WO2010130309A1 - Préparations aqueuses à propriétés cristallines liquides - Google Patents

Préparations aqueuses à propriétés cristallines liquides Download PDF

Info

Publication number
WO2010130309A1
WO2010130309A1 PCT/EP2010/001233 EP2010001233W WO2010130309A1 WO 2010130309 A1 WO2010130309 A1 WO 2010130309A1 EP 2010001233 W EP2010001233 W EP 2010001233W WO 2010130309 A1 WO2010130309 A1 WO 2010130309A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
mol
groups
aqueous preparations
water
Prior art date
Application number
PCT/EP2010/001233
Other languages
German (de)
English (en)
Inventor
Horst HINTZE-BRÜNING
Hans-Peter Steiner
Fabrice Leroux
Anne-Lise TROUTIER-THUILLIEZ
Thomas Stimpfling
Original Assignee
Basf Coatings Ag
Universite Blaise Pascal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Coatings Ag, Universite Blaise Pascal filed Critical Basf Coatings Ag
Publication of WO2010130309A1 publication Critical patent/WO2010130309A1/fr

Links

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
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • compositions based on inorganic layer fillers and polymers are known.
  • inorganic layer fillers such as talc or kaolin, for example, can bring about significant improvements in stiffness, impact strength, barrier action against mass transport, temperature and impact resistance, dimensional stability and / or scratch resistance of the polymers.
  • good incorporability of the layer fillers into the polymers is necessary, preferably good dispersion in the nanometer range.
  • additives based on inorganic layer fillers which bring about an improvement in the abovementioned properties, are likewise of great interest.
  • additives for aqueous coating compositions which have a permanently increasing share of the sweetener market, in particular due to their improved ecological properties.
  • the object of the present invention is to provide liquid-crystalline composites based on inorganic layer fillers and polymers which are easy to prepare and can be used without modification as a base for aqueous coating compositions or as an additive in them.
  • aqueous preparations (TM) having liquid-crystalline properties were found which achieve this object and which contain 10 to 99.9% by weight, based on the non-volatile constituents of (TM), of at least one water-dispersible polyester (PES), which is described in US Pat Contents 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 contains, and 0.1 to 30 wt .-%, based to the non-volatile fractions of (WZ), positively charged layered inorganic particles (AT), the non-intercalatable monolayers have a ratio D / d of the average layer diameter (D) to the layer thickness (d)> 50 and their charge at least partially with singly charged organic anions (OA) is compensated.
  • DME difunctional monomer units
  • SP aliphatic spacer groups
  • WZ non-volatile fractions of (WZ)
  • the water-dispersible polyester (PES)
  • the aqueous preparation according to the invention having liquid-crystalline properties contains from 10 to 99.9% by weight, based on the nonvolatiles of (WZ), of at least one water-dispersible polyester (PES), in its preparation in proportions of from 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.
  • WZ nonvolatiles of
  • PES water-dispersible polyester
  • DME difunctional monomer units
  • SP aliphatic spacer 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 have 15 to 60, very particularly preferably 18 to 50 carbon atoms. Furthermore, the spacer groups (SP) cylcoaliphatic or aromatic structural units with 4 to 12 carbon atoms, ethylenically unsaturated structural units in proportions of up to 30 mol%, preferably of up to 25 mol%, particularly preferably of up to 20 mol%, based on the total of the carbon atoms, and heteroatoms, as preferred 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 (DME) are diols and / or dicarboxylic acids or their anhydrides having spacer groups (SP) of 12 to 70, preferably 15 to 60, particularly preferably 18 to 50, carbon atoms. Very particular preference is given as monomer units (DME) to 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.
  • 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): in proportions of from 1 to 40 mol%, preferably from 2 to 35 mol%, particularly preferably from 5 to 30 mol%, based on the Total of the components of the water-dispersible polyester, unbranched aliphatic and / or cycloaliphatic diols (ME1) having 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, more preferably 1, 4-butanediol and / or 1, 6-hexanediol.
  • ME1 monomer units
  • Unbranched in the sense of the invention means that the aliphatic and / or cycloaliphatic carbon units have no further aliphatic substituents. in proportions of from 1 to 50 mol%, preferably from 2 to 40 mol%, particularly preferably from 5 to 35 mol%, based on the entirety of the components of the water-dispersible polyester, branched aliphatic and / or cycloaliphatic diols (ME2) 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
  • aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids having 4 to 12 carbon atoms, such as 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 acid or their anhydrides , Particularly preferably 1, 2-cyclohexanedioic acid, and
  • aliphatic, cycloaliphatic and / or aromatic polycarboxylic acids having at least 3 carboxylic acid groups, in particular benzenetricarboxylic 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 ren anhydrides, more preferably benzene tricarboxylic acids, such as benzene-1, 2,4-tricarboxylic acid and benzene-1, 3,5-tricarboxylic acid.
  • benzenetricarboxylic 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), (ME3) and optionally (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 alkoxylates, dialkyltin oxides or organic salts of the dialkyltin oxides ,
  • 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 (PES) bear crosslinkable functional groups (a), where in principle all groups are suitable which themselves and / or with further functional groups of the polyester (PES) and / or with others Duration- parts of the aqueous preparation according to the invention can react to form covalent bonds.
  • 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 preferred as groups (a). Hydroxyl groups are particularly preferred, the hydroxyl value of the water-dispersible polyester (PES) according to DIN EN ISO 4629 preferably being between 10 and 500, preferably between 50 and 200, KOH / g of non-volatile content.
  • the water-dispersible polyester (PES) is present in proportions of from 10 to 99.9% by weight, preferably from 15 to 95% by weight, based on the nonvolatiles of (WZ), in the aqueous preparation (WZ) ,
  • the inorganic particles (AT) are The inorganic particles (AT)
  • aqueous preparation according to the invention are from 0.1 to 30 wt .-%, preferably between 1 and 20 wt .-%, based on the nonvolatile Antei- Ie of (TM), solid or preferably in suspension present positively charged layered inorganic particles (AT) whose non-intercalatable individual layers have a ratio D / d of the average layer diameter (D) to the layer thickness (d)> 50 and whose charge is at least partially compensated with singly charged organic anions (OA) included.
  • TM nonvolatile Antei- Ie of
  • AT positively charged layered inorganic particles
  • D average layer diameter
  • d layer thickness
  • OA singly charged organic anions
  • the mean layer diameters (D) can be determined by the evaluation of SEM (scanning electron microscope) images, while the layer thickness (d) can be determined experimentally by X-ray structure analysis, AFM (atomic force microscopy) profile measurements on individual platelets and computational knowledge of the Molecular structure can be determined.
  • the mean layer diameter (D) of the positively charged which inorganic particles (AT) is preferably between 100 and 1000 nm, more preferably between 200 and 500 nm, the layer thickness (d) is preferably less than 1, 0 nm, preferably less than 0.75 nm.
  • the preparation of the positively charged inorganic Particles (AT) can be carried out by exchanging 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 isolated again ( Langmuir 21. (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.
  • positively charged inorganic particles are layered (AT), such as in particular the mixed hydroxides having the formula: (M (1 x) 2+ M x 3+ (OH) 2.) (A x / y y -) n H 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 trivalent cations M 3 + aluminum ions and as anions (A) phosphate ions, sulfate ions and / or carbonate ions, because these ions largely ensure that no change in hue 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.
  • the mixed hydroxide with intervening organic anions (coprecipitation method or template method) is generally obtained ).
  • An alternative route for the preparation of the mixed hydroxides consists in the hydrolysis of the metal alcoholates in the presence of the desired anions to be stored (US Pat. No. 6,514,473).
  • the simply charged organic anions (OA) to be stored by ion exchange on mixed hydroxides with incorporated carbonate ions (A). 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 0 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.
  • treatment with dilute mineral acids is necessary in order 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 water-dispersible polyester (PES) 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 see 3 and 18 carbon atoms, and / or the partial structures of the abovementioned cycloaliphatic and aromatic, wherein in the substructures are in particular at least 3 carbon atoms and / or heteroatoms between the functional group (c) and the anionic group (AG).
  • 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 is 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.
  • OA singly charged organic anion
  • 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.
  • 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, during each phase in the process according to the invention for the preparation of the coating composition are incorporated, that is, before, during and / or after the addition of the remaining components of the coating composition.
  • the crystallinity of the resulting layered double mixed hydroxides as modified positively charged inorganic particles (AT), which are usually not obtained as individual layers but as a layer stack and used depends on the selected synthesis parameters, the type of cations used, the ratio of M 2+ / M 3+ cations and the type and amount of anions used and should take on the largest possible values.
  • 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. For example, Eliseev et al.
  • aqueous preparation (WZ) according to the invention may contain crosslinking agents (V) which have at least two functional groups (b) which react as complementary groups with the functional groups (a) of the polyester (PES) during curing of the coating agent to form covalent bonds ,
  • the aqueous preparation (WZ) according to the invention can contain conventional coatings additives in effective amounts.
  • color and effect 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 (PU) with the abovementioned polyesters (PES) as building blocks, the polyurethanes (PU) preferably being used in proportions of up to 90% by weight, based on the non-volatile constituents of (TM), UV absorbers, free-radical scavengers, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, leveling agents, film-forming aids, rheology-controlling additives and preferably catalysts for the reaction of the functional groups (a), ( b) and / or groups (c) described below, and additional crosslinking agents for the functional groups (a), (b) and / or (c).
  • TM non-volatile constituents of
  • TM non-volatile constituents of (TM)
  • UV absorbers free-radical scavengers
  • the aqueous preparation (WZ) according to the invention contains water-miscible or water-soluble solvents in proportions of up to 30% by weight, preferably of up to 30% by weight, particularly preferably of up to 20% by weight, based on (WZ).
  • suitable coating additives are described, for example, in the textbook “Lackadditive” by Johan Bieleman, Verlag Wiley-VCH, Weinheim, New York, 1998.
  • the aqueous formulations (TM) of the present invention are prepared by first mixing all of the ingredients of the formulation except the modified positively charged layered inorganic particles (AT) and optionally the crosslinking agent (V).
  • the inorganic particles (AT) or preferably the suspension of the inorganic particles (AT) prepared preferably in the above-mentioned manner are introduced with stirring, preferably until the suspension is uniformly dispersed, by optical methods, in particular by visual inspection , is being tracked.
  • 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.
  • the crosslinker (V) is optionally added with stirring and the dispersion is preferably adjusted with water to a solids content of 10 to 70 wt .-%, preferably 15 to 60% by weight.
  • the Liquid Crystalline Properties of the Aqueous Formulations (WZ) have liquid-crystalline properties. In particular, they show under crossed polarizers to a birefringent phase, which may be present in addition to an isotropic phase, depending on the concentration of the inventive component (AT).
  • the texture of the birefringent phase is highly similar to those ascribed to nematic phases.
  • the typical lamellar layer structures can be imaged or characterized in terms of their mean layer spacings from the intensity maxima of the first order.
  • aqueous liquid-crystalline preparations (TM) can be used per se as a liquid medium in applications for liquid-crystalline media, for example in displays or polarizers for light.
  • the aqueous preparations (TM) are used as a basis in preferably aqueous coating compositions which, after removal of the volatile constituents from the aqueous preparations according to the invention, form functional layers, in particular for automotive finishing.
  • the aqueous preparations (WZ) are preferably applied in such a wet film thickness for the formation of such functional layers, that after the thermal treatment to remove the volatiles in the resulting layers between 1 and 100 microns, preferably between 5 and 75 microns , more preferably between 10 and 60 microns, in particular between 15 and 50 microns is present.
  • aqueous liquid-crystalline preparations according to the invention can be carried out by customary application methods, such as, for example, spraying, knife coating, brushing, pouring, dipping or rolling.
  • spray application methods such as, for example, spraying, knife coating, brushing, pouring, dipping or rolling.
  • spray application methods are used, compressed air spraying, airless spraying, high rotation spraying and electrostatic spraying (ESTA) are preferred.
  • aqueous preparations WZ
  • WZ aqueous preparations
  • the preferred thermal treatment of the applied layer of the aqueous preparation (TM) is carried out by the known methods, such as by heating in a convection oven or by irradiation with infrared lamps.
  • the thermal curing is carried out 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 layers of the aqueous preparations (WZ) prepared in this way exhibit particular properties, in particular as filler layers and / or as (effect) basecoat films in OEM coating compositions in automotive OEM finishing.
  • a reactor with anchor stirrer, nitrogen inlet, reflux condenser and distillation bridge is charged with 10.511 g of 1,6-hexanediol, 9,977 2,2-dimethyl-1,3-propanediol, 6.329 g of cyclohexane-1,2-dicarboxylic acid anhydride, 23.410 g of dimer fatty acid ( Pripol ® 1012 from Unichema, dimer content at least 97 wt .-%, trimer content at most 1 wt .-%, monomer content than traces) and 0.806 g of cyclohexane introduced.
  • 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 suspension of the white reaction product Zn 2 Al (OH) 6 (4-absa) 2H 2 O has a solids content of 27.1% by weight and a pH of 9.
  • the ultra-small angle X-ray scattering shows an intensity maxima 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 corresponding laminar structures can be seen in the associated cryo-SEM image (FIG. 2).
  • a drop of the dispersion was first snap-frozen in liquid ethane, then deep-frozen in liquid nitrogen and then cut in vacuum at -135 ° C using a stainless steel blade, coated with platinum by sputtering and imaged by scanning electron microscopy.
  • aqueous preparation is outstandingly suitable as a functional component for use in aqueous coating compositions, in particular in aqueous coating compositions for automotive OEM or automotive refinishing, in particular owing to its liquid-crystalline character.

Abstract

L'invention concerne des préparations aqueuses (WZ) qui contiennent 10 à 99,9 % en poids, par rapport à la fraction non volatile de (WZ), d'au moins un polyester hydrodispersable (PES) pour la production duquel on utilise, dans des proportions allant de 7 à 50 % en moles par rapport à la totalité des blocs polyester, des motifs monomères difonctionnels (DME) à groupes espaceurs aliphatiques (SP) ayant 12 à 70 atomes de carbone entre les groupes fonctionnels (Gr), ainsi que 0,1 à 30 % en poids, par rapport à la fraction non volatile de (WZ), de particules inorganiques (AT) lamellaires chargées positivement, solides ou de préférence en suspension, dont les couches individuelles ne pouvant plus faire l'objet d'une intercalation présentent un rapport D/d du diamètre de couche moyen (D) à la densité de couche moyenne (d) supérieur à 50 et dont la charge est au moins partiellement compensée par des anions organiques (OA) à charge simple.
PCT/EP2010/001233 2009-05-13 2010-02-27 Préparations aqueuses à propriétés cristallines liquides WO2010130309A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009021069A DE102009021069A1 (de) 2009-05-13 2009-05-13 Wäßrige Zubereitungen mit flüssigkristallinen Eigenschaften
DE102009021069.5 2009-05-13

Publications (1)

Publication Number Publication Date
WO2010130309A1 true WO2010130309A1 (fr) 2010-11-18

Family

ID=42110114

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/001233 WO2010130309A1 (fr) 2009-05-13 2010-02-27 Préparations aqueuses à propriétés cristallines liquides

Country Status (2)

Country Link
DE (1) DE102009021069A1 (fr)
WO (1) WO2010130309A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103930494A (zh) * 2011-10-19 2014-07-16 巴斯夫涂料有限公司 形成防腐涂层的方法
CN104619431A (zh) * 2012-04-17 2015-05-13 凯密特尔有限责任公司 使用含有层状双氢氧化物的颗粒的涂布组合物涂布金属表面的方法
EP2933300A1 (fr) * 2014-04-16 2015-10-21 BASF Coatings GmbH Composition à base d'hydroxydes et de polyesters en forme de couche, procédé de fabrication de la composition et son utilisation

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4421823A1 (de) * 1994-06-22 1996-01-04 Basf Lacke & Farben Aus mindestens 3 Komponenten bestehendes Beschichtungsmittel, Verfahren zu seiner Herstellung sowie seine Verwendung
WO2001002457A1 (fr) * 1999-07-02 2001-01-11 Basf Coatings Ag Materiau de revetement aqueux, notamment charge aqueuse ou base de protection contre la chute de pierres
US6514473B2 (en) 1995-02-03 2003-02-04 Sasol Germany Gmbh Process for producing hydrotalcites and the metal oxides thereof
EP1371683A1 (fr) * 2002-06-12 2003-12-17 E.I.Du pont de nemours and company Liants aqueux contenant du silicate feuilleté, et un procédé pour leur préparation et leur utilisation des compositions aqueuses
EP1389628A1 (fr) * 2002-08-15 2004-02-18 Eastman Kodak Company Matériau, article et procédé de préparation de matériels contenant des particules anisotropiques orientées
US6762233B2 (en) 2001-10-09 2004-07-13 The University Of Chicago Liquid crystalline composites containing phyllosilicates
WO2007065861A1 (fr) 2005-12-06 2007-06-14 Akzo Nobel N.V. Argile comprenant des ions organiques permettant d'equilibrer les charges et materiaux nanocomposites comprenant cette argile
EP1840113A1 (fr) * 2004-12-22 2007-10-03 Tayca Corporation Hydroxyde double lamellaire pelable dans l'eau, procede de production et utilisation de celui-ci
US20070232746A1 (en) * 2006-03-29 2007-10-04 Shanti Swarup Aqueous coating compositions
WO2009062621A1 (fr) * 2007-11-14 2009-05-22 Basf Coatings Ag Procédé d'ajustement de morphologies définies de phases séparées en couches minces

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1882717A1 (fr) * 2006-07-28 2008-01-30 DSMIP Assets B.V. Composition durcie de polyester du type ininflammable et sans halogènes.
DE102007043241A1 (de) * 2007-09-11 2009-03-12 Sylvia Pfennighaus Gebäude mit Wand aus lebenden Gehölzen

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4421823A1 (de) * 1994-06-22 1996-01-04 Basf Lacke & Farben Aus mindestens 3 Komponenten bestehendes Beschichtungsmittel, Verfahren zu seiner Herstellung sowie seine Verwendung
US6514473B2 (en) 1995-02-03 2003-02-04 Sasol Germany Gmbh Process for producing hydrotalcites and the metal oxides thereof
WO2001002457A1 (fr) * 1999-07-02 2001-01-11 Basf Coatings Ag Materiau de revetement aqueux, notamment charge aqueuse ou base de protection contre la chute de pierres
EP1192200A1 (fr) 1999-07-02 2002-04-03 BASF Coatings AG Materiau de revetement aqueux, notamment charge aqueuse ou base de protection contre la chute de pierres
US6762233B2 (en) 2001-10-09 2004-07-13 The University Of Chicago Liquid crystalline composites containing phyllosilicates
EP1371683A1 (fr) * 2002-06-12 2003-12-17 E.I.Du pont de nemours and company Liants aqueux contenant du silicate feuilleté, et un procédé pour leur préparation et leur utilisation des compositions aqueuses
EP1389628A1 (fr) * 2002-08-15 2004-02-18 Eastman Kodak Company Matériau, article et procédé de préparation de matériels contenant des particules anisotropiques orientées
EP1840113A1 (fr) * 2004-12-22 2007-10-03 Tayca Corporation Hydroxyde double lamellaire pelable dans l'eau, procede de production et utilisation de celui-ci
WO2007065861A1 (fr) 2005-12-06 2007-06-14 Akzo Nobel N.V. Argile comprenant des ions organiques permettant d'equilibrer les charges et materiaux nanocomposites comprenant cette argile
US20070232746A1 (en) * 2006-03-29 2007-10-04 Shanti Swarup Aqueous coating compositions
WO2009062621A1 (fr) * 2007-11-14 2009-05-22 Basf Coatings Ag Procédé d'ajustement de morphologies définies de phases séparées en couches minces

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
EILJI KANEZAKI: "Preparation of Layered Double Hydroxides in Interface Science and Technology", vol. 1, 2004, ELSEVIER, pages: 345
HINTZE-BRUENING H ET AL: "Layered particle-based polymer composites for coatings: Part II-Stone chip resistant automotive coatings", PROGRESS IN ORGANIC COATINGS, ELSEVIER BV, NL LNKD- DOI:10.1016/J.PORGCOAT.2008.09.020, vol. 64, no. 2-3, 1 February 2009 (2009-02-01), pages 193 - 204, XP025884318, ISSN: 0300-9440, [retrieved on 20081122] *
LANGMUIR, vol. 21, 2005, pages 8675
M.C.D.MOURAD ET AL., J. PHYS. CHEM., vol. 112, 2008, pages 10142 - 10152
T.-Y.TSAI ET AL., JOURNAL OF PHYSICS AND CHEMISTRY IN SOLIDS, vol. 67, 2006, pages 938 - 943
TROUTIER-THUILLIEZ A L ET AL: "Layered particle-based polymer composites for coatings: Part I. Evaluation of layered double hydroxides", PROGRESS IN ORGANIC COATINGS, ELSEVIER BV, NL LNKD- DOI:10.1016/J.PORGCOAT.2008.09.021, vol. 64, no. 2-3, 1 February 2009 (2009-02-01), pages 182 - 192, XP025884317, ISSN: 0300-9440, [retrieved on 20081120] *
VON JOHAN BIELEMAN: "Lackadditive", 1998, VERLAG WILEY-VCH

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103930494A (zh) * 2011-10-19 2014-07-16 巴斯夫涂料有限公司 形成防腐涂层的方法
CN104619431A (zh) * 2012-04-17 2015-05-13 凯密特尔有限责任公司 使用含有层状双氢氧化物的颗粒的涂布组合物涂布金属表面的方法
EP2933300A1 (fr) * 2014-04-16 2015-10-21 BASF Coatings GmbH Composition à base d'hydroxydes et de polyesters en forme de couche, procédé de fabrication de la composition et son utilisation
WO2015158466A1 (fr) * 2014-04-16 2015-10-22 Basf Coatings Gmbh Composition à base d'hydroxydes lamellaires et de polyesters, procédé de production de ladite composition et utilisation de cette dernière
CN106459657A (zh) * 2014-04-16 2017-02-22 巴斯夫涂料有限公司 基于层状氢氧化物和聚酯的组合物、所述组合物的制备方法及其用途
US10125269B2 (en) 2014-04-16 2018-11-13 Basf Coatings Gmbh Composition based on layered hydroxides and polyesters, process for preparing the composition, and use thereof

Also Published As

Publication number Publication date
DE102009021069A1 (de) 2010-11-18

Similar Documents

Publication Publication Date Title
EP2430120B1 (fr) Peintures d'apprêt à effet à base d'eau présentant des propriétés optiques améliorées
EP2430064A1 (fr) Agent de revêtement pour produire des couches à haute résistance aux chocs
EP2421924B1 (fr) Laques de base à teneur élevée en matières solides et exemptes d'eau, leur fabrication et leur utilisation pour l'enduction de laques en plusieurs couches ainsi que des laques en plusieurs couches contenant une laque de base à teneur élevée en matières solides et exempte d'eau
DE3828157A1 (de) Verwendung von polyurethanharzen fuer waessrige fuellerzusammensetzungen
EP1265967A2 (fr) Substance de revetement aqueuse, pouvant durcir par voie physique, thermique ou thermique et avec rayonnement actinique, et son utilisation
DE102007038313A1 (de) Anorganisch-modifizierte Polyesterbindemittelzubereitung, Verfahren zur Herstellung und ihre Verwendung
EP2768910B1 (fr) Procédé de fabrication d'un revêtement de protection anti-corrosion
EP2209564B1 (fr) Procédé de production de couches hautement résistantes aux chocs
EP2209857A1 (fr) Agents de revêtement aqueux et procédé de production de couches présentant une résistance aux jets de gravillons
WO2010130309A1 (fr) Préparations aqueuses à propriétés cristallines liquides
EP0548728B1 (fr) Composition d'enduit à base de polyester
EP3283575B1 (fr) Procédé de revêtement
EP2209858A1 (fr) Procédé d'ajustement de morphologies définies de phases séparées en couches minces
DE19515915A1 (de) Wäßrige fremdemulgierte Alkydharzemulsionen aus nachwachsenden Rohstoffen
EP2209859A1 (fr) Agents de revêtement à base de polymères incompatibles et de particules électriquement chargées
WO2010089293A1 (fr) Additif destiné à améliorer la résistance aux solvants et d'autres propriétés de systèmes de liants à base d'eau
WO2015158466A1 (fr) Composition à base d'hydroxydes lamellaires et de polyesters, procédé de production de ladite composition et utilisation de cette dernière
EP1389627A1 (fr) Microgel à base de polyuréthanne

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10706944

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10706944

Country of ref document: EP

Kind code of ref document: A1