EP0851881A1 - Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto - Google Patents

Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto

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Publication number
EP0851881A1
EP0851881A1 EP96934462A EP96934462A EP0851881A1 EP 0851881 A1 EP0851881 A1 EP 0851881A1 EP 96934462 A EP96934462 A EP 96934462A EP 96934462 A EP96934462 A EP 96934462A EP 0851881 A1 EP0851881 A1 EP 0851881A1
Authority
EP
European Patent Office
Prior art keywords
group
polyurethane
groups
compounds
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96934462A
Other languages
German (de)
English (en)
Inventor
Nicolas Kokel
Maria Gyopar Rau
Roland Ettl
Harald Larbig
Johann-Peter Melder
Erich Gulbins
Thomas Wirth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19618675A external-priority patent/DE19618675A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP0851881A1 publication Critical patent/EP0851881A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/5039—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds

Definitions

  • the present invention relates to aqueous dispersions containing a polyurethane (A) containing structural units which are derived from compounds of the formula (I)
  • R 1 , R 2 , R 3 each hydrogen, -C ⁇ ⁇ to C 24 alkyl or C ⁇ - to C 24 alkenyl
  • R 4 is hydrogen
  • R 5 , R 6 a) together C 4 - to Cio-alkanediyl
  • XC 2 - to Cg-alkanediyl means and R 7 is synonymous with R 5 or R 6 with the exception that R 7 is not a radical of the formula II,
  • radicals R 5 and R 6 carry a total of 2 to 5 hydroxyl groups bonded to an aliphatic carbon atom and
  • radical R 5 and / or R 6 1 or 2 aromatically bound hydroxyl groups or 1 nitrile, tertiary amino,
  • Carboxylic acid or sulfonic acid group which may be present in the form of their salts.
  • Aqueous dispersions which contain polyurethanes are generally known (cf. D. G. Oertel "Kunststoff Handbuch 7", 2nd edition, 1983, Carl Hanser Verlag Kunststoff Vienna, pp. 24 to 25 and pp. 571 to 574). It is also known to use the polyurethane dispersions as coating agents, e.g. to be used as varnishes or printing inks.
  • the lacquers should be storable over a longer period of time without changing their properties (e.g. theological properties) or the properties of the coatings produced with them.
  • the paints should contain the smallest possible amounts of solvents, leveling agents or other volatile organic components in order to minimize the emissions of organic compounds during the application and drying of the paints.
  • the varnish After application to the workpiece, the varnish should dry or harden quickly so that it is ready for use in a short time or can be processed further.
  • the lacquers should be able to be processed using the largest possible number of conventional processes.
  • the various methods associated with different efforts, the effort being corrected with the quality of the coatings produced with them, are required in order to be able to produce coatings that are very specific to one another in the most economical way possible
  • the method of cold curing (curing of the coating at room temperature) with a one-component coating system is the least complex and should meet medium quality requirements.
  • the method of cold curing with a two-component coating system which is associated with increased effort for the processor to mix the coating system and the narrowly limited processing time of the mixing, should meet the high quality requirements.
  • the baking process (curing at temperatures of usually 100 to 160 ° C.) is suitable for the production of coatings of the highest quality.
  • Printing inks are usually intended to meet the same requirements with regard to the properties of use which have already been mentioned for the coatings. In addition, the fulfillment of further requirements specific to printing inks is important:
  • Polyurethane dispersions which can be used as one-component systems for coating different substrates, are described in EP-B-0332326.
  • they In addition to a water-dispersible polyurethane, they contain a molecular weight of more than 2000, which carries carbonyl groups in keto or aldehyde function, another component which carries hydrazine or hydrazone groups or the polyurethane carries, in addition to the carbonyl groups in keto or aldehyde function, hydrazine or hydrazone groups.
  • this document proposes to incorporate keto groups into the polyurethane by using monomers such as the Michael adduct of diacetone acrylamide and diethanolamine.
  • monomers such as the Michael adduct of diacetone acrylamide and diethanolamine.
  • these can be processed by the method of cold curing as a one-component system to give coatings with satisfactory properties, they are not suitable as a component in two-component systems for producing coatings with a high level of properties. Processing by the stoving process also does not provide coatings that meet high standards.
  • aqueous dispersions containing a water-dispersible polyurethane with carbonyl groups and a polyhydrazide are known from DE-A-3 837 519.
  • the carbonyl function is inserted into the polyurethane by producing carbonyl groups during its preparation
  • Mono or poly alcohols are used, for example Hydroxyacetone, hydroxybenzaldehyde, acetoin, benzoin, adducts of diepoxides and ketocarboxylic acids and ketocarboxylic acid esters with at least one hydroxyl group.
  • these dispersions it is also recommended to use these dispersions as lacquer or printing ink.
  • the dispersions which contain polyurethanes built up from polyhydroxycarbonyl compounds, still leave something to be desired if increased demands are placed on the storage stability.
  • Coatings from dispersions which contain a polyurethane which are composed of the monohydroxycarbonyl compounds mentioned cannot yet completely satisfy the mechanical properties and the resistance to solvents. In addition, these dispersions tend to form coagulate.
  • EP-A-0646609 also recommends the use of polyurethane dispersions as printing inks.
  • the polyurethanes disclosed there have terminal hydrazine groups as functional groups and are water-dispersible because of their ionic group and polyalkylene oxide group content.
  • the object of the present invention was therefore to provide aqueous paints with an overall high level of application technology, which do not have the deficiencies of the prior art and which, when processed into glossy, highly stressable coatings, have no or only relatively little small amounts of volatile flow control agents must be used.
  • the coatings should be as flexible as possible, i.e. that the level of properties of the coatings that can be achieved with them should not lag behind that of the prior art when using various processing methods.
  • the object was to provide printing inks which do not have the deficiencies of the prior art and with which printed, non-polar substrates, in particular, can also be produced, on which the ink adheres permanently.
  • the dispersions contain a polyurethane (A) which contains structural units which differ from compounds of the formula (I)
  • R 1 , R 2 , R 3 are each hydrogen, -C ⁇ to C 24 alkyl or C ⁇ to C 24 alkenyl
  • R 4 means hydrogen
  • R 5 , R 6 generally mean:
  • each C - to 0 C ⁇ -alkyl particularly preferably C - and C 3 alkyl or C 5 - to C ⁇ cycloalkyl, preferably cyclopentyl or cyclohexyl, or C - to
  • R 7 has the same meaning as R 5 or R 6, with the exception of the radical of the formula II, c) in each case denotes a hydroxyl-terminated poly- (C 2 - to C 4 -alkylene oxide), preferably a radical of the formula III,
  • R 8 is hydrogen, methyl and / or ethyl
  • n 1 to 10
  • radicals R 5 and R 6 together carry 2 to 5 hydroxyl groups bonded to an aliphatic carbon atom and optionally the radical R 5 and / or R 6 carries 1 or 2 aromatically bound hydroxyl groups or 1 nitrile, tertiary amino, carboxylic acid or sulfonic acid group, which are optionally present in the form of their salts.
  • the content of the carbonyl groups of the structural elements derived from the compounds of the formula (I) in the polyurethane is chosen such that in general 3 to 140, preferably 6 to 100, particularly preferably 10 to 90 mmol of these groups are present per 100 g of polyurethane.
  • aqueous dispersions according to the invention are usually prepared by
  • bl 10 to 100 mol%, based on the total amount of polyols (b), have a molecular weight of 500 to 5000 and
  • Suitable monomers (a) are the polyisocyanates customarily used in polyurethane chemistry.
  • diisocyanates X (NCO) 2 where X is an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexaethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, l-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis- (4- isocyanate-cyclohexyl) propane, trimethylhexane diisocyanate, 1,4-diisocyanate-topzole, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, tetramethylxylylene diisocyanate (TMXDI), 2,4'-diisocyanato- diphenylmethane, p-xylylene diisocyanate, the isomers of bis- (4-iso
  • the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanate diphenylmethane are particularly important, in particular the mixture of 80 mol% of 2,4 diisocyanatotoluene and 20 mol% of 2,6-diisocyanatotoluene are suitable.
  • mixtures of aromatic isocyanates such as 2,4 diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to 1 : 4 is.
  • isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, e.g. Wear uretdione or carbodiimide groups.
  • those isocyanates can also be used which carry only one isocyanate group. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers.
  • the monoisocyanates usually carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane which enable the dispersion or crosslinking or further polymer-analogous reactions of the polyurethane.
  • monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI) are used.
  • isocyanates are e.g. obtained by reacting divalent isocyanates with one another by derivatizing part of their isocyanate groups to allophanate, biuret or isocyanurate groups.
  • Commercially available compounds are, for example, the isocyanurate or the biuret of hexamethylene diisocyanate.
  • Suitable higher functional polyisocyanates are e.g. Polyisocyanates containing urethane groups based on 2,4- and / or 2,6-diisocyanatotoluene, isophorone diisocyanate or tetra-methylene diisocyanate on the one hand and low molecular weight polyhydroxy compounds such as trimethylolpropane on the other.
  • the polyols (b) used are primarily higher molecular weight polyols, preferably diols (b1), which have a molecular weight of approximately 500 to 5000, preferably approximately 1000 to 3000 g / mol.
  • the polyols (b1) are, in particular, polyester polyols which are known, for example, from Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Volume 19, pp. 62 to 65. Polyester polyols which are obtained by reacting dihydric alcohols with dihydric carboxylic acids are preferably used. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • suberic acid azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexaprophthalic anhydride, tetrachlorophthalic anhydride, endo-methylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, fatty acid, maleic acid, fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid.
  • Dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
  • polyhydric alcohols examples include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol , Polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • x is a number from 1 to 20 / preferably an even number from 2 to 20.
  • polycarbonate diols such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as structural components for the polyester polyols.
  • Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones with terminal hydroxyl groups to suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20. Examples are ⁇ -caprolactone, ß-propiolactone, ⁇ -butyrolactone and / or methyl- ⁇ -caprolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the structural component for the polyester polyols. 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.
  • the corresponding chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.
  • the polyesterols can also be made up of minor amounts of mono- and / or higher-functional monomers.
  • polyether diols are suitable as monomers (b1). They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, optionally in a mixture or in succession, to starting components with reactive Hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 1,2-bis (4-hydroxydiphe- nyl) propane or aniline available.
  • Polytetrahydrofuran with a molecular weight of 240 to 5000, and especially 500 to 4500, is particularly preferred.
  • polyhydroxyolefins preferably those with 2 terminal hydroxyl groups, e.g. ⁇ -w-Dihydroxypolybutadien, ⁇ -w-Dihydroxypolymethacryles he or ⁇ -w-Dihydroxypolyacrylester as monomers (bl).
  • Such compounds are known for example from EP-A-0622378.
  • Other suitable polyols are polyacetals, polysiloxanes and alkyd resins.
  • the polyols can also be used as mixtures in any ratio.
  • the hardness and the modulus of elasticity of the polyurethanes can be increased if, in addition to the polyols (b1), low molecular weight diols (b2) with a molecular weight of about 62 to 500, preferably 62 to 200 g / mol, are used as polyols (b).
  • polyester polyols The structural components of the short-chain alkanediols mentioned for the production of polyester polyols are primarily used as monomers (b2), preference being given to neopentyl glycol and the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms.
  • the proportion of polyols (bl), based on the total amount of polyols (b), is preferably 10 to 100 mol% and the proportion of monomers (b2), based on the total amount of polyols (b), 0 to 90 mol%.
  • the ratio of the polyols (bl) to the monomers (b2) is particularly preferably 0.2: 1 to 5: 1, particularly preferably 0.5: 1 to 2: 1.
  • Compounds of the formula (I) are particularly suitable as component (c).
  • the compounds of formula (I) can be obtained by using a diketene of formula (IV)
  • a diketene is particularly preferably used in which the radicals R 1 , R 2 and R 3 are hydrogen or one of the radicals R 1 or R 2 is hydrogen and the other radical R 1 or R 2 and the radical R 3 are linear ⁇ rer, saturated, unsubstituted hexadecyl radical.
  • Particularly preferred amines are monoaminopolyols with two aliphatically bound hydroxyl groups, such as l-amino-2,3-propanediol, 2-amino-l, 3-propanediol, 2-amino-2-methyl-l, 3-propanediol,
  • monoaminopolyols with more than 2 aliphatically bound hydroxyl groups such as tris (hydroxymethyl) methyl-a in), 2- [tris (hydroxymethyl) methylamino] ethanesulfonic acid, 3- [tris (hydroxymethyl) methylamino] - propanesulfonic acid, N- [tris [hydroxymethyl) methyl] glycine, tris (3-hydroxypropyl) methylamine, glucamine and N- (2-hydroxyethyl) glucamine or diaminodiols, such as N, N'-bis- (2-hydroxyethyl) ethylenediamine, reaction products from a diprimary polyetherdiae in and per mole of polyetherdiamine 2 moles of ethylene, propylene and / or butylene oxide, the conditions for the reaction of the polyetherdiamine with the alkylene oxide to be selected so that highly selective the N, N'-bis (hydrooxyalkylamine)
  • polyether diamines examples are e.g. 4,7-dioxadecane-l, 10-diamine, 4,11-dioxatetradecane-l, 14-diamine, ⁇ - (2-aminomethyl-ethyl) - ⁇ - (2-aminomethyl-ethoxy) -poly [oxy (me- thyl-1,2-ethanediyl)] with a MW of 200 to 3000, and ⁇ - (3-aminopropyl) - ⁇ - (3-aminopropoxy) poly [oxy (1,4-butanediyl)] with a MG from 300 to 3000.
  • Monoaminopolyols with only one aliphatically bound hydroxyl group such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, N -butylethanolamine, leucinol, isoleucinol, valinol, Prolinol, hydroxy thylaniline, 2- (hydroxymethyl) piperidine, 3- (hydroxymethyl) piperidine, 2- (2-hydroxyethyl) piperidine, 2-amino-2-phenylethanol, 2-amino-l-phenylethanol, ephedrine, p-hydroxyephedrine, norephedrine, adrenaline, noradrenaline, serine, isoserine, phenylserine, 1,2-diphenyl-2-aminoethanol, 3-amino-l-propanol,
  • 2-amino-l-propanol 2-amino-2-methyl-l-propanol, isopropanolamine, N-ethyl-isopropanolamine, 2-amino-3-phenylpropanol, 4-amino-l-butanol, 2-amino-l- butanol, 2-aminoisobutanol, neopentanolamine, 2-amino-l-pentanol, 5-amino-l-pentanol, 2-ethyl-2-butyl-5-aminopentanol, 6-amino-l-hexanol,
  • Compounds of the formula (I) prepared from monoamino monoalcohols or polyamino monoalcohols, based on the amount of all monomers (c), are preferably used in amounts of not more than 50, particularly preferably not more than 20, mol%.
  • Such monomers (c) from mono- or polyaminomonoalcohols are used, for example, in minor amounts to control the viscosity of the polyurethane synthesis.
  • Preferred adducts of the formula I are those from the diketene in which the radicals R 1 , R 2 and R 3 are hydrogen and the compounds (Ia).
  • the compounds of the formula (I) can be prepared, for example, in the manner described for the acetoacetic acid amide derivatives in the patents DE 1 142 859 or GB 715 896.
  • condensates which contain structural elements which are derived from compounds of the formula (I) (condensates I) such as polyester compounds containing carbonyl groups uses polyols with a molecular weight of 300 to 5000 and which, for example, by polycondensation of
  • the monomers (d), which are different from components (b) and diols (c), are generally used for crosslinking or chain extension. They are generally more than dihydric non-aromatic alcohols, amines with 2 or more primary and / or secondary amino groups, and compounds which, in addition to one or more alcoholic hydroxyl groups, carry one or more primary and / or secondary amino groups.
  • Alcohols with a higher valence than 2, which can serve to set a certain degree of branching or crosslinking, are e.g. Trimethylolpropane, glycerin or sugar.
  • monoalcohols which, in addition to the hydroxyl group, carry a further group which is reactive toward isocyanates, such as monoalcohols with one or more primary and / or secondary amino groups, for example monoethanolamine.
  • monoalcohols with one or more primary and / or secondary amino groups for example monoethanolamine.
  • Polyamines with 2 or more primary and / or secondary amino groups are used above all when the chain extension or crosslinking is to take place in the presence of water, since amines generally react faster with alcohols or water with isocyanates. This is often necessary when aqueous dispersions of crosslinked polyurethanes or high molecular weight polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to disperse them rapidly in water and then to extend or crosslink them by adding 10 compounds with several isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines in the molecular weight range from 32 to 500 g / mol, preferably from
  • diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophorondia in,
  • Aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
  • the amines can also be in blocked form, e.g. in the form of the corresponding ketimines (see, for example, CA-1 129 128), ketazines (see, for example, US Pat. No. 4,269,748) or amine salts (see US Pat. No. 4,292,226).
  • Oxazolidines as are used, for example, in US Pat. No. 4,192,937, are blocked polyamines which can be used for the production of the polyurethanes according to the invention for chain extension of the prepolymers. When such capped polyamines are used, they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or part of the dispersion water, so that the corresponding polyamines are released hydrolytically.
  • the polyurethanes preferably contain no polyamine or 1 to 10, particularly preferably 4 to 8 mol%, based on the total amount of components (b), (c) and (d) of a polyamine with at least 2 40 amino groups reactive towards isocyanates as monomers ( d).
  • monoalcohols can be used for chain termination in minor amounts, ie preferably in amounts of less than 10 mol%, based on components (b) and (d). Their function is generally similar to that of monoisocyanates, that is, they serve mainly for the functionalization of the polyurethane with free-radically polymerizable C DoppelC double bonds.
  • monoalcohols are used for chain termination in minor quantities, i.e. preferably in amounts of less than 10 mol, based on the components (b) and (d). Their function is generally similar to that of monoisocyanates, i.e. they mainly serve to functionalize the polyurethane with free-radically polymerizable C polymerC double bonds.
  • the polyurethanes are composed of monomers different from components (a), (b), (c) and (d) (e) which carry at least one isocyanate group or at least one group which is reactive toward isocyanate groups and moreover at least one hydrophilic group or a group which can be converted into hydrophilic groups.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react with isocyanates much more slowly than the functional groups of the monomers which serve to build up the main polymer chain.
  • the proportion of the components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c), (d) and (e) is generally such that the molar amount of the (potentially) hydrophilic Groups, based on the amount by weight of all monomers (a) to (e), is 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 400 mmol / kg.
  • the (potentially) hydrophilic groups can be non-ionic or preferably (potentially) ionic hydrophilic groups.
  • Particularly suitable nonionic hydrophilic groups are polyethylene glycol ethers composed of preferably 5 to 100, preferably 10 to 80, repeating ethylene oxide units.
  • the content of polyethylene oxide units is generally from 0 to 10, preferably from 0 to 6,% by weight, based on the amount by weight of all monomers (a) to (e).
  • Preferred monomers with nonionic hydrophilic groups are the reaction products of a polyethylene glycol and a diisocyanate, which carry a terminally etherified polyethylene glycol residue.
  • diisocyanates and processes for their preparation Position are given in the patents US 3 905 929 and US 3 920 598.
  • Ionic hydrophilic groups are, above all, anionic groups such as the sulfonate, carboxylate and phosphate groups in the form of their alkali metal or ammonium salts, and also cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • ionic hydrophilic groups are above all those which can be converted into the above-mentioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, e.g. Carboxylic acid groups, anhydride groups or tertiary amino groups.
  • cationic monomers (e) especially monomers with tertiary amino groups are of particular practical importance, for example: tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl dialkylamines , Tris- (amino-alkyl) -amines, N, N'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, the alkyl radicals and alkanediyl units of these tertiary amines independently of one another from 2 to 6 carbon atoms consist.
  • polyethers having tertiary nitrogen atoms and preferably having two terminal hydroxyl groups such as those e.g. by alkoxylation of two amines containing hydrogen atoms bound to amine nitrogen, e.g. Methyl ⁇ amine, aniline, or N, N '-dimethylhydrazine, which are accessible in a conventional manner, into consideration.
  • polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are either treated with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids, or by reaction with suitable quaternizing agents such as C_ . - to
  • C 6 _ alkyl halides for example bromides or chlorides, are converted into the ammonium salts.
  • Suitable monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which have at least one alcoholic hydroxyl group or at least one wear primary or secondary amino group.
  • Dihydroxyalkylcarboxylic acids are preferred, especially those with 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054.
  • DMPA dimethylol propionic acid
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid are also suitable.
  • dihydroxyl compounds with a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups, which are known from DE-A 3 911 827. They can be obtained by reacting dihydroxyl compounds with tetracarboxylic acid dianhydrides such as pyromellitic acid dianhydride or cyclopentantetracarboxylic acid dianhydride in a molar ratio of 2: 1 to 1.05: 1 in a polyaddition reaction.
  • Particularly suitable dihydroxyl compounds are the monomers (b2) listed as chain extenders and the polyols (b1).
  • Suitable monomers (e) with amino groups that are reactive toward isocyanates are amino carboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimeric diamines mentioned in DE-A2034479 with ⁇ , ⁇ -unsaturated carboxylic acids such as the N- (2-amino- ethyl) -2-aminoethane carboxylic acid and the corresponding N-aminoalkylaminoalkylcarboxylic acids, where the alkanediyl units consist of 2 to 6 carbon atoms.
  • amino carboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimeric diamines mentioned in DE-A2034479 with ⁇ , ⁇ -unsaturated carboxylic acids such as the N- (2-amino- ethyl) -2-aminoethane carboxylic acid and the corresponding N-aminoalkyla
  • monomers with potentially ionic groups are used, they can be converted into the ionic form before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture.
  • the carboxylate groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as counterion. It is generally known in the field of polyurethane chemistry how the molecular weight of the polyurethanes can be adjusted by selecting the proportions of the monomers reactive with one another and the arithmetic mean of the number of reactive functional groups per molecule.
  • the ratio A: B is very particularly preferably as close as possible to 1: 1.
  • monomers with only one reactive group are generally used in amounts of up to 15 mol%, preferably up to 8 mol%, based on the Total amount of components (a), (b), (c), (d) and (e) used.
  • the polyaddition of components (a) to (e) generally takes place at reaction temperatures of 20 to 180 ° C., preferably 50 to 150 ° C. under normal pressure or under autogenous pressure.
  • reaction times can extend from a few minutes to a few hours. It is known in the field of polyurethane chemistry how the reaction time is influenced by a large number of parameters such as temperature, concentration of the monomers and reactivity of the monomers.
  • the customary catalysts such as dibutyltin dilaurate, stannous octoate or diazabicyclo (2,2,2) octane, can also be used.
  • Stirred kettles are suitable as polymerization apparatus, in particular when low viscosity and good heat dissipation are ensured by the use of solvents. If the reaction is carried out in bulk, extruders, in particular self-cleaning multi-screw extruders, are particularly suitable due to the usually high viscosities and the usually short reaction times.
  • the dispersions are prepared by one of the following processes:
  • an anionic polyurethane is produced from components (a) to (e) in a water-miscible solvent that boils at normal pressure below 100 ° C. Sufficient water is added until a dispersion is formed in which water is the coherent phase.
  • the "prepolymer mixing process” differs from the acetone process in that not a fully reacted (potentially) anionic polyurethane, but first a prepolymer is produced which carries isocyanate groups.
  • Components (a) to (d) are chosen so that the ratio A: B according to the definition is greater than 1.0 to 3, preferably 1.05 to 1.5.
  • the prepolymer is first dispersed in water and then crosslinked by reaction of the isocyanate groups with amines which carry more than 2 amino groups reactive towards isocyanates or chain-extended with amines which carry 2 amino groups reactive towards isocyanates. Chain extension also takes place when no amine is added. In this case, isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers to extend the chain.
  • the prepolymer is produced in two steps.
  • components (c) and optionally (b2) and part of component (a) are first reacted with one another until the isocyanate groups of component (a) are virtually completely reacted.
  • the progress of the reaction can be measured by measuring the NCO value, i.e. by determining the number of NCO groups still present.
  • the remaining components, if appropriate after reaction with one another are mixed into a prepolymer, the reaction mixture formed from (a), (c) and, if appropriate, (b2) is added, and the reaction is continued.
  • the Dispersions have a solvent content of less than 10% by weight and are very particularly preferably free of solvents.
  • the dispersions generally have a solids content of 10 to 75, preferably 20 to 65% by weight and a viscosity of 10 to 500 m Pas (measured at a temperature of 20 ° C. and a shear rate of 250 s " 1 ).
  • aqueous dispersions according to the invention are usually practically free of polyvalent metal ions.
  • Hydrophobic auxiliaries which can be difficult to distribute homogeneously in the finished dispersion, such as phenol condensation resins made from aldehydes and phenol or phenol derivatives or epoxy resins and others e.g. Polymers mentioned in DE-A-3903538, 43 09 079 and 40 24 567, which serve, for example, as adhesion improvers in polyurethane dispersions, can be applied to the polyurethane or the prepolymer before the dispersion by the methods described in the two abovementioned documents be added. Suitable hydrophobic auxiliaries are mentioned, for example, in DE-A-3903538, 4024567 and 43 09 079.
  • Suitable monomers (f) include the Ci to C ß alkyl esters of (meth) acrylic acid and lauryl acrylate, and butanediol diacrylate or carbonyl compounds such as methyl vinyl ketone, (meth) acrolein, crotonaldehyde, diacetone (meth) acrylamide, diacetone (meth ) acrylate.
  • vinyl esters of carboxylic acids containing up to 20 C atoms such as vinyl laurate, stearate, vinyl acetate and vinyl propionate
  • vinyl aromatics with up to 20 C atoms such as styrene and vinyl toluene
  • the monomer (f) can be added during the synthesis of the polyurethane (A), before the dispersion of the polyurethane (A) or the aqueous dispersion containing the polyurethane (A) and can be radically polymerized by conventional methods.
  • radical-forming polymerization initiators are added to the mixture of the polyurethane dispersion and the monomer (f).
  • the monomer (f) can be metered in as feed in an initiator-containing polyurethane dispersion.
  • the aqueous dispersion is usually a crosslinking agent (B) which has functional substituents which are linked to the structural units which are derived from compounds of the formula (I) in an addition or React condensation reaction, added.
  • crosslinking agents (B) are, for example
  • Suitable polyamines are e.g. non-polymeric amines, e.g. Ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, butylene diamine, 1,6-hexane diamine, 1,12-dodecane diamine, cyclohexylene diamine, piperazine, 2-methyl piperazine, isophorone diamine, phenylene diamine, tolylene diamine, xylylene diamine diamine, 4,4'-diamine diamine , Menthandiamine and m-xylenediamine.
  • the reactive amino compound can also be a polymer, such as e.g. an amino group-containing acrylic, polyester or polyurethane resin, a polypropylene oxide with amino groups (Jeffaine), or a polyethyleneimine.
  • amines can also be used in blocked form, ie in the form of their aldimines or ketimines.
  • blocked amines are generally known and are described, for example, by KJ Kim and RC Williams in “Proceedings of the annual Water-Borne and Higher Solids Symposium, New Jersey, 57, (1993)” and by B. Vogt-Birnbrich in “Proceedings of the 2nd International Conference in Organic Coatings, Athens, 55, (1995) "and in EP-A-552469 and EP-A-584818.
  • Amines blocked with aromatic aldehydes such as benzaldehyde are preferably used.
  • Suitable polyhydrazides are, for example, dicarboxylic acid dihydrazides as described, for example, in EP-A-442 652, page 11, line 52 to page 12, line 1. These are preferably derived from dicarboxylic acids, from which the polyester diols which can be used as component (b1) are also built up.
  • the corresponding polyhydrazone derivatives can also be used, for example those derived from acetone or butanone.
  • crosslinking agents (B) are polyisocyanates, which have a crosslinking effect through re-elimination. Such compounds are described, for example, in DE-A-4121946.
  • Crosslinking agents with aminooxy groups which can also be used in the form of their salts, are e.g. known from EP-A-516 074 or from DE-A-4219384.
  • a further crosslinking option is the addition of aldehydes with one or more aldehyde groups, which may also be protected, to the dispersion according to the invention.
  • Suitable monoaldehydes are, for example, compounds of the formula XR 9 -CHO, in which R 9 is a C 1 -C 10 -alkanediyl radical and X is a hydrogen atom or a hydroxycarbonyl radical.
  • Preferred aldehydes are formaldehyde, acetaldehyde and benzaldehyde.
  • Suitable multi-functional aldehydes are low molecular weight compounds, in particular aliphatic aldehydes of the formula OCH- (CH) n -CHO, where n is an integer from 0 to 8, preferably from 0 to 4, such as glyoxal or glutardialdehyde.
  • oligomers, polymers or copolymers of ethylenically unsaturated, free-radically polymerizable aldehydes are, for example, acrolein, methacrolein, formylstyrene and hydroxymethylfurfuryl (meth) acrylate.
  • Crosslinking components of this type if they are not sufficiently soluble, can be dispersed in the aqueous phase of the dispersion and, when used as binders, can take part in the film formation. Oligomeric or polymeric crosslinking components th of this type with a molecular weight of 1000 to 500,000 (weight average) are preferred.
  • Protected aldehyde groups are understood to mean corresponding derivatives which have a comparable reactivity to the free aldehyde groups themselves. Acetals, mercaptals and mercaptols, dioxolanes and dithiolanes. Acetal or dioxolane groups which have arisen from the reaction of aldehyde groups with alkanols having 1 to 4 carbon atoms in the alkyl radical or with alkanediols with 2 or 3 carbon atoms in the alkylene radical are preferred.
  • Examples of unsaturated monomers with protected aldehyde functions are diethoxypropyl acrylate and methacrylate and acryloyl- or methacryloyl-oxypropyl-1,3-dioxolane.
  • aldehyde derivatives are aldimine compounds which are obtained by the reaction of an optionally substituted, aromatic or heteroaromatic aldehyde with an optionally polyfunctional primary amine. These compounds are well known and are e.g. in EP 552 469 A3 or in US Pat. No. 5,451,653
  • Suitable Michael acceptors are generally known compounds which are described in DE-A-42 37 492.
  • the crosslinking is generally carried out by Michael addition in the presence of a catalyst.
  • Suitable catalysts are Lewis bases or Brönstedt bases, as described in DE-A-42 37 492.
  • the amounts of components (A) and (B) are preferably selected such that the molar ratio of the carbonyl groups of the structural elements derived from the compounds of the formula (I) to the functional substituents of the compounds (B) 0.1: 1 to 10: 1 is preferably 1.5: 1 to 0.5: 1.
  • crosslinking agents (B) are aminoplast resins, for example melamine-formaldehyde condensation products as described in DH Solomon, The Chemistry of Organic Filmpolymers, p. 235 ff, John Wiley & Sons, New York, 1967. They are preferably melamine-formaldehyde condensation resins with a molecular weight of preferably 250 to 1000, particularly preferably their partially or completely etherified derivatives. The degree of etherification is preferably at least 45% based on the maximum possible etherification.
  • the melamine-formaldehyde condensate onproducts are etherified with monoalcohols of 1 to 4 carbon atoms, such as, for example, with methanol, ethanol, propanol and preferably with butanol, and / or monoethers of diols with a total of 2 to 7 carbon atoms.
  • melamine-formaldehyde condensation products can also be partially replaced by other crosslinking aminoplasts, such as those e.g. in "Methods of Organic Chemistry” (Houben-Weyl), Vol. 14/2, Part 2, 4th Edition, Georg Thieme Verlag, Stuttgart 1963, p. 319 ff.
  • Suitable isocyanate compounds are, in particular, the generally known commercially available "high-solid isocyanates", hydrophilized and / or blocked isocyanates (cf. DE-A-4216536).
  • Suitable isocyanates are the isocyanates listed as monomers (a), which are used to build up the polyurethane. Among them, the polyvalent isocyanates with more than 2 isocyanate groups are particularly preferred.
  • blocking agents for the isocyanates are alcohols and oximes, e.g. Acetone oxime or methyl ethyl ketone oxime.
  • Crosslinking agents (B) can furthermore be polymeric resins which carry oxime-blocked isocyanate groups, as are described in DE-A-4237030, DE-A-3345448, WO 93/01245 and in US Pat. No. 5,358,997.
  • crosslinking of the polyurethanes (A) contained in the aqueous dispersion according to the invention with a polyisocyanate is usually carried out in the presence of a basic catalyst, e.g. a tertiary alkylamine.
  • the dispersions according to the invention are generally mixed with the crosslinking agent at any time before processing. It is also possible to add the crosslinking agent to the polyurethane (A) even before it is dispersed in water.
  • the dispersions according to the invention can also contain other water-emulsifiable or dispersible resins, such as polymer, polyurethane, polyester, epoxy or alkyd resins, as well as commercially available auxiliaries and additives such as blowing agents, defoamers, emulsifiers. gates, thickeners, leveling agents and thixotropic agents, colorants such as dyes and pigments.
  • other water-emulsifiable or dispersible resins such as polymer, polyurethane, polyester, epoxy or alkyd resins
  • auxiliaries and additives such as blowing agents, defoamers, emulsifiers. gates, thickeners, leveling agents and thixotropic agents, colorants such as dyes and pigments.
  • Dispersions according to the invention which contain, as crosslinking agent (B), a compound having aldehyde, primary or secondary amino, hydrazine, aminoxy, hydrazide or ketoxime-blocked isocyanate groups or an aminoplast resin are so-called one-component components Systems since they can be processed within any period after their manufacture.
  • crosslinking agent (B) a compound having aldehyde, primary or secondary amino, hydrazine, aminoxy, hydrazide or ketoxime-blocked isocyanate groups or an aminoplast resin are so-called one-component components Systems since they can be processed within any period after their manufacture.
  • the dispersions according to the invention to which a compound with non-blocked isocyanate groups has been added as crosslinking agent (B), are so-called two-component systems, because because of the limited period within which the corresponding mixture should be processed (approx 8 hours), the mixing is usually carried out by the processor of the dispersions
  • the coating compositions produced in this way are generally applied to the workpiece to be coated by the processes customary in the paint industry, for example by rolling, spraying, brushing, casting, dipping.
  • the subsequent drying or curing of the lacquer can be carried out either by cold curing (ie by drying at temperatures from 0 to 80 ° C., preferably at room temperature) or by the so-called baking process (ie by drying usually at temperatures from 80 to 280 ° C).
  • Cross-linking agents with aldehyde, aldimine, primary or secondary amino, hydrazine, aminoxy or hydrazide groups are particularly suitable for cold curing.
  • the coating compositions therefore represent a one-component system consisting of binder and crosslinker.
  • Cold curing can also be carried out in the presence of crosslinking agents (B) with free isocyanate groups.
  • the dispersion according to the invention should be applied to the workpiece at the latest within a period of approximately 8 hours after mixing with the crosslinking agent.
  • Cold curing can also be carried out when using (hetero) aromatic crosslinking agents (B) containing aldimine groups.
  • the storage time of the dispersions according to the invention in this case is from one hour to several weeks, depending on the composition.
  • the above-mentioned aminoplast resins, blocked and unblocked polyisocyanates and the Michael acceptors are particularly suitable as crosslinking agents.
  • a certain amount of crosslinking of the polyurethane takes place under the conditions of the stoving process even in the absence of a crosslinking agent. This is particularly the case if the crosslinking is carried out in the presence of the Lewis or Brönstedt bases described in DE-A-42 37 492, such as tertiary amines, e.g. 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) takes place.
  • the Lewis or Brönstedt bases described in DE-A-42 37 492 such as tertiary amines, e.g. 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) takes place.
  • the coating compositions according to the invention are particularly suitable for the coating of wood, metal, plastics, for the coating of paper, leather, textile, for the production of moldings, printing inks and as adhesives.
  • the dispersions according to the invention are notable for the fact that even those which contain no or only relatively small amounts of leveling agent can be processed into high-quality lacquer coatings.
  • dispersions according to the invention can be processed both as a one-component and as a two-component system using the cold curing method and also using the stoving method. This is advantageous for processors who use different of these 4 processing variants, because it only has to store a small number of polyurethane dispersions for different processing methods.
  • aqueous dispersions containing the polyurethane (A) are ideal for the production of printing inks.
  • These printing inks are preferably composed as follows:
  • crosslinking agents (B) used are preferably the polyhydrazides described in more detail above in the proportions already mentioned.
  • auxiliaries and additives as are generally used in printing inks, that is to say, for example, waxes, anti-foaming agents, dispersing and wetting agents and microcides.
  • the components (ii) to (v) used in the printing inks are those generally used in printing inks, for example from Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A22; 1993 VCH Publishers, Inc .; Pages 143 to 155 are known.
  • printing inks are particularly suitable for printing on plastic films such as polyethylene or polypropylene films which have a surface tension of 30 to 50, preferably 35 to 40, particularly preferably 37 to 39 mN / m (measured with water at a temperature of 23 ° C) have.
  • Printing can be carried out using the generally customary methods (cf. loc. Cit. Pp. 145 and 146).
  • the plastic films with such surface tensions are commercially available films that have been corona-treated.
  • these printing inks In combination with the recommended substrates, these printing inks have favorable wetting behavior.
  • the printed foils are resistant to the usual mechanical stresses and solvents.
  • ADDH Adipic acid dihydrazide
  • Basonat PLR 8878 water emulsifiable isocyanate crosslinker from
  • BHAA adduct of one mole of diethanolamine and one mole of diketene
  • IPDI Vestanat IPDI from Hippos / isophorone diisocyanate
  • Luhydran ® A 848 S Aqueous, self-crosslinking polymer dispersion of
  • Neutral.1 Neutralizing agent for neutralizing the ionic groups of the polyurethane
  • Neutral.2 Like Neutral.1
  • NVD Theor. Crosslinking density from the implementation of ADDH with built-in BHAA (in mmol / kg solid)
  • Pluriol ® P 600 polypropylene glycol from BASF
  • P-THF 2000 Polytetrahydrofuran 2000 from BASF PUD: polyurethane dispersion
  • Wacoblau ® 9A 918 018 Blue pigment paste from BASF K + E.
  • Pluriol P 600 was aminated: in a 1.2 1 tube reactor filled with 500 ml of catalyst consisting of 50% NiO, 20% CuO and 30% Zr0 2 , 150 ml / h Pluriol P 600 was mixed with 450 ml / h ammonia continuously implemented.
  • the reaction temperature in the reactor was between 205 and 215 ° C.
  • the pressure was 200 bar and the amount of hydrogen was 50 l / h.
  • the volatile constituents water, ammonia
  • the product is characterized by the following key figures: Total amine number: 174.1 mg KOH / G; tertiary amine number: 1.3 mg KOH / G; secondary amine number: 6.3 mg KOH / g; Hydroxyl number: 30.2 mg KOH / g and water content 0.06% by weight.
  • the resulting polyetheramino polyol had the following characteristics: hydroxyl number: 291 mg KOH / g; Amine number: 147 mg KOH / g; tertiary amine number: 36.3 mg KOH / g; secondary amine number: 102.9 mg KOH / g; Water content 0.12% by weight; Density 1,000 g / cm 3 ; pH 11.4 and viscosity 326 mPa.s.
  • the resulting prepolymer was then diluted with 200 g of acetone and neutralized with 6.5 g of triethylamine (0.063 mol). Before the neutralization, the isocyanate content was 0.92 g / 100 g (th. 0.68%).
  • 3 g of diethylenetriamine (0.029 mol) in 16.7 g of water dissolved and subsequent removal of the acetone gave an opalescent dispersion with a solids content of 37.5% and a pH of 7.8.
  • the keto group content is th. 245, the salinity th. 214 mmol / kg solid.
  • Dispersion la polyurethane dispersion with carbonyl groups and adipic acid dihydrazide as crosslinking agent.
  • adipic dihydrazide 0.82 g was added to 100 g of dispersion 1 (molar ratio of the hydrazide groups to the carbonyl groups of 1: 1).
  • Dispersion lb polyurethane dispersion with carbonyl groups and polyethyleneimine as crosslinker.
  • Dispersion 2 reproduction of dispersion 1 with direct addition of adipic acid dihydrazide.
  • the dispersion was made from 400 g of polytetrahydrofuran 2000, 41.8 g of compound Ia, 32.19 g of dimethylolpropionic acid, 63.08 g of 1,4-butanediol, 331.23 g of isophorone diisocyanate and 19.43 g of triethylamine and 8.94 g of diethylene triamine. 24.38 g of adipic acid dihydrazide (78.5%) was added before the acetone was removed by distillation. An opalescent dispersion was obtained with a solids content of 36.6 and a pH of 7.8.
  • Dispersion 3 reproduction of dispersion 2 with addition of adipic acid dihydrazide after distillation.
  • Dispsersion 3 was prepared according to the preparation instructions for dispersion 2, with the difference that compound I.b was used instead of compound I.a and the adipic dihydrazide was added before the acetone was removed by distillation.
  • Dispersion 4 polyurethane dispersion with carbonyl groups. To a template from 400 g of polytetrahydrofuran (0.2 mol), 81.7 g of compound Ia (0.43 mol), 32.19 g of dimethylolpropionic acid (0.24 mol), 38.75 g of butanediol-1 , 4 (0.43 mol) and 130 g of methyl ethyl ketone were added at a temperature of 59 ° C 317.89 g of isophorone diisocyanate (1.43 mol) and 0.2 g of dibutyltin dilaurate in 50% strength in xylene. The mixture was reacted at 92 ° C. for 5 hours.
  • the mixture was then diluted with 600 g of acetone and neutralized with 19.43 g of triethylamine (0.19 mol).
  • the isocyanate content before neutralization was 0.87 g / 100 g (th. 0.68%).
  • the keto group content is th. 478, the salinity th. 214 mmol / kg solid.
  • the molar ratio of the hydrazide groups to the keto groups is 1: 1.
  • Dispersion 4a was prepared in the same way as dispersion 4, but with the difference that no ADDH was added. In addition, it was mixed with 0.5% by weight, based on the solid DBU.
  • Dispersion 5 polyurethane dispersion with carbonyl groups
  • the mixture was then diluted with 700 g of acetone and neutralized with 28.33 g of triethylamine (0.28 mol). Before neutralization, the isocyanate content was 0.90 g / 100 g (th. 0.79%). Dissolved in 50 g water by adding 1800 g demineralized water, 13.76 g diethylenetriamine (0.13 mol), then removing the acetone and adding 59.57 g adipic acid dihydrazide (84.7%, 29 mol) an opalescent dispersion with a solids content of 41% and a pH of 7.8 was obtained. The keto group content is th. 480, the salinity th. 232 mmol / kg solid.
  • Example 8 from EP-A-332326 was reproduced without the addition of adipic dihydrazide.
  • the reactive keto compound was first prepared from 21.75 g of diethanolamine (0.207 mol) and 35.05 g of diacetone acrylamide (0.207 mol) in 35.05 g of methyl ethyl ketone.
  • Capa 210 is a polycaprolactone from Interox, with a molecular weight of 1000 g / mol (example 910 g / mol).
  • the prepolymer was made from 400 g Capa 210 (0.4 mol), the adduct solution (0.207 mol),
  • Comparative Example 2a Treatment of the Dispersion from Comparative Example 2 (V): with Adipic Dihydrazide
  • adipic dihydrazide was added to 100 g of the dispersion from comparative example 2 (molar ratio of the hydrazide groups to the keto groups of 1: 1).
  • the isocyanate content was 0.88 g / 100 g (th. 0.68%).
  • the mixture was then neutralized with 19.43 g of triethylamine and dispersed by adding 1500 g of demineralized water. An additional 8.94 g of diethylene triamine were added for crosslinking. After removing the solvents, a white dispersion with many specks was obtained. The polyurethane partially settled overnight.
  • the keto group content is th. 245, the salt content th. 214 mmol / kg solid.
  • the prepolymer solution was colored brown.
  • the isocyanate content was 0.79 g / 100 g (th. 0.68%). It was neutralized with 19.43 g of triethylamine (0.19 mol) and dispersed with 1500 g of demineralized water. Then 8.94 g of diethylenetriamine dissolved in 50 g of water were added. After removing the solvents, a yellow Obtained light white dispersion with a solids content of 37.1% and a pH of 8.1. The keto group content is th. 245, the salinity th. 214 mmol / kg solid. A yellowish-colored film with an orange peel structure was obtained by knife coating on a glass plate with a dry layer thickness of approximately 50 ⁇ m.
  • Diacetone acrylamide a dispersion with a theoretically calculated keto group content of 335 mmol / kg solid from the following components for prepolymer synthesis: A pre-adduct of 34.7 g diethanolamine and 55.85 g diacetone acrylamide was in 60 g N -Methylpyrrolidone 7h at 85 ° C implemented.
  • the isocyanate value was 0.81 g / 100 g (th. 0.64%). 19.43 g of triethylamine (0.192 mol) were added for neutralization.
  • the dispersion was formed by adding 1650 parts of demineralized water, followed by crosslinking with 8.94 g of diethylenetriamine (0.09 mol) dissolved in 50 g of water. After removal of the acetone, a slightly opalescent milky white dispersion with a solids content of 37.4% and a pH of 7.9 was obtained.
  • the keto group content is th. 308, the salinity th. 197 mmol / kg solid.
  • Example No. 6a or 6b 9.64 g were added to 400 g of a dispersion prepared according to dispersion 6
  • ADDH (Ex. 6a) or 24 ml InNaOH and then 48 g of polyethyleneimine as a 10% aqueous solution (molar ratio of amino groups to carbonyl groups about 1: 1) Ex. 6b) added.
  • Dispersion 11 was prepared analogously to dispersion 6, but 5 with the difference that no ADDH was added. Solids content: 39.6% pH: 7.9
  • Dispersion 11a was obtained by mixing dispersion 11 with 0.5% by weight based on solid resin DBU.
  • Dispersion 11b was prepared by mixing 100 parts of dispersion 11 with 2.45 parts of adipic dihydrazide (molar ratio of the hydrazide groups to the carbonyl groups of 1: 1).
  • the dispersion 12 was produced analogously to dispersion 11. Solids content: 40.8% pH: 7.9.
  • Dispersion 12a was prepared by mixing 100 parts of dispersion 12 with 2.52 parts of adipic dihydrazide (molar ratio of the hydrazide groups to the carbonyl groups of 1: 1).
  • a dispersion was prepared from the following components using the process given in Example 3: 678.4 g of compound II, 53.65 g of DMPA, 87.42 g of 1,4-butanediol, 537.97 g of IPDI, 35 40 , 48 g TEA and 17.2 g DETA.
  • An opalescent dispersion with a solids content of 23.9% and a pH of 8.4 was obtained.
  • the keto group content is th. 952, the salt content th. 228 mmol / kg solid.
  • a dispersion was prepared from the following components using the process given in Example 3: 400 g of polytetrahydrofuran 2000, 368.33 g of compound III, 83.16 g of DMPA, 36.05 g of 1,4-butanediol, 455 , 72 g IPDI, 50.19 g TEA and 17th, 2 g DETA.
  • An opalescent dispersion with a solids content of 24.9% and a pH of 8.0 was obtained.
  • the content of keto groups is th. 400, the salinity th. 352 mmol / kg solid.
  • the printing inks were, if appropriate after storage, applied to corona-treated polyethylene with a surface tension of 38 mN / m by knife coating, then dried forcibly at 60 or 90 ° C. for 2 minutes.
  • the dry layer thickness was ⁇ 6 ⁇ m.
  • the dispersions according to the invention are superior to those of the prior art, in particular with regard to the wet rub crease resistance.
  • the dispersions were applied onto glass plates with a dry layer thickness of approximately 50 ⁇ m without addition and dried in a standard climate.
  • the films were assessed optically after drying. If there were defects in the film (specks, stress cracks, turbidity, orange peel structure, craters etc.), just enough butylglycol was added to the dispersions until after drying the film surface was clear, shiny and free of defects.
  • the amount of butyl glycol required is given as M requirement in% by weight.
  • the dispersions were applied with a film pulling frame onto normal sheet metal parts or onto gradient oven sheets with a bad thickness of generally 150-200 ⁇ m, predried for 10 min at room temperature and then baked.
  • Acetone / MEK test an iron sheet of quality St 1405 was coated with the dispersion or preparation to be tested. After drying, a wad of cotton soaked in acetone was rubbed back and forth on a selected lacquer layer of the coated sheet with slight pressure (lxhin, lxher, is 1 double stroke DH). This test extends over 50 to 100 DH. If the film has not been removed by then, the film is considered to be cross-linked or hardened.
  • the run-out time was determined in accordance with DIN 53 211 using a Din 4 cup.
  • the adhesive strength was assessed in% using the tesa tear-off method.
  • a tape of 20 - 25 mm width (Tesafilm 104-Beiersdorf AG) was glued to the pressure to be tested, evenly pressed on and pulled off abruptly. The test was carried out 1. after drying, 2. after water storage.
  • the still wet print was placed on a smooth, firm surface. Wiping 50 times in the same direction with a soft, damp paper towel under gentle pressure. It was visually assessed whether and to what extent the paper was colored or the print wiped off the substrate.
  • the test was carried out after the wet adhesion test, and in such a way that the knife-coat coating against coating "under water” could be rubbed 20 times in a circular motion.
  • the dried doctor blade was placed in a bucket of water. By lightly rubbing the paint "in the water” with the thumb it was assessed whether the wet coating could be rubbed off the surface or not. Testing was carried out after 30 minutes and 24 hours of water storage.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des dispersions aqueuses qui contiennent un polyuréthane (A), comprenant des unités structurales dérivées de composés de la formule (I) dans laquelle les substituants ont la notation suivante: R?1,RE2, R3¿ désignent chacun hydrogène, alkyle C¿1? à C24 ou alkényle C6 à C24, R?4¿ désigne hydrogène, R5, R6 désignent a) conjointement, alcanediyle C¿4? à C10, b) chacun, alkyle C2 à C10, cycloalkyle C5 à C8 ou aralkyle C7 à C20, c) chacun, un poly(oxyde d'alkyle) C2 à C4 terminé par hydroxyle, d) un reste R?5 ou R6¿ ayant la notation mentionnée sous a) jusqu'à c), l'autre reste désignant hydrogène ou un reste de la formule (II) dans laquelle X désigne alcanediyle C¿2? à C6, R?7¿ a la même notation que R5 ou R6, sous réserve que R7 ne désigne pas un reste de la formule (II), les restes R5 et R6 portent au total 2 à 5 groupes hydroxyle liés à des atomes aliphatiques de carbone et éventuellement le reste R5 et/ou R6 porte 1 ou 2 groupes hydroxyle liés de manière aromatique ou 1 groupe nitrile, 1 groupe amino tertiaire, 1 groupe acide carboxylique ou un groupe acide sulfonique, éventuellement présents sous la forme de leurs sels.
EP96934462A 1995-09-22 1996-09-13 Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto Ceased EP0851881A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19535159 1995-09-22
DE19535159 1995-09-22
DE19618675 1996-05-09
DE19618675A DE19618675A1 (de) 1995-09-22 1996-05-09 Dispersionen enthaltend Polyurethane mit Carbonylgruppen in Ketofunktion
PCT/EP1996/004031 WO1997011103A1 (fr) 1995-09-22 1996-09-13 Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto

Publications (1)

Publication Number Publication Date
EP0851881A1 true EP0851881A1 (fr) 1998-07-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96934462A Ceased EP0851881A1 (fr) 1995-09-22 1996-09-13 Dispersions contenant des polyurethanes ayant des groupes carbonyle en fonction ceto

Country Status (6)

Country Link
EP (1) EP0851881A1 (fr)
JP (1) JPH11512475A (fr)
CN (1) CN1197463A (fr)
AU (1) AU7281296A (fr)
CA (1) CA2230827A1 (fr)
WO (1) WO1997011103A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999033930A1 (fr) * 1997-12-24 1999-07-08 Essex Specialty Products, Inc. Adhesif sans couche de fond pour une surface peinte
DE19847791A1 (de) * 1998-10-16 2000-04-20 Bayer Ag Wäßrige Polyurethandispersionen
JP2005015626A (ja) * 2003-06-26 2005-01-20 Dai Ichi Kogyo Seiyaku Co Ltd 一液性水系ポリウレタン樹脂組成物及び該組成物を含有する水性樹脂組成物
DE102004060139A1 (de) * 2004-12-13 2006-06-29 Bayer Materialscience Ag Festkörperreiche Polyurethanpolyharnstoff-Dispersionen
JP2006306943A (ja) * 2005-04-27 2006-11-09 Nippon Kasei Chem Co Ltd 水性ウレタン樹脂の製造方法
CN101157749B (zh) * 2007-09-10 2011-08-10 浙江新力化工有限公司 一种聚氨酯改性的丙烯酸乳液及其制备方法
WO2021035662A1 (fr) * 2019-08-30 2021-03-04 Dow Global Technologies Llc Procédés de réduction des émissions d'aldéhyde dans des polyols de polyéther et des mousses de polyuréthane
CN112538152B (zh) * 2019-09-20 2022-09-20 万华化学集团股份有限公司 一种水性聚氨酯-聚脲分散体及制备方法和应用

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Publication number Priority date Publication date Assignee Title
GB8904102D0 (en) * 1988-03-09 1989-04-05 Ici Resins Bv Polyurethane coating compositions
GB9101204D0 (en) * 1990-02-14 1991-02-27 Ici Plc Production of polyurethane polymers,the polymers so produced and compositions containing them
DE4336206A1 (de) * 1993-10-23 1995-04-27 Hoechst Ag Wäßrige selbstvernetzende Polyurethan-Vinyl-Hybrid-Dispersionen

Non-Patent Citations (1)

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Title
See references of WO9711103A1 *

Also Published As

Publication number Publication date
CA2230827A1 (fr) 1997-03-27
AU7281296A (en) 1997-04-09
JPH11512475A (ja) 1999-10-26
CN1197463A (zh) 1998-10-28
WO1997011103A1 (fr) 1997-03-27

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