 2024-05-30 Michael Windsor Symons Compositions d'imprégnation de bois

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