Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/147—Polyurethanes; Polyureas
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/675—Low-molecular-weight 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes

Definitions

• the present invention relates to a new aqueous coloring and / or effect coating material based on polyurethane and its use for the production of single and multi-layer coloring and / or effect coatings in automotive coating, industrial painting, including coil coating and container coating, plastic coating , the painting of buildings inside and outside, the furniture painting and the painting of hollow glass bodies.
• Aqueous coloring and / or effect-imparting coating materials in particular water-based paints, which comprise a water-dispersible, ionically or non-ionically stabilized polyurethane or a water-dispersible (meth) acrylate copolymer as a binder, at least one dispersing aid for the color and / or effect pigments, selected from the group from the reaction products of
• (c11) at least one polymerized olefinically unsaturated monomer selected from the group consisting of olefinically unsaturated monomers containing at least one reactive functional group selected from the group consisting of isocyanate groups, anhydride groups and epoxy groups; and (c12) at least one copolymerized olefinically unsaturated monomer which is free from isoeyanate, anhydride and epoxy-reactive functional groups;
• variables R from the group consisting of hydrogen atoms and saturated and unsaturated, substituted and unsubstituted, aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic-aromatic radicals, the at least one amino group -NH-, at least one Containing oxygen atom -O- and / or at least one sulfur atom -S- and / or can be cyclically linked to one another, at least one of the radicals R comprising at least one reactive functional group selected from the group consisting of isoeyanate, anhydride and epoxy-reactive groups , contains; to be selected; and layered silicates, in particular montmorillonites, as rheology-controlling additives, and the color and / or effect coatings produced therefrom are known from European patent application EP 0 589 340 A1.
• Aqueous coloring and / or effect-imparting coating materials in particular water-based paints, which have a water-dispersible (meth) acrylate copolymer as a binder and a non-associative rheology aid based on (meth) acrylate copolymers based on (C ⁇ -C 6 ) alkyl (meth) acrylic acid and (meth) acrylic acid, as well as the coloring and / or effect paints are known from German patent applications DE 197 41 554 A1 or DE 196 52 842 A1.
• the known coating materials have to be further improved with regard to their shear stability during stirring and their settling behavior when stored at room temperature and when stored in the oven at 40 ° C, so that the user, especially the automobile manufacturer, has no problems such as loss of structural viscosity or phase separation the line occur more.
• the object of the present invention is to provide new, aqueous, coloring and / or effect-imparting coating materials which are very suitable as a water-based lacquer or as a solid-color topcoat for the production of single- or multi-layered color and / or effect coatings.
• the new aqueous, color and / or effect coating materials should outperform the known coating materials in terms of their storage stability, in particular their shear stability and their settling behavior.
• the new one- or multi-layer color and / or effect coatings are said to be the known ones Varnishes in their adhesion properties, especially after exposure to condensation, exceed this, which should be the case both with the original paintwork and with the refinish paints.
• the new, aqueous, coloring and / or effect-imparting coating material free from rheology aids based on phyllosilicates, was found to contain
• At least one water-soluble, water-dilutable and / or water-dispersible polyurethane selected from the group consisting of grafted with olefinically unsaturated compounds, ionically or ionically and nonionically stabilized polyurethanes based on polyisocyanates, selected from the group consisting of aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic-aromatic polyisocanates;
• (c11) at least one polymerized olefinically unsaturated monomer selected from the group consisting of olefinically unsaturated monomers containing at least one reactive functional Group selected from the group consisting of isocyanate groups, anhydride groups and
• (c12) at least one copolymerized olefinically unsaturated monomer which is free from isoeyanate, anhydride and epoxy-reactive functional groups;
• R or at least one of R contains at least one reactive functional group selected from the group consisting of isoeyanate, anhydride and epoxy reactive groups; to be selected; and (D) at least one rheology aid based on (meth) acrylic copolymers.
• coating material which is free from rheology aids based on layered silicates.
• the coating material according to the invention had better storage stability than that of the known coating materials both when stored at room temperature and when stored at 40 ° C. Last but not least, the shear stability was improved. A phase separation was no longer observed in the coating material of the invention. Above all, however, it was surprising that the coatings according to the invention produced from the coating material according to the invention, in particular the base coats and solid-color top coats, were free from wetting disorders, runners, stoves, needle sticks, clouds, effect disorders, water stains and color shifts. They also met all the requirements placed on wet grip and stone chip resistance after exposure to a constant temperature condensation and after exposure to boiling water and subsequent irradiation with a high-pressure steam jet, and exceeded the known coatings in this regard.
• the coating material of the invention is curable thermally or thermally and with actinic radiation. It can be thermally self-crosslinking or externally crosslinking.
• actinic radiation means electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, and corpuscular radiation such as electron beams.
• NIR near infrared
• UV radiation visible light
• UV radiation UV radiation
• X-rays UV radiation
• corpuscular radiation such as electron beams.
• the term “self-crosslinking” denotes the property of a binder to undergo crosslinking reactions with itself.
• the prerequisite for this is that the binders already contain both types of complementary reactive functional groups which are necessary for crosslinking, or reactive functional groups which react “with themselves”.
• such coating materials are referred to as “externally crosslinking”, in which one type of the complementary reactive functional groups is present in the binder and the other type is in a hardener or crosslinking agent und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening”, pages 274 to 276, in particular page 275, below.
• the coating material of the invention is curable thermally and with actinic radiation, this is also referred to by experts as "dual cure”.
• the coating material of the invention is aqueous. This means that its constituents are dissolved and / or dispersed in water or in an aqueous medium which consists of water and minor amounts of at least one water-miscible organic solvent.
• minor amounts are to be understood as amounts that do not destroy the aqueous nature of the medium.
• the coating material of the invention is a one-component system.
• a one-component system is to be understood as a physically curing coating material or a thermally or thermally and with actinic radiation coating material, in which the binder and the crosslinking agent coexist, i.e. in one component.
• the prerequisite for this is that the two components only crosslink with one another at higher temperatures and / or when irradiated with actinic radiation.
• the coating material of the invention is a two- or multi-component system.
• two- or multi-component systems are understood to mean coating materials, the Crosslinking agent must be kept separate from other components of the coating materials due to its high reactivity until application.
• variable R 1 stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araiiphatic) radical
• the variables R 2 and R 3 represent the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
• One-component systems crosslinking temperatures of 100 to 180 ° C applied There are therefore preferably binders (A) with thio, hydroxyl, N-methylolamino, N-alkoxymethylamino and / or carboxyl groups, preferably hydroxyl groups, on the one hand and preferably crosslinking agents with anhydride, carboxyl, epoxy, blocked isoeyanate, methylol -, Methylolether-, siloxane, carbonate, amino, hydroxy and / or beta-hydroxyalkylamide groups, preferably blocked isoeyanate or alkoxymethylamino groups, on the other hand applied.
• binders (A) with thio, hydroxyl, N-methylolamino, N-alkoxymethylamino and / or carboxyl groups preferably hydroxyl groups
• crosslinking agents with anhydride, carboxyl, epoxy, blocked isoeyanate, methylol -, Methylolether-
• the binders (A) contain in particular methylol, methylol ether and / or N-alkoxymethylamino groups.
• Multicomponent systems crosslinking temperatures below 100 ° C applied.
• complementary reactive functional groups there are preferably thiol, hydroxyl or primary and secondary Amino groups, in particular hydroxyl groups, on the one hand and isocyanate groups on the other hand.
• the first essential component of the coating material of the invention is the polyurethane (A), which acts as a binder. According to the invention, it is selected from the group consisting of grafted with olefinically unsaturated compounds, ionically and ionically and nonionically stabilized polyurethanes based on polyisocyanates, selected from the group consisting of aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic aromatic
• the polyurethane (A) is linear, branched or comb-like.
• the production of the polyurethanes (A) to be used according to the invention has no special features, but takes place, for example, as in the patents EP 0 089 497 A1, DE 197 22 862 C2, DE 196 45 761 A1, DE 43 39 870 A1, DE 197 36 535 A1 or DE 44 37 535 A1, EP 0 522 419 A1 or EP 0 522 420 A1.
• (a1) at least one polyisocyanate, in particular a diisoeyanate, and optionally a monoisocyanate
• polyurethanes (A) prepared from the compounds (a1) to (a8) described above are grafted with olefinically unsaturated monomers (a9), resulting in polyurethane (meth) acrylate graft copolymers (A).
• Diisocyanates derived from dimer fatty acids such as those sold by Henkel under the trade name DDl 1410 and described in international patent applications WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1- pentyl-cyclohexane, or 1, 2-, 1, 4- or 1, 3-
• TXDI® Tetramethylxylylidene diisocyanate
• CYTEC Tetramethylxylylidene diisocyanate
• tolylene diisocyanate tolylene diisocyanate
• xylylene diisocyanate bisphenylene diisocyanate
• naphthylene diisocyanate diphenylmethane diisocyanate
• suitable polyisocyanates (a1) based on the diisocyanates (a1) described above are polyurethane prepolymers containing isocyanate groups, which have been prepared by reacting polyols with an excess of at least one of the diisocyanates described above, and / or isocyanurate, biuret, allophanate, Polyisocyanates containing iminooxadiazinedione, urethane, urea and / or uretdione groups, such as those formed by catalytic oligomerization of diisocyanates using suitable catalysts.
• suitable polyisocyanates (A) of this type and processes for their preparation are, for example, from the patents and patent applications CA 2,163,591 A 1, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A 1, US 4,801, 675 A, EP 0 183 976 A 1.
• DE 40 15 155 A 1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A, US 5,290,902 A, EP 0 649 806 A 1, DE 42 29 183 A 1 or EP 0 531 820 A 1 are known.
• Polyisocyanates are preferably used which have a statistical average of 2.5 to 5 isocyanate groups per molecule and viscosities of 100 to 10,000, preferably 100 to 5000 mPas.
• the polyisocyanates can be modified in a conventional and known manner to be hydrophilic or hydrophobic.
• Suitable monoisocyanates (a1) are phenyl isocyanate, cyclohexyl isocyanate or stearyl isocyanate or vinyl isocyanate, methacryloyl isocyanate and / or 1 - (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC),
• Suitable polyols (a2) are saturated or olefinically unsaturated polyester polyols which are obtained by reacting
• suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. Aromatic and / or aliphatic polycarboxylic acids are preferably used.
• aromatic polycarboxylic acids examples include phthalic acid, isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid or terephthalic acid monosulfonate, or halophthalic acids, such as tetrachloroborus or. Tetrabromophthalic acid, of which isophthalic acid is advantageous and is therefore used with preference.
• Suitable acyclic aliphatic or unsaturated polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid or dimer fatty acid or maleic acid, fumaric acid, sebacic acid, which is adacic acid, of which adasic acid, of which
• Dimer fatty acids and maleic acid are advantageous and are therefore used with preference.
• Suitable cycloaliphatic and cyclic unsaturated polycarboxylic acids are 1,2-cyclobutanedicarboxylic acid, 1,3-
• Cyclohexanedicarboxylic acid 1, 4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, tricyclodecanedicarboxylic acid,
• Tetrahydrophthalic acid or 4-methyltetrahydrophthalic acid can be used both in their ice and in their trans form and as a mixture of both forms.
• esterifiable derivatives of the above-mentioned polycarboxylic acids such as e.g. their mono- or polyvalent esters with aliphatic alcohols with 1 to 4 carbon atoms or hydroxy alcohols with 1 to 4 carbon atoms.
• anhydrides of the above-mentioned polycarboxylic acids can also be used if they exist.
• Monocarboxylic acids are used, such as, for example, benzoic acid, tert-butylbenzoic acid, lauric acid, isononanoic acid, fatty acids of naturally occurring oils, acrylic acid, methacrylic acid, ethacrylic acid or Crotonic.
• Isononanoic acid is preferably used as the monocarboxylic acid.
• Suitable polyols are diols and triols, especially diols.
• triols are usually used in minor amounts in order to introduce branches into the polyester polyols (a2).
• Suitable diols are ethylene glycol, 1, 2- or 1, 3-propanediol, 1, 2-, 1, 3- or 1, 4-butanediol, 1,2-, 1, 3-, 1, 4- or 1, 5 -Pentanediol, 1, 2-, 1, 3-, 1, 4-, 1, 5- or 1, 6-hexanediol, hydroxypivalic acid neopentyl ester, neopentyl glycol, diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol , 1,2-, 1, 3- or 1, 4-cyclohexanedimethanol, trimethylpentanediol,
• Ethylbutylpropanediol the positionally isomeric diethyloctanediols 2-butyl-2-ethylpropanediol-1, 3, 2-butyl-2-methylpropane-diol-1, 3, 2-phenyl-2-methylpropane-diol-1, 3, 2-propyl-2- ethyl propanediol-1, 3, 2-di-tert-butyl-propanediol-1, 3, 2-butyl-2-propyl-propanediol-1, 3,
• diols 1,3-bis (2'-hydroxypropyl) benzene.
• diols 1,3-bis (2'-hydroxypropyl) benzene.
• diols a2 1,3-bis (2'-hydroxypropyl) benzene.
• hexanediol and neopentyl glycol are particularly advantageous and are therefore used with particular preference.
• triols examples include trimethylolethane, trimethylolpropane or glycerol, in particular trimethylolpropane.
• the triols mentioned above can also be used as such for the production of the polyurethanes (triols a2; cf. patent EP 0339433 A1).
• monools can also be used.
• suitable monools are alcohols or phenols such as ethanol, propanol, n-butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, fatty alcohols, allyl alcohol or phenol.
• the polyester polyols (a2) can be prepared in the presence of small amounts of a suitable solvent as entrainer.
• a suitable solvent as entrainer z.
• suitable polyols (a2) are polyester diols which are obtained by reacting a lactone with a diol. They are characterized by the presence of any hydroxyl groups and recurring polyester components of the formula - (- CO- (CHR 4 ) m - CH2-O -) -.
• No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.
• the unsubstituted ### -caprolactone in which m has the value 4 and all R 4 substituents are hydrogen, is preferred.
• the reaction with lactone is started by low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1, 4-butanediol or dimethylolcyclohexane.
• low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1, 4-butanediol or dimethylolcyclohexane.
• Reaction components such as ethylenediamine, alkyldialkanolamines or urea are reacted with caprolactone.
• polylactam diols which are produced by reacting, for example, epsilon-caprolactam with low molecular weight diols.
• suitable polyols (a2) are polyether polyols, in particular with a number average molecular weight from 400 to 5,000, in particular from 400 to 3,000.
• Linear or branched polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and
• the polyether diols (a2) should not introduce excessive amounts of ether groups, because otherwise the coatings produced using the polyurethane (meth) acrylate graft copolymers (A) are swollen by water.
• they can be used in amounts which contribute to stabilizing the dispersions of the polyurethanes (A) (compounds a6).
• Suitable functional groups to be used according to the invention which can be converted into anions by neutralizing agents, are carboxylic acid, sulfonic acid or phosphonic acid groups, in particular carboxylic acid groups.
• suitable anionic groups to be used according to the invention are carboxylate, sulfonate or phosphonate groups, in particular carboxylate groups.
• neutralizing agents for functional groups which can be converted into anions are ammonia, ammonium salts, such as, for example, ammonium carbonate or ammonium bicarbonate, and amines, such as, for example, Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, methyidiethanolamine, triethanolamine and the like.
• the neutralization can take place in the organic phase or in the aqueous phase.
• Dimethylethanolamine is preferably used as the neutralizing agent.
• Suitable isocyanate-reactive functional groups are in particular hydroxyl groups, thiol groups and primary and / or secondary amino groups, of which the hydroxyl groups are preferably used.
• alkanoic acids with two substituents on the alpha carbon atom can be used, for example.
• the substituent can be a hydroxyl group, an alkyl group or preferably an alkyl group.
• These alkanoic acids have at least one, in general 1 to 3 carboxyl groups in the molecule. They have 2 to about 25, preferably 3 to 10, carbon atoms.
• suitable alkanoic acids are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid.
• a particularly preferred group of alkanoic acids are the alpha.alpha-dimethylolalkanoic acids of the general
• R 6 represents a hydrogen atom or an alkyl group having up to about 20 carbon atoms.
• R 6 represents a hydrogen atom or an alkyl group having up to about 20 carbon atoms.
• alkanoic acids are 2,2-dimethylol acetic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid and 2,2-dimethylol pentanoic acid.
• the preferred dihydroxyalkanoic acid is 2,2-dimethylol propionic acid.
• Compounds containing amino groups are, for example, alpha.omega-dia inovaleric acid, 3,4-
• Diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diamino-diphenyl ether sulfonic acid are examples of diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diamino-diphenyl ether sulfonic acid.
• Suitable functional groups to be used according to the invention which can be converted into cations by neutralizing agents and / or quaternizing agents are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, in particular tertiary amino groups or secondary sulfide groups.
• Suitable cationic groups to be used according to the invention are primary, secondary, tertiary or quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or tertiary sulfonium groups, but in particular tertiary ammonium groups.
• Suitable neutralizing agents for functional groups which can be converted into cations are inorganic and organic acids such as Sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or citric acid.
• (Potential) cationic groups are introduced into the polyurethanes (A) by incorporating compounds (a4) which contain at least one, in particular two, groups which are reactive toward isocyanate groups and at least one group capable of forming cations in the molecule; the amount to be used can be calculated from the desired amine number.
• Suitable isocyanate-reactive functional groups are those described above.
• Suitable compounds (a4) are 2,2-dimethylolethyl- or - propylamine, which are blocked with a ketone, the resulting ketoxime group being hydrolyzed again before the formation of the cationic group, or N, N-dimethyl-, N, N- Diethyl or N-methyl-N-ethyl-2,2-dimethylolethyl or propylamine.
• the total amount of neutralizing agent used in the coating material of the invention is chosen so that 1 to 100 equivalents, preferably 50 to 90 equivalents, of the potent anionic or cationic functional groups of the polyurethane (A) are neutralized.
• Polyols, polyamines and amino alcohols (a5) can be used for chain extension.
• Suitable polyols (a5) for chain extension are polyols with up to 36 carbon atoms per molecule, such as ethylene glycol, diethylene glycol,
• Triethylene glycol 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2- Butylene glycol, 1, 6-hexanediol, trimethylolpropane, castor oil or hydrogenated castor oil, di-trimethylolpropane ether, pentaerythritol, 1, 2-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentylglycol, hydroxypivalic acid or neopentylated glycol Bisphenol A, hydrogenated bisphenol A or mixtures thereof (cf. patent specifications EP 0 339433 A1, EP 0 436 941 A1 or EP 0 517 707 A1).
• polyamines (a5) have at least two primary and / or secondary amino groups.
• Polyamines (a5) are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that have no hydrogen atoms that are reactive with isocyanate groups.
• Examples are polyamines (a5) with a linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.
• diamines (a5) are hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, hexamethylenediamine-1,6, trimethylhexamethylenediamine, menthandiamine, isophoronediamine, 4,4'-diaminodiaminodicyclohexylmethane and amino cyclohexylmethane , Preferred diamines (a5) are hydrazine, alkyl- or cycloalkyldiamines such as propylenediamine and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.
• polyamines (a5) which contain more than two amino groups in the molecule. In these cases, however - for example by using monoamines (a5) - care should be taken to ensure that no crosslinked polyurethane resins (A) are obtained.
• useful polyamines (a5) are diethylene triamine, triethylene tetramine, Dipropylenediamine and dibutylenetriamine.
• An example of a monoamine is ethylhexylamine (cf. patent EP-A-0 089497).
• Suitable amino alcohols (a5) are ethanolamine or diethanolamine.
• Suitable compounds (a ⁇ ) through which hydrophilic nonionic functional groups are introduced into the polyurethanes (A) are the above-described polyether diols or alkoxypoly (oxyalkylene) alcohols with the general formula R 7 O - (- CH2-
• R 8 stands for a hydrogen atom or an alkyl radical with 1 to 6 carbon atoms and the index r stands for a number between 20 and 75, (cf. the patents EP 0 354 261 A1 or EP 0 424 705 A1).
• the polyurethanes (A) can contain terminal and / or lateral olefinically unsaturated groups. Groups of this type are introduced with the aid of compounds (a7) which have at least one, in particular two, isocyanate-reactive group (s), in particular hydroxyl groups, and at least one, in particular one, olefinically unsaturated group. However, it is also possible to use compounds (a ⁇ ) which contain at least one isocyanate group and at least one, in particular one, olefinically unsaturated group. Compounds (a7) are preferred.
• all groups which contain at least one, in particular one, double bond are suitable as olefinically unsaturated groups.
• a double bond is understood to mean a carbon-carbon double bond.
• highly suitable olefinically unsaturated groups are (Meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, vinyl, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl and / or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups and / or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl and / or butenyl ester groups.
• the compounds (a7) or (a ⁇ ) described above are preferably used in amounts that give polyurethanes (A) with an average of at least 0.5, preferably at least 1 and in particular at least 1, 5 olefinically unsaturated double bonds in the molecule.
• the polyurethanes (A) can be grafted with olefinically unsaturated monomers (a9).
• suitable monomers (a9) are:
• higher-functional monomers (a91) are generally used only in minor amounts.
• minor amounts of higher-functional monomers are understood to mean amounts which do not lead to crosslinking or gelling of the polyacrylate resins.
• the proportion of trimethylolpropane diallyl ether can be 2 to 10% by weight, based on the total weight of the monomers (a91) to (a96) used to prepare the polyacrylate resin.
• higher-functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-dioI, hexane-1, 6-diol, octahydro- 4,7-methano-1 H-inden- dimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di, tri or tetra (meth) acrylate; contain.
• minor amounts of higher-functional monomers (a2) are to be understood as those amounts which do not lead to crosslinking or gelling of the polyacrylate resins.
• Monomers (a93) at least one acid group, preferably a carboxyl group, ethylenically unsaturated monomer carrying per molecule or a mixture of such monomers.
• Acrylic acid and / or methacrylic acid are particularly preferably used as monomers (a93).
• other ethylenically unsaturated carboxylic acids with up to 6
• C atoms can be used in the molecule.
• examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
• ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a3).
• Monomers (a3) are furthermore maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester.
• Vinyl esters of alpha-branched monocarboxylic acids with 5 to 16 carbon atoms in the molecule can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
• paraffinic hydrocarbons such as mineral oil fractions
• olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
• the vinyl esters can also be prepared from the acids in a manner known per se, for example by letting the acid react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
• Reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 1 ⁇ C atoms per molecule The reaction of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be carried out before, during or after the polymerization reaction.
• the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid is preferably used as component (a5). This glycidyl ester is commercially available under the name Cardura® E10.
• Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene,
• (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N-cyclohexyl and / or N, N-cyclohexylmethyl (meth) acrylic acid amide;
• Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid,
• vinyl aromatic hydrocarbons such as styrene, alpha-alkylstyrenes, in particular alpha-methylstyrene and / or vinylitoluole;
• Diarylethylenes especially those of the general formula II:
• radicals R 9 , R 10 , R 1 and R 12 each independently of one another represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl,
• Aryl, alkylaryl, cycioalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R 9 , R 10 , R 11 and R 12 are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted Aryl residues, stand.
• suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
• Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
• suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable ones
• Cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylcyclohex-1-yl.
• suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl.
• suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene.
• suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.
• Suitable arylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylphen-1-yl.
• suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.
• the aryl radicals R 9 , R 10 , R 11 and / or R 12 are preferably phenyl or naphthyl radicals, in particular
• the substituents optionally present in the radicals R 9 , R 10 , R 11 and / or R 12 are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or completely halogenated alkyl, cycloalkyl,
• Arylalkyl and arylcycloalkyl radicals Aryloxy, alkyloxy and
• cycloalkyloxy radicals Arylthio, alkylthio and cycloalkylthio residues and / or primary, secondary and / or tertiary amino groups.
• These monomers (a6) are preferably not used as the sole monomers, but always together with other monomers (a), and they regulate the copolymerization advantageously in such a way that radical copolymerization in a batch mode is also possible;
• Nitriles such as acrylonitrile and / or methacrylonitrile; Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
• Versatic® acids which are sold under the brand name VeoVa® by Deutsche Shell Chemie (reference is also made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1996, page 59 ⁇ and pages 605 and 606) and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid; and or
• Molecular weight Mn from 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular
• Monomers (a9) which are particularly suitable for the intended use easily select their known physicochemical properties and reactivities. If necessary, he can carry out a few preliminary tests for this purpose. In particular, he will ensure that the monomers (a9) do not contain any functional groups, in particular (potentially) cationic or anionic functional groups, which have undesirable interactions with the (potentially) anionic or cationic functional groups in the polyurethanes (A).
• the monomers (a9) are selected such that the profile of properties of the grafted (co) polymers is essentially determined by the (meth) acrylate monomers (a9) described above, the other monomers (a9) advantageously varying this profile of properties widely.
• the preparation of the polyurethane (meth) acrylate graft copolymers (A) has no special features, but instead takes place according to the customary and known methods of free-radical (co) polymerization in bulk, solution or emulsion in the presence of at least one polymerization initiator.
• the polyurethane (meth) acrylate graft copolymer (A) is dispersed in an aqueous medium, resulting in a secondary dispersion.
• the (co) polymerization is preferably carried out in emulsion, such as, for example, in the patent DE 197 22 862 C1 or the Patent applications DE 19645761 A1, EP-A 522 419 A1 or EP 0 522 420 A1 described, or carried out in mini-emulsion or micro-emulsion.
• the miniemulsion and microemulsion are supplemented by the patent applications and the references DE 196 28 142 A1, DE 196 28 143 A1 or EP 0 401 565 A1, emulsion polymerization and emulsion polymers, editors. PA Lovell and Mohamed S. El-Aasser, John Wiley and Sons, Chichester, New York, Weinheim, 1997, pages 700 and following; Mohamed S.
• the graft copolymers according to the invention are obtained in the form of primary dispersions.
• Reactors for the (co) polymerization processes are the customary and known stirred kettles, stirred kettle cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents DE 1 071 241 A1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Volume 50, Issue 9, 1995, pages 1409 to 1416.
• the (co) polymerization is advantageously carried out at temperatures above room temperature and below the lowest decomposition temperature of the monomers used, preferably a temperature range from 30 to 180 ° C., very particularly preferably 70 to 150 ° C. and in particular ⁇ O to 110 ° C. becomes.
• the (co) polymerization can also be carried out under pressure, preferably under 1.5 to 3,000 bar, particularly preferably 5 to 1,500 and in particular 10 to 1,000 bar.
• suitable polymerization initiators are free radical initiators such as dialkyl peroxides, such as di-tert-butyl peroxide or
• Dicumyl peroxide Dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert.
• the initiators are preferred in an amount of
• the quantitative ratio of polyurethane (A) to grafted monomers (a9) can vary widely, which is a particular advantage of the polyurethane (meth) acrylate graft copolymers (A).
• This ratio is preferably 1: 100 to 100: 1, preferably 1:50 to 50: 1, particularly preferably 30: 1 to 1:30, very particularly preferably 20: 1 to 1:20 and in particular 10: 1 to 1: 10.
• Very special advantages result if this ratio is approximately 3.5: 1 to 1: 3.5, in particular 1.5: 1 to 1: 1.5.
• the proportion of the polyurethanes (A) or the polyurethane (meth) acrylate graft copolymers (A) to be used according to the invention in the coating materials according to the invention can vary widely and depends primarily on the intended use of the coating materials, the curing mechanism and the functionality the binder (A) with respect to the crosslinking reaction with the crosslinking agents which may be present. It is advantageous according to the invention to use the binders (A) in an amount of 5 to 70, preferably 6 to 65, particularly preferably 7 to 60 and in particular ⁇ to 55% by weight, in each case based on the solids of the coating material according to the invention.
• the binders (A) are preferably used in the form of their aqueous dispersions for the preparation of the coating material of the invention.
• the further essential component of the coating material of the invention is at least one coloring and / or effect pigment (B).
• the pigments (B) can consist of inorganic or organic compounds.
• the coating material of the invention in particular the waterborne basecoat and solid-color topcoat of the invention, especially the waterborne basecoat of the invention, therefore ensures a universal range of use on account of this large number of suitable pigments (B) and enables the realization of a large number of colors and optical and other physical effects.
• the effect pigments (B) are preferably selected from the group consisting of organic and inorganic, colored and achromatic, optically effect, electrically conductive, magnetically shielding and fluorescent pigments.
• suitable optically effect-giving effect pigments (B) are metal plate pigments, such as commercially available aluminum bronzes, according to
• fluorescent pigments (B) are bis (azomethine) pigments.
• Examples of suitable electrically conductive pigments (B) are titanium dioxide / tin oxide pigments.
• Examples of magnetically shielding pigments (B) are pigments based on iron oxides or chromium dioxide.
• Inorganic and organic pigments can be used as coloring pigments (B)
• White pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone;
• Black pigments such as carbon black, iron-mahgan black or spinel black;
• Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or Ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
• suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, azomethane pigments, iso-pigment pigments, iso-pigment pigments
• Thioindigo pigments metal complex pigments, perinone pigments, and
• Perylene pigments phthalocyanine pigments or aniline black.
• pigments (B) can also be used, which are selected from the group of filling, rheology-controlling, scratch-proofing, transparent or opaque and corrosion-protecting pigments, such as metal powder, organic and inorganic, transparent or opaque fillers or nanoparticles.
• suitable metal powders (B) are powders made of metals and metal alloys, such as aluminum, zinc, copper, bronze or brass.
• An example of a corrosion protection pigment (B) is zinc phosphate.
• suitable organic and inorganic fillers (B) are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polylamide or polyacrylonitrile.
• Suitable organic and inorganic fillers (B) are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polylamide or polyacrylonitrile.
• Mica and talc are preferably used if the scratch resistance of the color and / or effect layers produced from the basecoats is to be improved.
• platelet-shaped inorganic fillers such as talc or mica
• non-platelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfate or barium sulfate
• Suitable transparent fillers (B) are those based on silicon dioxide, aluminum oxide or zirconium oxide.
• Suitable nanoparticles (B) are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, nanoparticles based on silicon dioxide, aluminum oxide, zinc oxide, zirconium oxide and the polyacids and heteropolyacids of transition metals, preferably of molybdenum and tungsten, with a Primary article size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
• the hydrophilic nanoparticles preferably have no matting effect. Nanoparticles based on silicon dioxide are particularly preferably used.
• Hydrophilic fumed silicon dioxides are very particularly preferably used, the agglomerates and aggregates of which have a chain-like structure and which can be produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame. These are sold, for example, by Degussa under the Aerosil ® brand. Precipitated water glasses, such as nanohectorites, which are sold, for example, by Südchemie under the Optigel ® brand or by Laporte under the Laponite ® brand, are also used with particular preference. Further examples of nanoparticles (B) are from the German patent applications
• the surface of the nanoparticles can be modified.
• Organic silicon compounds can be used for this.
• Coating material can vary very widely and depends primarily on the effect that is to be set and / or that
• the Pigment concentration at a total of 3 to 90% by weight, based on the solids of the coating material of the invention.
• the coating material according to the invention contains at least one, in particular one, dispersion aid for the color and / or effect pigments (B) selected from the group consisting of the reaction products of
• (c11) at least one, especially one, copolymerized olefinically unsaturated monomer selected from the group consisting of olefinically unsaturated monomers containing at least one reactive functional group selected from the group consisting of isocyanate groups, anhydride groups and epoxy groups; and
• (c12) at least one, in particular one, copolymerized olefinically unsaturated monomer which is free from isoeyanate, anhydride and epoxy-reactive functional groups;
• NR 2 -C (O) -NR 2 (I) wherein the variables R from the group consisting of hydrogen atoms and saturated and unsaturated, substituted and unsubstituted, aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic-aromatic radicals, the at least one amino group -NH-, at least one Oxygen atom -O- and / or at least one sulfur atom -S- and / or may be cyclically linked to one another, at least one organic radical R being present and the radical R or at least one of the radicals R having at least one reactive functional group selected from the group Group consisting of isoeyanate, anhydride and epoxy reactive groups contains; to be selected.
• Suitable olefinically unsaturated monomers (c .11) and the amounts in which they are preferably used are known from European patent application EP 0 5 ⁇ 9 340 A1, page 3, lines 35 to 54.
• Suitable olefinically unsaturated monomers (c 12) and the amounts in which they are preferably used are known from European patent application EP 0 569 340 A1, page 3, line 54, to page 4, line 6.
• Suitable homopolymeric polyalkylene glycols (c 2) are the polyalkylene glycols described above for polyols (a 2) and those described in European patent application EP 0 569340 A1, page 4, lines 17 to 26.
• the dispersion aids (C) are preferably prepared in accordance with the methods described in European Patent Application EP 0 569 340 A1, page 3, line 30, to page 6, line 31, and page 7, line 32, to page 9, line 2 described method. They preferably have a number average molecular weight of 3,000 to 25,000, in particular 5,000 to 12,000, daltons.
• the content of the dispersing aid (C) in the coating material of the invention can vary very widely and depends on the requirements of the individual case, in particular on the dispersibility of the pigments (B).
• the dispersing aids (C) are preferably used in an amount of 0.01 to 10, preferably 0.02 to 5 and in particular 0.02 to 2% by weight, in each case based on the solids of the coating material of the invention.
• the dispersing aids (C) are particularly preferred via the pigment preparations (cf. Römpp Online, Georg Thieme Verlag, Stuttgart, New York, 2002, "pigment preparations") or pigment pastes incorporated into the coating material of the invention.
• the coating material of the invention contains at least one rheology aid (D) based on (meth) acrylate copolymers.
• rheology aid (D) based on (meth) acrylate copolymers.
• Rheology aids are published in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Thickener”, pages 599 to 600, and "Polyacrylic acids", page 457, German patent applications DE 196 52 642 A1 and DE 197 41 554 A1 and in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 31 to 34. Polyacrylic acid salts are preferably used.
• the rheology aids (D) are commercially available products and are sold, for example, under the brand Viscalex ® HV30 by Allied Colloids. They are used in the customary and known amounts in the coating material of the invention.
• the coating material of the invention can also contain at least one crosslinking agent.
• crosslinking agents are aminoplast resins, as described, for example, in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 199 ⁇ , page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., The book “Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP 0 245 700 A1 as well as in the article by B.
• the content of crosslinking agents in the coating material of the invention can vary very widely and depends primarily on its functionality on the one hand and the functionality of the polyurethanes (A) on the other.
• the coating material of the invention may further contain at least one organic solvent (cosolvent).
• the cosolvent is preferably miscible with water. Examples of common and known cosolvents are given in D. Stoye and W. Freitag, (ed.), »Paints, Coatings and Solvente, 2nd Completely Revised Editon, Wiley-VCH, Weinheim New York, 1998,» 14.9. Solvent Groups «, pages 327 to 373. They are preferably used in the coating material of the invention in an amount of 1 to 20, in particular 2 to 18,% by weight, based on the coating material of the invention.
• the coating material according to the invention can contain at least one neutralizing agent. Examples of suitable neutralizing agents are those described above for the polyurethanes (A). A degree of neutralization of 50 to 150 mol%, based on the potentially ionic groups present in the polyurethane (A), is preferably set.
• the coating material according to the invention can contain at least one additive typical of lacquer, which is selected from the group of inorganic and organic additives.
• paint-typical additives are additional binders curable thermally and / or with actinic radiation, reactive thinners for thermal curing or curing with actinic radiation, UV absorbers, light stabilizers, radical scavengers, initiators for radical polymerization, catalysts for thermal crosslinking, photoinitiators and -coinitiators, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and diperging agents, adhesion promoters, flow control agents, film-forming aids, additional rheology-controlling additives (thickeners), except layered silicates, flame retardants, siccatives, drying agents, skin preventives, corrosion inhibitors, for example wax inhibitors, wax inhibitors from the textbook "Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.
• the content of the additives described above in the coating material of the invention can vary very widely and depends primarily on the function of the additive used in each case.
• the amounts specified in the prior art listed above are advantageously used.
• the above-described essential constituents (A) to (D) and any other constituents of the coating material according to the invention that are present are dispersed and / or dissolved in water.
• the solids content of the coating material of the invention can vary widely. It depends primarily on the viscosity required for storage, transport and application. On the one hand, this is to prevent the components from settling during storage and transport. On the other hand, it should ensure problem-free application with a good flow of the resulting lacquer layers.
• the coating material of the invention can be produced by all customary and known processes for the production of waterborne basecoats.
• a conventional and known mixing unit such as a stirred tank, a homogenizer, a dissolver, an agitator mill, a Supraton or an Ultraturrax can be used for shearing the dispersions.
• It is a particular advantage of the coating material of the invention that the intrinsic viscosity builds up comparatively quickly even in a relatively weak shear field, which is provided by a simple stirrer. This means that expensive and maintenance-intensive devices that are necessary for the generation of strong shear fields can be dispensed with. Surprisingly, skin formation is also avoided.
• the coating material according to the invention in particular the waterborne basecoat according to the invention, is outstanding for the production of color and / or effect multilayer coatings on primed and unprimed substrates after wet-on-wet. Suitable method. Furthermore, the coating material according to the invention, in particular the solid-color topcoat according to the invention, is outstandingly suitable for the production of single-layer color and / or effect coatings.
• the coating material of the invention exhibits particular advantages in its use as a water-based lacquer in the wet-on-wet process in which the water-based lacquer is applied to the primed or unprimed substrate, after which the water-based lacquer layer is dried but not hardened, and a clear lacquer is applied to the water-based lacquer layer and the resulting clear lacquer layer cures together with the water-based lacquer layer thermally or thermally and with actinic radiation (dual cure).
• the primer in particular the filler layer, can be overcoated in the uncured or only partially hardened state with the water-based lacquer according to the invention and the clear lacquer, after which all three layers are baked together.
• a first water-based lacquer layer is applied to a primer which is not or only partially hardened, in particular an electrodeposition lacquer layer, on the substrate, after which the two layers are thermally hardened together.
• the resulting paint is then overcoated with a second water-based paint and clear coat, as described above.
• the first or the second waterborne basecoat can be produced from a waterborne basecoat according to the invention.
• both waterborne basecoats can be produced from one and the same waterborne basecoat of the invention or from two waterborne basecoats of different materials according to the invention.
• Suitable substrates are all surfaces to be painted which are not damaged by hardening of the layers thereon using heat or the combined application of heat and actinic radiation (dual cure).
• Suitable substrates are e.g. B. from metals, plastics, wood, ceramics, stone, textile, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials.
• the coating materials according to the invention are therefore outstanding for the production of decorative, functional and / or protective coatings for motor vehicle bodies and parts thereof, motor vehicles in interior and exterior areas, buildings in interior and exterior areas, doors, windows, furniture and hollow glass bodies and in the context of industrial painting small parts, coils, containers, packaging, electrical components and white goods.
• primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
• ETL electrocoat materials
• ATL anodic
• KTL cathodic
• Electrophoretic paints and fillers can also be applied wet-on-wet and thermally cured together.
• Primed or unprimed plastic parts can also be used if they are used under the thermal conditions
• Hardening are dimensionally stable.
• these can be subjected to a pretreatment, such as with a plasma or with flame treatment, in a known manner before the coating, or they can be provided with a hydro primer.
• the application of the coating materials according to the invention can be carried out by all customary application methods, e.g. Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling.
• the substrate to be coated can rest as such, with the application device or system being moved. However, the substrate to be coated, in particular a coil, can also be moved, the application system being at rest relative to the substrate or being moved in a suitable manner. If the coating materials according to the invention contain constituents which can be activated with actinic radiation, the application is preferably carried out with the exclusion of actinic radiation.
• the electrocoat layer, filler layer, solid-color topcoat according to the invention, waterborne basecoat layer and clearcoat layer are applied in a wet-layer thickness such that after curing, coatings with the necessary and advantageous layer thicknesses for their functions result.
• this layer thickness is 10 to 100, preferably 10 to 80, particularly preferably 10 to 60 and in particular 10 to 40 ⁇ m.
• filler coating it is 10 to 150, preferably 10 to 120, particularly preferably 10 to 100 and in particular 10 to 90 ⁇ m.
• solid-color topcoats according to the invention it is 10 to 100, preferably 10 to 80, particularly preferably 10 to 60, and in particular 10 to 40 ⁇ m.
• the waterborne basecoat according to the invention it is 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 ⁇ m.
• clearcoats it is 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 ⁇ m.
• lacquer layers according to the invention are preferably cured thermally or thermally and with actinic radiation (dual cure).
• Curing can take place after a certain period of rest. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min.
• the rest period is used, for example, for the course and degassing of the paint layers or for the evaporation of volatile
• the rest period can be supported and / or shortened by the use of elevated temperatures up to 90 ° C and / or by a reduced air humidity ⁇ 10g water / kg air, in particular ⁇ 5g / kg air, provided there is no damage or Changes in the lacquer layers occur, such as premature complete networking.
• the thermal hardening has no special features in terms of method, but is carried out according to the usual and known methods such as heating in a forced air oven or irradiation with IR lamps.
• the thermal hardening can also be carried out in stages.
• the thermal crosslinking of the one-component systems according to the invention is preferably carried out at temperatures above 100.degree. In general, it is advisable not to exceed temperatures of 180 ° C., preferably 160 ° C. and in particular 155 ° C.
• the curing with actinic radiation is preferably carried out with UV radiation and / or electron beams.
• a dose of 1,000 to 3,000, preferably 1,100 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm 2 is preferably used here. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources.
• work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the lacquer layers.
• shadow areas such as cavities, folds and other undercuts due to construction
• shadow areas can be combined with point, small area or all-round emitters with an automatic movement device for irradiating cavities or Edges are (partially) cured.
• the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.
• thermal curing and curing with actinic radiation are used together, these methods can be used simultaneously or alternately. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, curing may prove beneficial to begin and end with actinic radiation. Special advantages result if the lacquer layers are cured in two separate process steps first with actinic radiation and then thermally.
• the application and curing processes described above can also be used for the production of filler coatings and clear coats.
• the single- and multi-layer coatings according to the invention have excellent optical, mechanical and chemical properties. They are free from wetting disorders, runners, stoves, pinpricks, clouds, effect disorders, water stains and color shifts. They also meet all the requirements placed on wet grip and stone chip resistance after exposure to a constant temperature condensation and after exposure to boiling water and subsequent irradiation with a high-pressure steam jet. In particular, no delamination of the layers during hot steam high-pressure cleaning can be observed in the multi-layer coatings according to the invention due to their excellent wet adhesion properties.
• the coatings according to the invention offer further advantages. So they are an effective physical barrier against that
• plasticizers Diffusion of plasticizers, adhesives, antioxidants or solvents and of high heat resistance. They have good antistatic properties and a significantly improved corrosion protection effect and significantly improved wetting properties.
• the substrates according to the invention in particular bodies of automobiles and commercial vehicles, structures indoors and outdoors, industrial components, including plastic parts, small parts, packaging, coils, white goods and electrical components, or furniture, doors, windows and hollow glass bodies, also have the coated at least one coating according to the invention, special technical and economic advantages, in particular a long service life, which makes it particularly attractive for the user.
• polyurethane (meth) acrylate graft copolymer (A) was prepared analogously to the instructions given in German patent application DE 44 37 535 A1 on page 7, lines 36 to 53, “C Preparation of an Acrylated Polyurethane Dispersion”.
• a polyester diol was first prepared from 29.41 parts by weight of neopentyl glycol, 16.7 parts by weight of 1, 6-hexanediol and 44.2 parts by weight of adipic acid in 8.8 parts by weight of methyl isobutyl ketone and 0.86 parts by weight of cyclohexane as an entrainer.
• a polyurethane from 1.87 parts by weight of neopentyl glycol, 17.4 parts by weight of Polyesterdiol solution, 0.6 parts by weight of trimethylolpropane monoallyl ether and 12.82 parts by weight of isophorone diisocyanate in the presence of 0.010 parts by weight of dibutyltin dilaurate and 20.527 parts by weight of methyl isobutyl ketone and chain extended with 3.056 parts by weight of trimethylolpropane.
• the resulting polyurethane solution was used as a template for the copolymerization of a monomer mixture of 14.041 parts by weight of n-butyl acrylate, 14.04 parts by weight of methyl methacrylate, 3.36 parts by weight of hydroxypropyl methacrylate and 2.62 parts by weight of acrylic acid.
• a mixture of 6.72 parts by weight of methyl isobutyl ketone and 1.02 parts by weight of tert-butyl peroxy-2-ethylhexanoate was used as the initiator solution.
• the dispersing aid (C) was prepared according to the method described in European Patent Application EP 0 589 340 A1, page 7, lines 33 to 45, "Example 1, Preparation of Isocyanate Functional Acrylic Copolymer 1", and page 8, lines 28 to 42, " Example 5, Preparation of Modified Copolymer (Grind Resin) 1 ', specified specification.
• a pigment paste was mixed by mixing 7.5 parts by weight of the dispersing aid (C).
• Preparation example 2 6 parts by weight of the binder dispersion (A) acc.
• Preparation example 1 35 parts by weight of a commercially available green pigment, 0.3 part by weight of ligroin, 1, 3 parts by weight of methyl isoamyl ketone, 0.1 part by weight
• the waterborne basecoat material according to the invention was produced by mixing 4.56 parts by weight of Cymel® 327 (90% in isobutanol) in a stirred kettle,
• Aerosil paste (6% by weight Aerosil R 972/431 in water; Degussa), 9.6 Parts by weight of the binder dispersion (A) from preparation example 1, 31 parts by weight of the pigment paste from preparation example 3, 18 parts by weight of Viscalex® HV30 from Allied Colloids and 2.5 parts by weight of a neutralizing agent solution (dimethylethanolamine, 10% strength in water) were mixed together in a stirred tank.
• a neutralizing agent solution dimethylethanolamine, 10% strength in water
• the green water-based lacquer according to the invention was completely stable when stored at room temperature and 40 ° C. It could be sheared at these temperatures without problems, without components settling out or phase separation occurring. The required structural viscosity could be built up by simply stirring. No skin formation was observed.
• Example 2 The waterborne basecoat of Example 1 was used to produce the multi-layer paint system of Example 2.
• the waterborne basecoat was processed in a first series immediately after its production.
• the relevant multi-layer coating formed the standard against which the other multi-layer coatings of the second and third series were compared.
• the waterborne basecoats were stored at 40 ° C for seven days (temperature load).
• they were stirred for two weeks at low shear forces (shear stress).
• the color tones of the multi-layer coatings were measured with an X-Rite color measuring device using the CIELAB method. Standardized types of light were used. The differences from the standard were then calculated. The results can be found in the table.
• water-based paints were applied to test the wetting properties in wedge shape on glass plates and test panels with burned-in filler paints.
• Test boards measuring 10 x 20 cm. For this purpose
• the unpolluted waterborne basecoat was applied, flashed off at 20 ° C and a relative humidity of 65% for five minutes and dried in a forced-air oven at 80 ° C for five minutes, so that the dried waterborne basecoat film had a dry film thickness of about 15 ⁇ m.
• the water-based lacquer layers were covered with a powder slurry clear coat in accordance with international patent application WO 96/32452.
• the resulting powder slurry clearcoat films were flashed off at 20 ° C. and a relative atmospheric humidity of 65% for 3 minutes and dried in a forced air oven at 55 ° C. for five minutes.
• the dry layer thickness of the resulting clear lacquer layers was 55 to 57 ⁇ m.
• test panels are referred to below as "original panels”. Before the test and the application of the refinish coatings, they were stored for 24 hours in a climatic room at 23 ° C. and a relative humidity of 50%.
• test panels were produced in the manner described above, the clear lacquer being applied in a wedge shape.
• repair boards Some of the original panels were given a repair coating in accordance with ISO 1520. These boards are referred to below as “repair boards”.
• the original panels and the repair panels were subjected to the NedCar stone chip test VCKN4441 after exposure to a constant temperature condensation (SKK).
• This stone chip test, its evaluation and the grading of the results are generally known in the professional world.
• the adhesion properties of the multi-layer paint system of the original panels and the repair panels after exposure to boiling water were checked using the high-pressure test.
• a cross was carved into the multi-layer paintwork after each load.
• the scratched areas were sprayed with a water jet (device from Walter type LTA2; pressure: 80 bar; water temperature: 80 ° C; distance from nozzle tip / test board: 12 cm; load duration: 30 seconds; device setting: F 2).
• the degree of flaking was assessed visually and graded as follows:

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
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• 2002
  • 2002-12-09 DE DE10257377A patent/DE10257377A1/de not_active Withdrawn
• 2003
  • 2003-07-17 MX MXPA05005555A patent/MXPA05005555A/es active IP Right Grant
  • 2003-11-05 AU AU2003285313A patent/AU2003285313A1/en not_active Abandoned
  • 2003-11-05 US US10/537,070 patent/US7485679B2/en not_active Expired - Fee Related
  • 2003-11-05 CA CA002506786A patent/CA2506786A1/en not_active Abandoned
  • 2003-11-05 EP EP03778299A patent/EP1570013A1/de not_active Withdrawn
  • 2003-11-05 WO PCT/EP2003/012310 patent/WO2004053007A1/de not_active Application Discontinuation

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