Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/542—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31609—Particulate metal or metal compound-containing

Definitions

• inorganic layer composites such as, for example, clay minerals, in particular naturally occurring smectite types, such as, for example, montmorillonite, saponite or hectoht, or synthetically produced smectite types , such as Laponite, for the adjustment of the rheology of the coloring aqueous basecoats of high importance.
• the abovementioned minerals have a negative surface charge as well as a positive edge charge, which positively influences the adjustment of the rheology of the basecoats, in particular in application methods in which a high shear stress of the basecoats occurs.
• aqueous lacquers containing the abovementioned minerals tend to form a gel, which can impair the processability of the aqueous basecoat or limit the content of nonvolatile material in the aqueous basecoat for a given workability.
• effect pigments in particular anisotropic effect pigments
• aqueous basecoats such as aluminum flakes or mica pigments
• the use of the abovementioned minerals is critical since there are often impairments in the metallic effect, in particular in the flop behavior and in the brightness and cloud formation , that is, in the formation of light-dark shades, occur in the baked paint layers.
• effect waterborne basecoats Laponite-containing effect pigment-containing waterborne basecoats (hereinafter effect waterborne basecoats) are described which contain a mixture of at least two neutralized fatty acids in order to prevent clouding.
• WO-A-2007/065861 describes mixed hydroxides, in particular hydrotalcate types, which have at least 2 organic anions having at least 8 carbon atoms as counterions, where the anions contain further functional groups, for example hydroxyl, amino or epo - Have xid phenomenon can have.
• the use of the thus modified hydrophobic hydrotalcites are described as intercalatable fillers for polymers, in particular for rubbery polymers.
• the use of the hydrotalcites in coating compositions is generally described in WO-A-2007/065861.
• the hydrophobic hydrotalcites are only conditionally suitable for use in aqueous coating compositions for OEM layer structures, since they are poorly compatible with the preferably water-dispersible binders at the molecular level.
• a use of the coating compositions to improve the optical properties, in particular the production of an excellent metallic effect (flop) with a high brightness in bmwwasserbasislacken, is not described in WO-A-2007/065861. Task and solution
• the object of the present invention is to provide effect waterborne basecoats with a high proportion of nonvolatile constituents which, in particular as a basecoat film in a paint finish of the automotive OEM finish, have an excellent metallic effect (flop) combined with high brightness exhibit.
• effect aqueous basecoat materials have been found which achieve these objects and which contain liquid-crystalline aqueous preparations (WZ) in proportions of from 1 to 99% by weight, based on the aqueous basecoat, and at least one effect pigment, which achieve this object, wherein the liquid-crystalline aqueous preparations (US Pat.
• WZ preferably 10 to 99.9 wt .-%, based on the non-volatile components of (WZ), at least one water-dispersible polyester (PES), in its preparation in proportions of 7 to 50 mol%, based on the totality of the polyester - stones, difunctional monomer units (DME) with aliphatic spacer groups (SP) of 12 to 70 carbon atoms between the functional groups (Gr) are used, and 0.1 to 30 wt .-%, based on the non-volatile components of (TM), positively charged layered inorganic particles (AT), whose not further intercalatable Einzelschich- th a ratio D / d of the middle Schichtd diameter (D) to the average layer thickness (d)> 50 and whose charge is at least partially compensated with singly charged organic anions (OA) included.
• DME difunctional monomer units
• SP aliphatic spacer groups
• the aqueous coating composition according to the invention contains as further constituent at least one film-forming preferably water-dispersible polymer (FP), preferably a water-dispersible polyurethane (PUR), which particularly preferably contains at least one water-dispersible polyester building block (PESB) with difunctional monomer units (DME).
• FP water-dispersible polymer
• PUR water-dispersible polyurethane
• DME difunctional monomer units
• the effect water basecoat according to the invention contains the liquid-crystalline aqueous preparation (WZ) in proportions of from 1 to 99% by weight, preferably from 5 to 95% by weight, based on the effect water basecoat.
• WZ liquid-crystalline aqueous preparation
• the liquid-crystalline aqueous preparation (WZ) preferably contains from 10 to 99.9% by weight, preferably from 15 to 95% by weight, based on the non-volatile constituents of (WZ), of at least one water-dispersible polyester (PES), during its preparation in proportions of 7 to 50 mol%, based on the totality of the polyester building blocks, difunctional monomer units (DME) with aliphatic spacer groups (SP) of 12 to 70 carbon atoms between the functional groups (Gr) are used, and 0.1 to 30 wt %, preferably between 1 and 20% by weight, based on the nonvolatiles of (WZ), of solid or preferably in suspension positive positively charged stratiform inorganic particles (AT) whose single layers, which are not further intercalatable, have a ratio D / d of the average layer diameter (D) to the average layer thickness (d)> 50 and whose charge is at least partially compensated with singly charged organic anions (OA).
• DME difunctional monomer units
• the water-dispersible polyester (PES)
• the preferred liquid-crystalline aqueous preparation (WZ) contains from 10 to 99.9% by weight, preferably from 15 to 95% by weight, based on the nonvolatiles of (WZ), of at least one water-dispersible polyester (PES), during its preparation in proportions of 7 to 50 mol%, based on the totality of the polyester building blocks, of difunctional monomer units (DME) having aliphatic spacer groups (SP) of 12 to 70 carbon atoms between the functional groups (Gr).
• DME difunctional monomer units
• SP aliphatic spacer groups
• Gr functional groups
• water-dispersible means that the polyesters (PES) in the aqueous phase form aggregates with an average particle diameter of ⁇ 500, preferably ⁇ 200 and particularly preferably ⁇ 100 nm, or are molecularly dissolved.
• the size of the aggregates consisting of the polyesters (PES) can be controlled in a conventional manner by introducing hydrophilic groups on the polyester (PES).
• the water-dispersible polyesters (PES) have the groups preferably capable of anion formation which, after neutralization, ensure that the polyesters (PES) can be stably dispersed in water.
• Suitable groups capable of forming anions are preferably carboxylic acid groups.
• the water-dispersible polyesters preferably have mass-average molecular weights M w (determined by gel permeation chromatography according to standards DIN 55672-1 to -3 with polystyrene as standard) of from 1,000 to 100,000 daltons, more preferably from 1,500 to 50,000 daltons.
• the difunctional monomer units (DME) of the polyesters according to the invention have aliphatic spacer groups (SP) with 12 to 70 carbon atoms between the functional groups (Gr).
• Preferred aliphatic spacer groups (SP) have 15 to 60, very particularly preferably 18 to 50 carbon atoms.
• the spacer groups (SP) cylcoaliphatic or aromatic structural units having 4 to 12 carbon atoms, ethylenically unsaturated structural units in proportions of up to 30 mol%, preferably up to 25 mol%, particularly preferably up to 20 mol%, based on the totality of coal nitrogen atoms, and heteroatoms, such as preferably oxygen, sulfur and / or nitrogen.
• Preferred functional groups (Gr) of the monomer units (DME) are hydroxyl and / or carboxylic acid groups or carboxylic anhydride groups. Monomer units each having 2 hydroxyl groups or 2 carboxylic acid groups are particularly preferred.
• Preferred monomer units are diols and / or dicarboxylic acids or their anhydrides with spacer groups (SP) of 12 to 70, preferably 15 to 60, particularly preferably 18 to 50 carbon atoms.
• SP spacer groups
• monomer units are dimeric fatty alcohols and / or dimeric olefinically unsaturated fatty acids and / or their hydrogenated derivatives which satisfy the abovementioned criteria, such as, in particular, dimeric fatty acids of the Pripol.RTM. Series from Unichema.
• the monomer units (DME) are used in proportions of from 7 to 50 mol%, preferably from 8 to 45 mol%, particularly preferably from 9 to 40 mol%, based on the entirety of the building blocks of the water-dispersible polyester (PES).
• the water-dispersible polyester preferably contains the following monomer units (MEn):
• unbranched aliphatic and / or cycloaliphatic diols with 2 to 12 carbon atoms, in particular ethylene glycol, diethylene glycol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol and / or 1,4-dimethylolcyclohexane, particularly preferably 1, 4-butanediol and / or 1,6-hexanediol.
• Unbranched in the sense of the invention means that the aliphatic see and / or cycloaliphatic carbon units have no further aliphatic substituents.
• branched aliphatic and / or cycloaliphatic diols with 4 to 12 carbon atoms, in particular neopentyl glycol, 2-methyl-2-propylpropanediol, 2-ethyl-2-butylpropanediol, 2,2,4-trimethyl-1,5-pentanediol, 2,2,5-trimethyl-1 , 6-hexanediol, more preferably neopentyl glycol.
• Branched in the context of the invention means that the aliphatic and / or cycloaliphatic carbon units have further aliphatic substituents,
• Dicarboxylic acids having 4 to 12 carbon atoms, in particular oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, isophthalic acid, terephthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1, 2-cyclohexanedioic acid, 1, 4-cyclohexanedioic be - Or their anhydrides, particularly preferably 1, 2-cyclohexanedioic acid, and
• Polycarboxylic acids having at least 3 carboxylic acid groups, in particular benzene tricarboxylic acids, such as benzene-1, 2,4-tricarboxylic acid and benzene-1, 3,5-tricarboxylic acid, trimellitic acid, pyromellitic acid, glyceric acid, malic acid or their anhydrides, particularly preferably benzene tricarboxylic acids such as benzene-1, 2,4-tricarboxylic acid and benzene-1, 3,5-tricarboxylic acid.
• benzene tricarboxylic acids such as benzene-1, 2,4-tricarboxylic acid and benzene-1, 3,5-tricarboxylic acid.
• the reaction of the monomer units (DME), (ME1), (ME2), and optionally (ME3) and (ME4) is carried out according to the generally well-known methods of polyester chemistry.
• the reaction temperature is preferably 140 to 240 ° C., preferably 150 to 200 ° C.
• it is expedient to catalyze the esterification reaction using as catalysts, for example, tetraalkyl titanates, zinc or tin alkoxides, dialkyltin oxides or organic salts of the dialkyltin oxides Use come.
• the monomer units (DME), (ME1), (ME2) and optionally (ME3), if appropriate in a suitable solvent, are first together in a suitable solvent to give a polyester polyol, which per se is used as the aqueous polyester (PES) according to the invention.
• the polyester polyol with the monomer units (ME4) to form the water-dispersible polyester (PES) according to the invention is implemented.
• the acid number of the water-dispersible polyesters (PES) according to DIN EN ISO 3682 is preferably between 10 and 80 mg KOH / g, more preferably between 20 and 60 mg KOH / g nonvolatile fraction.
• the water-dispersible polyesters carry crosslinkable functional groups (a), wherein in principle all groups are suitable which contain themselves and / or further functional groups of the polyester (PES) and / or with other constituents of the effect water basecoats according to the invention, in particular with crosslinking agents (V), react to form covalent bonds can.
• crosslinkable functional groups a
• groups are introduced via the already mentioned monomer building blocks (DME) and / or (MEn) or via further building blocks having such groups.
• groups which react with themselves (a) are: methylol, methylol ether, N-alkoxymethylamino and in particular alkoxysilyl groups.
• hydroxyl, amino and / or epoxy groups are as
• Groups (a) preferred are hydroxyl groups, wherein the hydroxyl value of the water-dispersible polyester (PES) according to DIN EN
• ISO 4629 preferably between 10 and 500, preferably between 20 and 200 KOH / g nonvolatile fraction. is.
• the inorganic particles (AT) are The inorganic particles (AT)
• liquid-crystalline aqueous preparation WZ
• WZ liquid-crystalline aqueous preparation
• the non-intercalatable monolayers have a ratio D / d of the average layer diameter (D) to the average layer thickness (d)> 50 and whose charge is at least partially compensated with simply charged organic anions (OA) , contain.
• the mean layer diameters (D) can be determined by the evaluation of SEM (scanning electron microscope) images, while the layer thicknesses (d) are determined experimentally by X-ray structure analysis, AFM (Atomic Force Microscopy) profile measurements on individual platelets and computationally Molecular structure are determined.
• the average layer diameter (D) of the positively charged inorganic particles (AT) is preferably between 100 and 1000 nm, more preferably between 200 and 500 nm, the average layer thickness (d) is preferably less than 1.0 nm, particularly preferably less than 0 , 75 nm.
• the preparation of the positively charged inorganic particles (AT) can be achieved by replacing the naturally occurring or the synthesis-related counterions (A) of the layered minerals with the singly charged organic anions (OA) according to methods known per se or by synthesis in the presence of the singly charged organic anions (OA).
• the positively charged inorganic particles (AT) in a suitable liquid medium which is able to swell the interstices between the individual layers and in which the organic anions (OA) are dissolved, suspended and then again isolated (Langmuir 2J. (2005), 8675).
• the layer structures are generally widened, wherein the distance between the electrically charged layers is preferably widened by at least 0.2 nm, preferably by at least 0.5 nm.
• Layer-shaped positively charged inorganic particles are preferred according to the invention, in particular the mixed hydroxides of the formula: (M (1-x ) 2 + M x 3 + (OH) 2 ) (A x / y y ) nH 2 o
• M 2+ divalent cations, M 3+ represent trivalent cations and as counterions anions (A) with a valence y, where x takes a value of 0.05 to 0.5, and a part of the counterions (A) by the simple charged organic anions (OA) is replaced.
• divalent cations M 2+ calcium, zinc and / or magnesium ions as divalent cations M 2+ calcium, zinc and / or magnesium ions, as trivalent cations M3 + aluminum ions and as anions (A) phosphate ions, sulfate ions and / or carbonate ions, because these ions largely ensure that no change in the Coloring occurs during curing of the layer according to the invention.
• the synthesis of the mixed hydroxides is known (for example, Eilji Kanezaki, Preparation of Layered Double Hydroxides in Interface Science and Technology, VoM, Chapter 12, page 345ff - Elsevier, 2004, ISBN 0-12-088439-9). It usually takes place from the mixtures of the salts of the cations in the aqueous phase at defined, constant basic pH values.
• the mixed hydroxides containing the anions of the metal salts are obtained as interstitial inorganic counterions (A). If the synthesis is carried out in the presence of carbon dioxide, the mixed hydroxide with embedded carbonate ions (A) is generally obtained. If the synthesis is carried out in the absence of carbon dioxide or carbonate in the presence of singly charged organic anions (OA) or their acidic precursors, the mixed hydroxide with intervening organic anions (OA) (coprecipitation method or template method) is generally obtained.
• An alternative synthetic route for preparing the mixed hydroxides is the hydrolysis of the metal alcoholates in the presence of the desired anions to be incorporated (US Pat. No. 5,514,473).
• OA simply charged organic anions
• A incorporated carbonate ions
• This can be done, for example, by rehydrating the amorphous calcined mixed oxide in the presence of the desired anions (OA) to be incorporated.
• the calcination of the mixed hydroxide containing embedded carbonate ions (A), at temperatures ⁇ 800 ° C provides the amorphous mixed oxide to obtain the layer structures (rehydration method).
• the ion exchange can be carried out in an aqueous or alcoholic aqueous medium in the presence of the acid precursors of the organic anions to be stored.
• the acid precursors of the organic anions to be stored.
• treatment with dilute mineral acids necessary to remove the carbonate ions (A).
• the singly charged organic anions (OA) used for at least partial compensation of the charge and for widening the abovementioned mixed hydroxides have anionic groups (AG) as charge carriers, more preferably singly charged anions of the carboxylic acid, the sulfonic acid and / or the phosphonic acid.
• the singly charged organic anions (OA) preferably have molecular weights of ⁇ 1,000 daltons, more preferably ⁇ 500 daltons.
• the singly charged organic anions (OA) additionally carry functional groups (c) which optionally react with functional groups (a) of the polymer (FP) during curing of the coating agent to form covalent bonds.
• the functional groups (c) are particularly preferably selected from the group of hydroxyl, epoxy and / or amino groups.
• the functional groups (c) are preferably separated from the anionic groups (AG) of the singly charged organic anions (OA) by a spacer, the spacer being selected from the group of optionally heteroatoms, such as nitrogen, oxygen and / or Sulfur, modified and optionally substituted aliphatic and / or cycloaliphatic having a total of 2 to 30 carbon atoms, preferably between 3 and 20 carbon atoms, optionally with heteroatoms, such as nitrogen, oxygen and / or sulfur, modified and optionally substituted aromatics with in total 2 to 20 carbon atoms, preferably between 3 and 18 carbon atoms, and / or the substructures of the abovementioned cycloaliphatic and aromatic compounds, wherein in the substructures in particular at least 3 carbon atoms and / or heteroatoms between the functional group (c) and the anionic group (AG ) are located.
• optionally heteroatoms such as nitrogen, oxygen and / or Sulfur
• the spacers of the singly charged organic anions (OA) are particularly preferably substituted or unsubstituted phenyl or cyclohexyl radicals which have the functional group (c) in the m- or p-position relative to the anionic group (AG).
• the functional group (c) in the m- or p-position relative to the anionic group (AG).
• carboxyl group and / or sulfonate groups are used here as functional group (c) hydroxyl and / or amino groups and as anionic group (AG).
• the organic anions (OA) have at least two of the abovementioned functional groups (c).
• OA simply charged organic anions having a functional group (c): m- or p-aminobenzenesulfonate, m- or p-hydroxybenzenesulfonate, m- or p-aminobenzoate and / or m- or p-hydroxybenzoate, or as singly charged organic anions (OA) having two functional groups (c): 3-hydroxy-4-aminobenzenesulfonate, 3-amino-4-hydroxybenzenesulfonate, 3-hydroxy-4-aminobenzene benzoate and / or 3-amino-4-hydroxybenzoate .
• the modification of the cationically charged inorganic particles (AT) is preferably carried out in a separate process before incorporation into the coating composition according to the invention, this process being particularly preferably carried out in an aqueous medium.
• the electrically charged inorganic particles (AT) modified with the singly charged organic anions (OA) are preferably prepared in a synthesis step.
• the particles thus produced have only a very low intrinsic color, they are preferably colorless.
• the positively charged particles (AT) modified with singly charged organic anions (OA) can be prepared in a synthesis step, in particular from the metal salts of the cations and the organic anions.
• an aqueous alkaline solution of the singly charged organic anion (OA) is used.
• an aqueous mixture of salts of divalent cations M 2+ and trivalent cations M3 + is added until the desired stoichiometry is established.
• the addition is preferably carried out in CO 2 -free atmosphere, preferably under an inert gas atmosphere, for example under nitrogen, with stirring at temperatures between 10 and 100 degrees C, preferably at room temperature, the pH of the aqueous reaction mixture, preferably by adding alkaline hydroxides, preferred NaOH, in the range of 8 to 12, preferably between 9 and 11 is maintained.
• the resulting suspension is aged at the aforementioned temperatures for a period of 0.1 to 10 days, preferably 3 to 24 hours, the resulting precipitate, preferably by centrifugation, isolated and deionized several times Washed water. Thereafter, a suspension of the positively charged particles (AT) modified with the singly charged organic anions (OA) having a solids content of from 5 to 50% by weight, preferably from 10 to 40% by weight, is adjusted from the purified precipitate with water ,
• the suspensions of the modified positively charged inorganic particles (AT) prepared in this way can in principle be incorporated during each phase in the process according to the invention for preparing the coating composition, that is before, during and / or after the addition of the other components of the coating composition.
• the crystallinity of the layered double mixed hydroxides obtained as modified positively charged inorganic particles (AT), which are generally not obtained as individual layers but as layer stacks, is dependent on the synthesis pathway selected. rameters, the type of cations used, the ratio of M 2 VM 3+ cations and the type and amount of anions used, and should be as large as possible.
• the crystallinity of the mixed hydroxide phase can be expressed as the calculated size of the coherent scattering domains from the analysis of the corresponding X-ray diffraction lines, for example, reflections [003] and [110] in the case of the Mg-AI-based mixed double hydroxide.
• Eliseev et al. explain the influence of thermal aging on the increase of the domain size of the investigated Mg-Al-based mixed double hydroxide and explain this with the progressive incorporation of still existing tetredrically coordinated aluminum in the mixed hydroxide layer as octahedrally coordinated aluminum, as evidenced by the relative intensities of the corresponding Signals in the 27 Al NMR spectrum (Doklady Chemistry 387 (2002), 777).
• liquid-crystalline aqueous preparation can be customary in practice
• liquid-crystalline aqueous preparations in addition to the preferred inorganic particles (AT), the preferred polyesters (PES) and the film-forming polymers (FP), in particular the water-dispersible polyurethanes (PUR), in particular water-miscible or water-soluble solvents in proportions of bis to 30 wt .-%, preferably of up to 30 wt .-%, particularly preferably of up to 20 wt .-%, based on the nonvolatiles of (WZ), be contained.
• suitable coating additives are described, for example, in the textbook “Lackadditive” by Johan Bieleman, Verlag Wiley-VCH, Weinheim, New York, 1998.
• the preparation of the liquid-crystalline aqueous preparations (TM) are preferably prepared by first mixing all constituents of the preparation apart from the modified electrically charged inorganic particles (AT). In the resulting mixture, the modified positively charged inorganic particles (AT) or preferably the suspension of the modified electrically charged inorganic particles (AT) preferably prepared above are added with stirring, preferably until the suspension is uniformly dispersed, which by optical Methods, in particular by visual inspection.
• the resulting mixture is preferably heated at temperatures between 10 and 50 degrees C, preferably at room temperature, for a period of 2 to 30 minutes, preferably 5 to 20 minutes with ultrasonic stirring to obtain a finer, more homogeneous dispersion of the preparation of the inorganic particles AT, wherein in a particularly preferred embodiment, the tip of an ultrasonic source is immersed in the mixture.
• the temperature of the mixture may rise by 10 to 60K.
• the dispersion thus obtained is preferably aged for at least 12 hours with stirring at room temperature. Thereafter, the dispersion is preferably adjusted with water to a solids content of 10 to 70 wt .-%, preferably 15 to 60 wt .-%
• the preparations (TM) have liquid-crystalline properties.
• they show a birefringent phase under crossed polarizers which, depending on the concentration of the component (AT) according to the invention, can be present in addition to an isotropic phase.
• the texture of the birefringent phase is very similar to that ascribed to nematic phases.
• the film-forming water-dispersible polymer (FP) is the film-forming water-dispersible polymer (FP)
• the effect water basecoat material according to the invention preferably contains from 5 to 80% by weight, particularly preferably from 10 to 60% by weight, based on the nonvolatile constituents of the effect water basecoat, of a water-dispersible film-forming polymer (FP).
• FP water-dispersible film-forming polymers
• Such water-dispersible film-forming polymers are described, for example, in WO-A-02/053658, in the present invention preferably film-forming polymers (FP) from the group of water-dispersible polyesters which differ from the above-described polyesters (PES), the water-dispersible polyacrylates, the water-dispersible polyurethanes and / or the water-dispersible acrylated polyurethanes are used.
• the water-dispersible film-forming polymer comprises at least one water-dispersible polyurethane (PUR), which particularly preferably at least one polyester building block (PESB) with the above-described difunctional monomer units (DME) in proportions of from 1 to 40 mol %, preferably from 2 to 35 mol%, particularly preferably from 5 to 30 mol%, based on the totality of the building blocks of the polyester building block (PESB).
• PUR water-dispersible polyurethane
• DME difunctional monomer units
• water-dispersible means that the polyurethane (PU) in the aqueous phase form aggregates having an average particle diameter of ⁇ 500, preferably ⁇ 200 and particularly preferably ⁇ 100 nm, or are dissolved in molecular dispersion.
• the size of the aggregates consisting of the polyurethane (PUR) can be determined in a manner known per se. be controlled by introduction of hydrophilic groups on the polyurethane (PUR).
• the water-dispersible polyurethane (PUR) contains the groups which are preferably capable of forming anions and, after their neutralization, ensure that the polyurethane (PUR) can be stably dispersed in water.
• Suitable groups capable of forming anions are preferably carboxylic acid groups.
• ammonia, amines and / or amino alcohols for example di- and triethylamine, dimethylaminomethanolamine, diisopropanolamine, morpholines and / or N-alkylmorpholines.
• the difunctional monomer units (DME) of the polyester building block (PESB) of the polyurethane (PUR) have aliphatic spacer groups (SP) with 12 to 70 carbon atoms between the functional groups (Gr).
• SP aliphatic spacer groups
• DME monomer units
• Very particularly preferred monomer units (DME) of the polyester building block (PESB) are dimeric fatty alcohols and / or dimeric olefinically unsaturated fatty acids and / or their hydrogenated derivatives which satisfy the abovementioned criteria, in particular dimeric fatty acids of the Pripol.RTM. Unichema.
• Dimethylolcyclohexane more preferably 1, 4-butanediol and / or 1, 6-hexanediol.
• Unbranched in the sense of the invention means that the aliphatic and / or carbon moieties have no further aliphatic substituents.
• the reaction of the monomer units (DME), (ME11), (ME22) and optionally further monomer units is carried out according to the generally well-known methods of polyester chemistry.
• the reaction temperature is preferably 140 to 240 degrees C, preferably 150 to 200 degrees C.
• it is expedient to catalyze the esterification reaction as catalysts, for example tetraalkyl titanates, zinc or zinc nalkoxylates, Dialkylzinnoxide or organic salts of dialkyltin oxides to Use come.
• the water-dispersible polyurethanes are preferably composed of the polyester units (PESB) and, if appropriate, further low molecular weight and / or higher molecular weight polyols having at least 2 hydroxyl groups per polyol unit, preferably with bisisocyanato compounds and / or mixtures thereof and / or their dimeric, trimeric or tetrameric adducts, such as, in particular, diurets or isocyanurates, such as preferably hexamethylene diisocyanate, isophorone diisocyanate, TMXDI, 4,4 * -methylene bis (cyclohexyl isocyanate), 4,4 * -methylene bis (phenylyl isocyanate), 1,3 bis (1- isocyanato-1-methylethyl) benzene), particularly preferably hexamethylene diisocyanate and / or isophorone diisocyanate, and compounds capable of forming anions, in particular 2,2-
• the polyurethanes (PU) are preferably branched by the proportionate use of polyols, preferably triols, more preferably 1,1,1-tris (hydroxymethyl) -propane.
• the water-dispersibility of the polyurethanes is achieved by neutralization of the groups capable of forming anions, preferably with amines, particularly preferably with diethanolamine, a degree of neutralization of between 80 and 100%, based on the total of the neutralizable groups, being preferred.
• Effect pigments are all pigments which give special surface effects to a surface coating.
• the effect pigments (EP) are, for example, all effect pigments which can usually be used in vehicle and industrial coating or in ink and dye production.
• Examples of such effect pigments (EP) are pure metal pigments, such as, for example, aluminum, iron or copper pigments, interference pigments, such as, for example, titania-coated pigments.
• Preferred as effect pigments (EP) according to the invention are platelet-shaped metal pigments, preferably aluminum pigments, in particular leafing or nonleafing pigments (cf.
• the content of the effect pigments (EP) in the effect water basecoat according to the invention can vary widely and depends firstly on the hiding power of the effect pigment (EP) and on the intensity of the optical effect which one wishes to achieve.
• the effect water basecoat material according to the invention preferably contains from 0.1 to 50% by weight, based on the nonvolatile constituents of the effect water basecoat, preferably from 0.5 to 40% by weight, more preferably from 1 to 30% by weight and most preferably 2 to 25% by weight of effect pigment (EP) or mixtures of different effect pigments (EP).
• EP effect pigment
• EP mixtures of different effect pigments
• the waterborne basecoat material according to the invention may further comprise crosslinking agents (V) which have at least two functional groups (b) which are complementary groups with the functional groups (a) of the polyester (PES) and / or of the film-forming polymer (FP) , in particular of the polyurethane (PUR), react during curing of the coating agent to form covalent bonds.
• V crosslinking agents
• the aqueous preparation according to the invention may also contain conventional lacquer additives in effective amounts.
• further coloring pigments and conventional fillers in known amounts may be part of the coating composition.
• the pigments and / or fillers can consist of organic or inorganic compounds and are listed by way of example in EP-A-1 192 200.
• Further usable additives are, for example, further binders, such as, for example, polyurethanes or polyacrylates, in particular polyurethanes, UV absorbers, free-radical scavengers, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, leveling agents, film-forming auxiliaries, rheology-controlling additives and preferably catalysts for the reaction of functional groups (a), (b) and / or groups (c) described below, and additional crosslinking agents for the functional groups (a), (b) and / or (c).
• suitable coating additives are described, for example, in the textbook “Lackadditive” by Johan Bieleman, Verlag Wiley-VCH, Weinheim, New York, 1998.
• the preparation and application of the effect water basecoat according to the invention and the characterization of the resulting basecoat films can be prepared by any conventional methods known in the paint art in suitable mixing units, such as stirred tanks, dissolvers or Ultraturrax.
• the aqueous preparation (TM) is initially charged and the film-forming water-dispersible polymer (FP), the effect pigment (EP) and, if appropriate, the further constituents described above are added with stirring.
• the protagonistwasserbasislack invention is preferably adjusted with water to a solids content of preferably 5 to 50 wt .-%, particularly preferably from 10 to 45 wt .-%, in particular from 20 to 40% by weight.
• the resulting admiradosislack invention in particular the precursor consisting of a mixture of the aqueous preparation (TM) and the film-forming polymer (FP) prior to the addition of the effect pigment (EP), also liquid crystalline properties.
• TM aqueous preparation
• FP film-forming polymer
• EP effect pigment
• the effect water basecoat materials according to the invention are preferably applied in such a wet film thickness for the formation of the basecoat films, that after the thermal treatment to remove the volatiles in the resulting layers, a dry film thickness between 5 and 50 .mu.m, preferably between 6 and 40 .mu.m, more preferably between 7 and 30 microns, in particular between 8 and 25 microns is present.
• the application of the effect water basecoats according to the invention can be carried out by customary application methods, such as, for example, spraying, knife coating, brushing, casting, dipping or rolling. If spray application methods are used, compressed air spraying, airless spraying, high-speed spraying and electrostatic spraying (ESTA) are preferred.
• effect water basecoats according to the invention is usually carried out at temperatures of at most 70 to 80 degrees C, so that suitable application viscosities can be achieved without a change or damage of the coating agent and its optionally reprocessed overspray occurs in the momentarily acting thermal load ,
• the preferred thermal treatment of the applied layer of the bmwwasserbasislack invention is carried out by the known methods, such as by heating in a convection oven or by irradiation with infrared lamps.
• the thermal curing takes place at temperatures between 80 and 180 degrees C, preferably between 100 and 160 degrees C, for a time between 1 minute and 2 hours, preferably between 2 minutes and 1 hour, more preferably between 10 and 45 minutes.
• substrates such as, for example, metals
• the thermal treatment can also be carried out at temperatures above 180 ° C. In general, however, it is recommended not to exceed temperatures of 160 to 180 degrees C.
• the temperature and the time required for the curing process must be matched to this maximum limit.
• the thermal curing can take place after a certain rest period of 30 seconds to 2 hours, preferably from 1 minute to 1 hour, in particular from 2 to 30 minutes.
• the rest period is used in particular for the course and degassing of the applied basecoat films or for the evaporation of volatile constituents, such as solvents or water. Resting time can be assisted and shortened by using elevated temperatures up to 80 degrees C, provided that no damage or changes in the applied layers occur, such as premature complete crosslinking.
• the effect water basecoat according to the invention is suitable for numerous applications in the fields of automotive OEM finishing, automotive repair coating, and industrial coating, in particular metal coating (coil coating).
• the terrorismwasserbasislack invention is preferably used as a basecoat layer in OEM layer structures on metallic substrates and / or plastic substrates, seen in the case of metal substrates of substrate from an electrolytically deposited corrosion protection layer, preferably a cathodic deposited layer, from a filler layer applied thereto and one on the Filler layer applied topcoat lacquer layer, which is preferably composed of the bmwwasserbasislack invention and a final clearcoat exist.
• the electrodeposition coating in particular the cathodic dip coating, is preferably cured before the filler is applied.
• the filler is applied and the filler layer formed is preferably cured.
• the effect water basecoat of the invention and finally a clearcoat are applied in two further stages first.
• the effect water basecoat according to the invention is applied and flashed off at a time between 1 to 30 minutes, preferably between 2 and 25 minutes, at temperatures between 20 and 90 ° C., preferably between room temperature and 85 ° C. and in a subsequent step with a clearcoat, preferably a two-component clearcoat, overcoated, wherein basecoat and clearcoat are cured together.
• the OEM layer structures produced in this way show a significantly increased angle-dependent reflection behavior (brightness) of the basecoat layer in comparison with OEM layer structures with smectite-containing basecoats.
• the brightness L * is determined depending on the angle with a spectrophotometer.
• the ratio of the low-viewing-angle to the high-viewing-angle (flop) has values corresponding to the excellent values of the smectite-containing basecoats.
• the coatings produced according to the effect water-based paints excellent resistance to condensation, excellent adhesion to the filler layer and in particular to the clearcoat layer and excellent stability of the inherent color after curing. Furthermore, coatings with a comparatively low stoving temperature and good topcoat level can be realized with the effect water basecoat according to the invention.
• the reactor contents are heated in a nitrogen atmosphere while stirring to 220 degrees C until the reaction mixture has an acid number according to DIN EN ISO 3682 of 8 to 12 mg KOH / g nonvolatile content and a viscosity of 3.7 to 4.2 dPas (measured as 80 % By weight solution of the reaction mixture in 2-butoxyethanol at 23 ° C. in a cone-plate viscometer from the company ICI). After that, the cyclohexane is distilled off and the reaction mixture is cooled to 160 ° C.
• the reaction mixture is cooled to 130 ° C and 2.369 g of N, N-dimethylamino-2-ethanol are added. After further cooling to 95 degrees C, 17.041 deionized water and 19.046 2-butoxyethanol are added added. The resulting dispersion is adjusted by addition of further N 1 N-dimethylamino-2-ethanol and deionized water to a pH of from 7.4 to 7.8 and a nonvolatile content of 60 wt .-%.
• the resulting polyester solution has a nonvolatile content of 73% by weight.
• the reactor contents are heated in a nitrogen atmosphere with stirring until 82 degrees C until the reaction mixture as a 2: 1 dilution in N-methylpyrrolidone an isocyanate content of 0.8 to 1, 1 wt .-% and a viscosity of 5 to 7 dPas ( measured at 23 degrees C in a cone-plate viscometer from the company ICI). Thereafter, 0.554 g of 1,1,1-tris (hydroxymethyl) propane are added to the reaction mixture, heated to 82 ° C.
• reaction mixture as an 1: 1 dilution in N-methylpyrrolidone has an isocyanate content of less than 0.3 wt .-% and a viscosity of 12 to 13 dPas (measured at 23 degrees C in a cone-plate viscometer from Fa. ICI) has.
• the reaction mixture is diluted with 5.365 g of 2-butoxyethanol and 0.639 g of N, N-dimethylamino-2-ethanol are added.
• the resulting mixture is introduced into 60 g of deionized water while maintaining the temperature at 80 degrees C. Thereafter, the 2-butoxyethanol is distilled off to a residual content of less than 0.25 wt .-%, based on the reaction mixture.
• the resulting dispersion is adjusted to a pH of 7.2 to 7.4 and a nonvolatile content of 27% by weight by addition of further N, N-dimethylamino-2-ethanol and deionized water.
• the resulting suspension of the white reaction product Zn 2 Al (OH) 6 (4-absa) 2H 2 O (LDH suspension) has a solids content of 27.1% by weight and a pH of 9.
• Example 4 Formulation of the precursor for the effect aqueous basecoat according to the invention
• liquid-crystalline aqueous preparation WZ
• 13.5 g of the hydrotalcite suspension prepared according to Preparation 3 are added with stirring to a mixture of 15.0 g of the aqueous polyester dispersion (PES) according to Preparation Example 1, which is 9.0 g Was diluted deionized water, added at room temperature and stirred for 12 hours.
• PES aqueous polyester dispersion
• the result is a viscous white dispersion having streaks, as often observed in liquid crystalline preparations.
• Under crossed polarizers a nematic liquid-crystalline, birefringent phase next to an isotropic, non-birefringent phase can be seen.
• the ultra-small-angle X-ray scattering shows an intensity maximum typical of lamellar structures.
• the intensity maximum of the first order with a scattering vector q - 0.085 [1 / nm] corresponds to an interlayer distance of 75 nm ,
• the intensity maximum of the first order with a scattering vector q - 0.30 [1 / nm] corresponds to an interlayer distance of 21 nm.
• no birefringent phase is discernible.
• the still homogeneous phase under identically Lung of the crossed polarizing filter and the exposure parameters to an increased intensity.
• Example 5 (comparative example): Preparation of a PES / PUR dispersion with smectite component
• Example 6 For the preparation of the effect water basecoat materials according to Examples 6 (inventive) and 7 (comparative example), 5.0 g of a titania-coated mica pigment (Exterior Mearlin) are prepared in Preparation (WZ) according to Example 4 and in the dispersions according to Example 5 (Comparative Example) Fine Pearl from BASF SE).
• WZ Preparation
• Example 5 Comparative Example
• pre-treated steel plates provided by cathodic dip painting from Chemetall are used (thickness of the steel panel: 750 ⁇ m, thickness of the cathodic dip coating 21 +/- 2 ⁇ m).
• a commercial two-component clearcoat (FF99-0140 and SC29-0199 from BASF Coatings AG) is applied by spray application to the steel panels coated with the aqueous basecoat.
• the resulting clearcoat is dried for 10 minutes at room temperature.
• the mixture is then cured at 140 degrees C for 20 minutes.
• the dry layer thickness of the resulting clearcoat layer is 45 +/- 5 ⁇ m.
• the spectral photometer (MA 68 II from X-Rite) is used to determine the brightnesses L1 * to L * 5 at 5 viewing angles as shown in Table 1 below.
• the measured data show a significantly improved brightness of the structures with a layer of the effect water basecoat according to the invention according to Example 6 compared to those with a layer of smectite-containing aqueous basecoat of the prior art according to Example 7.
• the ratio L * 5 / L * 1 of the brightness values L5 * (at an angle of 115 degrees) to L1 * (at an angle of 15 degrees) the inventive effect aqueous basecoat according to Example 6 is equal to the smectite-containing aqueous basecoat of the prior art according to Example 7.

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• 2009
  • 2009-05-13 DE DE200910021071 patent/DE102009021071A1/de not_active Withdrawn
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