WO1990002159A1 - Procede pour fabriquer des materiaux de revetement diluables a l'eau et stables au stockage, ainsi que leur emploi - Google Patents

Procede pour fabriquer des materiaux de revetement diluables a l'eau et stables au stockage, ainsi que leur emploi Download PDF

Info

Publication number
WO1990002159A1
WO1990002159A1 PCT/EP1989/000962 EP8900962W WO9002159A1 WO 1990002159 A1 WO1990002159 A1 WO 1990002159A1 EP 8900962 W EP8900962 W EP 8900962W WO 9002159 A1 WO9002159 A1 WO 9002159A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
dilutable
weight
meth
acrylic
Prior art date
Application number
PCT/EP1989/000962
Other languages
German (de)
English (en)
Inventor
Heinz Waringer
Reiner Felten
Matthias Massoné
Original Assignee
Bollig & Kemper Kg
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 Bollig & Kemper Kg filed Critical Bollig & Kemper Kg
Publication of WO1990002159A1 publication Critical patent/WO1990002159A1/fr
Priority to KR1019900700792A priority Critical patent/KR900701950A/ko

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates

Definitions

  • the present invention relates to a process for the production of storage-stable, water-dilutable coating compositions and the use of these coating compositions for the production of a water-dilutable basecoat.
  • these known coating agents also have disadvantages.
  • a modified or adapted spray technique must be used compared to solvent-based coating agents and that longer flash-off times are required before baking and / or pre-drying. It is also problematic the achievement of sufficient water resistance in coatings produced therewith. This applies particularly to the high quality requirements of the automotive industry.
  • a serious disadvantage is above all that due to their content of inert, water-dilutable aminoplasts, for example hexamethoxymethylmelamine, which require a catalyst additive and / or hardener additive, for example p-toluenesulfonic acid, to be baked at relatively high baking temperatures, for example 160.degree. C., to obtain qualitatively satisfactory coatings, for example with regard to water resistance.
  • a catalyst additive and / or hardener additive for example p-toluenesulfonic acid
  • These known coating agents are used for the production of water-thinnable base coats for the production of a base coat for multi-coat painting, for example a two-coat metallic paint, especially in the wet-on-wet process, on a substrate, for example phosphated and primed and / or coated with filler if only because - depending on the automobile plant - stoving temperatures of 120 to 140 oC for the first coat and only 30 to 100 ° C for the refinish are used for the series painting.
  • a substrate for example phosphated and primed and / or coated with filler if only because - depending on the automobile plant - stoving temperatures of 120 to 140 oC for the first coat and only 30 to 100 ° C for the refinish are used for the series painting.
  • water-borne basecoats have recently been developed for use in the automotive industry, which are mostly based on patented and complex processes, for example microgel technology or the use of complex processes prepared aqueous polyurethane dispersions.
  • the object of the present invention is to produce storage-stable, water-dilutable coating compositions which are particularly stable and low in temperature, for example 80 ° C., and which nevertheless produce high-quality coatings, in particular with respect to very good water resistance, in the simplest and most economical manner. It is also an object of the present invention to use the coating compositions thus obtained for the production of storage-stable, water-dilutable basecoats for producing a basecoat for multi-coat painting, especially in the wet-on-wet process, on a substrate, the basecoats thus obtained being used in application technology as well as the qualitative properties of coatings produced therefrom with solvent-based basecoats should be comparable.
  • the storage-stable, water-dilutable coating compositions produced according to the invention should, if they have the appropriate composition, also be air-drying in spite of their content of aminoplasts.
  • the invention thus relates to a process for the preparation of storage-stable, water-dilutable coating compositions based on carboxyl- and hydroxyl-containing acrylate resins prepared by solution polymerization and / or their copolymers, fully or partially etherified and water-dilutable aminoplasts, water-miscible organic solvents, amines and water, which is characterized in that that non-water-dilutable, fully or partially etherified aminoplasts are used and the coating agent obtained is precondensed at an elevated temperature in the alkaline range.
  • polyethylene waxes which were optionally copolymerized with the acrylate resin or its copolymer during its production, can preferably be used as a further component.
  • non-water-dilutable, fully or partially etherified aminoplasts should be understood to mean that these are used in whole or in part instead of water-dilutable, fully or partially etherified aminoplasts, for example hexamethoxymethylmelamine. In general and preferably only non-water-dilutable, fully or partially etherified aminoplasts are used.
  • the coating agent is in the form of a water-dilutable, solvent-containing, non-gelled, aqueous and storage-stable dispersion.
  • the duration of the precondensation depends not only on the temperature used, but also on the reactivity of the components and can vary within wide limits, for example only 10 minutes or several days. For better control of larger batches, precondensation is generally carried out for several hours and the temperature selected accordingly, which can easily be determined by simple experiments. The criteria listed above are decisive for the temperature and duration of the precondensation. If precondensation is insufficient, no dispersions stable in storage are obtained. If the precondensation is too long or the temperature is too high, the danger of gel formation is reached.
  • the coating agent is first precondensed in the neutral or acidic range, if appropriate also in the solvent phase, and then further precondensed in the alkaline range, this is of course also the inventive method, since only the precondensation in alkaline range leads to storage-stable dispersions which have a defined average particle size on iron.
  • alkaline range is carried out using amines, for example trimethylamine, triethylamine, N-ethyldimethylamine.
  • Alkanolamines for example 2-amino-2-methyl-1-pro, are preferred panol, (dimethylamino) propanols, 3- (diethylamino) -1-propanol, 2-2-iminodiethanol, 2-amino-2-methylpropane-1,3-diol or tris (hydroxymethyl) aminomethane are used.
  • tertiary alkanolamines in particular of, is very particularly preferred
  • 2- (dimethylamino) ethanol The nurse can be used individually or in a mixture with each other.
  • other basic compounds for example ammonia, 2-ethylimidazole, can be used.
  • the pH is adjusted to more than 7 to 10, preferably 7.5 to 9.0 and especially to a pH around 8.
  • the polyethylene waxes which may be used or which are copolymerized with the acrylic resin and / or its copolymer are homopolymers or copolymers of ethylene, for example with vinyl acetate and / or (meth) acrylic acid.
  • a variety of suitable products are commercially available. It is preferred to use polyethylene waxes containing carboxyl groups based on a copolymer of ethylene and (meth) acrylic acid, e.g. with an acid number of 40-120, preferably in an amount of 5 to 30% by weight, in particular 5 to 20% by weight, based on the binder.
  • the procedure is expediently such that the still warm acrylate resin solution or its copolymer solution, immediately after its preparation, the polyethylene wax in the form of the melt, optionally diluted with solvents, with vigorous stirring is added, whereupon the claimed aminoplasts, amines and water are added and precondensed in the alkaline range.
  • the polyethylene wax preferably a carboxyl group-containing one, for example a copolymer based on ethylene and (meth) acrylic acid, in particular with an acid number of around 40, with the acrylate resin and / or its copolymer is preferred.
  • the polyethylene wax is preferably introduced with the solvent, optionally with the addition of a polymerization initiator, for example cumene hydroperoxide, and / or with the addition of some of the polymerization initiator-containing monomers, for example about 20% by weight of the monomers to be used, with heating to the desired polymerization temperature and then the remaining amount of monomers copolymerized with the polyethylene wax under customary process conditions.
  • a polymerization initiator for example cumene hydroperoxide
  • a carboxyl- and hydroxyl-containing acrylate resin and / or its copolymer is preferably produced by copolymerization of acrylic and / or methacrylic acid, acrylic and / or methacrylic acid alkyl esters, hydroxyalkyl (meth) acrylates and the like optionally vinyl aromatics, for example styrene, ⁇ -methylstyrene, vinyl toluene, and / or acrylonitrile and / or diacrylates of (meth) acrylic acid with diols and / or unsaturated dicarboxylic acids, in the presence of water-miscible organic solvents.
  • acrylic acid and methacrylic acid the acid half esters of unsaturated dicarboxylic acids with aliphatic alcohols with 1-10 carbon atoms can also be used in whole or in part.
  • acrylate resins or their copolymers it is also possible to use minor amounts, for example 1 to 20% by weight, based on the other monomers used, of further copolymerizable monomers, for example vinyl esters of branched carboxylic acids having 9-10 carbon atoms, as are commercially available are, glycidyl (meth) acrylate, n-methylol- (meth) acrylamide, divinylbenzene, methacrylonitrile, can also be used.
  • Methacrylic acid with diols e.g. B. butanediol diacrylate
  • Hexanediol diacrylate the total amount of the components always being 100% by weight, and where appropriate in the course of the polymerization 0.1 to 30% by weight, based on the monomer mixture of a carboxyl-containing polyethylene wax, were copolymerized.
  • the alkyl esters of (meth) acrylic acid with aliphatic monoalcohols with 1 to 18 carbon atoms are methyl methacrylate, tert-butyl acrylate, and the ethyl esters, propyl esters, n-butyl esters, isobutyl esters, 2-ethylhexyl esters, lauryl esters and stearyl esters of acrylic acid or methacrylic acid.
  • hydroxyalkyl (meth) acrylates hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate as well as the reaction products of lactones, especially caprolactone, with hydroxyalkyl (meth) acrylates, where the reaction products contain a hydroxyl group in addition to the double bond.
  • unsaturated dicarboxylic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic anhydride. The use of maleic anhydride and / or fumaric acid is preferred.
  • water-miscible solvents for example butanol
  • non-water-miscible solvents for example aliphatic and / or aromatic hydrocarbons, for example petroleum distillates, xylene and / or terpene hydrocarbons, for example Pineoil
  • water-miscible solvents for example butanol
  • non-water-miscible solvents for example aliphatic and / or aromatic hydrocarbons, for example petroleum distillates, xylene and / or terpene hydrocarbons, for example Pineoil
  • the organic solvents are used in an amount such that solutions of the acrylate resin and / or its copolymer are obtained with a solids content of 50 to 85% by weight, preferably 65 to 75% by weight.
  • the solution polymerization of the monomers used to produce the acrylic resin or its copolymer is carried out under customary process conditions and with the use of conventional equipment using polymerization initiators, e.g. B. azo-iso-butyronitrile, tert-butyl perbenzoate, tert-butyl peroctoate, cumene hydroperoxide, di-tert-butyl peroxide.
  • polymerization initiators e.g. B. azo-iso-butyronitrile, tert-butyl perbenzoate, tert-butyl peroctoate, cumene hydroperoxide, di-tert-butyl peroxide.
  • polymerization is carried out at temperatures of 80-160 ° C., preferably at 100-140 ° C.
  • non-water-dilutable fully or partially etherified aminoplasts to be used according to the invention
  • the term “not water-dilutable” is to be understood as meaning that these aminoplasts cannot be diluted by themselves or cannot be diluted sufficiently.
  • This non-water dilutability or water dilutability of aminoplasts can easily be determined by simple experiments, for example in that the aminoplasts to be considered, which are usually in the form of solutions in organic solvents, in a weight ratio of 1: 1 to 1: 5, based on solid resin, be diluted with water and checked for storage stability, flocculation and / or precipitation and for possible formation of 3ode sets and / or separation in two phases.
  • aminoplasts which are virtually impossible to dilute with water
  • aminoplasts etherified with monohydric C 2 -C 4 alcohols for example urea-formaldehyde resins, benzoguanamine resins, melamine-formaldehyde resins.
  • urea-formaldehyde resins for example urea-formaldehyde resins, benzoguanamine resins, melamine-formaldehyde resins.
  • melamine-formaldehyde resins wholly or partly etherified with n-butanol or isobutanol is particularly preferred, in particular those which are classified as highly reactive and cure at temperatures of 80-120 ° C. without addition of hardener.
  • aminoplastics suitable for the production process according to the invention are commercially available in the form of their solutions in isopropanol, butanol or isobutanol, sometimes also with an additional content of other solvents, for example xylene. It is therefore clear to the person skilled in the art that these aminoplasts are at least partially etherified with these alcohols.
  • water-dilutable polyesters containing carboxyl groups and hydroxyl groups, preferably in an amount of 5 to 50% by weight. -%, based on acrylic resin or its copolymer, can also be used. Polyester which can be thinned to a limited extent can also be used, since in the process according to the invention in particular the acrylate resin used or its copolymer acts as a dispersion stabilizer.
  • Saturated polyesters with an acid number of 30-60 and a hydroxyl content of 1 to 6% by weight are preferably used. These polyesters can also be modified, for example using monocarbon acids, for example fatty acids, ethylhexanoic acid, benzoic acid, tert-butylbenzoic acid, hydroxycarboxylic acids, for example 4-hydroxybenzoic acid, 2-hydroxybenzoic acid, and / or acrylic acid and / or methacrylic acid and / or styrene and / or vinyl toluene.
  • monocarbon acids for example fatty acids, ethylhexanoic acid, benzoic acid, tert-butylbenzoic acid, hydroxycarboxylic acids, for example 4-hydroxybenzoic acid, 2-hydroxybenzoic acid, and / or acrylic acid and / or methacrylic acid and / or styrene and / or vinyl toluene.
  • polyesters and / or alkyd resins can also be modified by partial urethanization, so that they also contain urethane groups in addition to the carboxyl and hydroxyl groups.
  • Such polyesters can usually be prepared, for example, by reacting hydroxyl-containing polyesters with urea or by transesterifying alkyl urethanes, for example butyl urethane, with hydroxyl-containing polyesters or by proportionally replacing polycarboxylic acids with polyisocyanates in the preparation of polyesters.
  • polyesters instead of these or in addition to these polyols, for example ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, hydroxypivalic acid neopentyl glycol ester, neopentyl glycol, hexanediol-1,6, cyclohexanedimethanol, of caprolactone, glycerol, trimethylolpropane, trishydroxyethyl isocyanurate, preferably in an amount of 1 to 20% by weight, based on the binder.
  • the polyols can be used individually or as a mixture of at least two polyols, e.g. B. propylene glycol and trishydroxyethyl isocyanurate and / or polyethylene glycol and / - or glycerin can be used.
  • Preferred is the use of polyols based on caprolactone, in particular diols, optionally in a mixture with other polyols, in particular propylene glycol and / or polyethylene glycol and / or glycerin.
  • thermosetting water-dilutable coating compositions can also be produced by the process according to the invention with a suitable composition, the production of thermosetting water-dilutable coating compositions is preferred.
  • the weight ratio of acrylic resin to the non-water-thinnable aminoplast depends not only on their composition and / or the type of aminoplast, but also on the intended use of the water-thinnable coating agent and can vary within wide limits.
  • the binder of the coating composition consists of 60 to 90% by weight of the acrylate resin or its copolymer and 40 to 10% by weight of the non-water-dilutable aminoplast, with mixing ratios of 65 to 80% by weight of acrylate resins or its copolymer 35 to 20% by weight of aminoplast are preferred.
  • the water-dilutable coating compositions prepared according to the invention can also, in conjunction with customary additives and auxiliaries, for example pigments such as titanium dioxide, carbon black, graphite, iron oxides, metal pigments and / or pearlescent pigments, organic pigments, for example phthalocyanine pigments, fillers, for example barium sulfate, wetting and dispersing auxiliaries, Leveling agents, thickening agents, anti-abhesives, thixotropic agents, which must be sufficiently stable in the alkaline range, are used.
  • customary additives and auxiliaries for example pigments such as titanium dioxide, carbon black, graphite, iron oxides, metal pigments and / or pearlescent pigments, organic pigments, for example phthalocyanine pigments, fillers, for example barium sulfate, wetting and dispersing auxiliaries, Leveling agents, thickening agents, anti-abhesives, thixotropic agents, which must be sufficiently stable in the alkaline range, are
  • the water-thinnable coating compositions prepared according to the invention can be used both as clearcoats, for example for decorative protection of aluminum or tinplate or as clearcoat for a multi-layer coating, and for example as a primer, filler or topcoat.
  • solids content, solvent content and water content of the storage-stable, water-dilutable coating compositions produced according to the invention depend on the intended use and the required processing consistency, and on the rheological properties required, so that no generally applicable information can be given here.
  • Storage-stable, water-thinnable coating compositions produced according to the invention can be applied to a wide variety of substrates or substrates using all customary techniques, for example brushing, knife coating, spraying, including airless and / or electrostatic, electrostatic spraying, dipping, rolling, electrophoretic application (only on metal) , for example paper, cardboard, textile, glass, wood, particle board, but especially on metal or plastic.
  • the coating compositions produced according to the invention can also be used for producing coatings on sheet metal strips in the so-called coil coating process, in particular for producing a primer layer on galvanized steel sheets or for producing a base layer for multi-layer coating. Because of their excellent rheological properties, the coating compositions prepared according to the invention are particularly suitable for spray application.
  • the dry film layer thickness is generally, depending on the intended use, about 4 to 50 microns.
  • the optimum dry film layer thicknesses for the respective application are known to the person skilled in the art.
  • thermosetting coating compositions produced according to the invention are comparable with those of known coating compositions.
  • thermosetting coating agents are relatively insensitive to fluctuating relative atmospheric humidity, so that costly air conditioning of spray booths may not be necessary.
  • the stoving conditions when using storage-stable, water-dilutable, heat-curable coating compositions produced in accordance with the invention are, depending on the particular intended use, comparable to those of conventional, solvent-containing, heat-curing coating compositions and cover the range from 20 minutes at 80 ° C. to 30 seconds at 250 ° C. Object temperature.
  • the storage-stable, water-dilutable, heat-curable coating compositions produced according to the invention are particularly well suited for use in the low temperature range, for example baking conditions of 40 minutes at 80 ° C. or 17 minutes at 130 ° C. or 25 minutes at 140 ° C. circulating air temperature, which at For example, it meets the requirements of the automotive industry for the use of conventional solvent-borne stoving enamels for the initial series painting and for refinishing, and also for the use of the water-dilutable, thermosetting coating agents produced according to the invention for auto refinishing at dealers and in other areas of application, for example plastic painting, where low Baking temperatures are required or desirable.
  • polyethylene waxes used which have preferably been copolymerized with the acrylic resin or its copolymer used in the production of the latter, generally improve inter alia the drying, surface smoothness and water resistance of the coatings produced from these coating compositions. It is noteworthy here that considerable amounts of polyethylene waxes can optionally be used or polymerized into the acrylic resin or its copolymer during its production.
  • polyethylene waxes depends on the intended use of the storage-stable, water-thinnable coating compositions produced according to the invention and their composition and is not always advisable, since the use of polyethylene waxes can also be disadvantageous, for example impairing the adhesion of any coatings that follow the first coating.
  • the surprising effect of the present invention is that very good, storage-stable, aqueous dispersions are obtained from the unforeseeable use of water-thinnable aminoplasts and the precondensation of the coating agent in the alkaline range, from which coatings with excellent properties can also be obtained.
  • a particular use of the storage-stable, water-thinnable coating compositions produced according to the invention is their use for producing a water-thinnable basecoat for producing a base layer for the multi-layer coating, especially in the wet-on-wet process, on a substrate.
  • the production of multi-layer coatings, also in the wet-on-wet process, on a substrate, for example phosphated and / or primed and / or filler-coated body panels or metal strips to be coated in the coil coating process, is likewise already known.
  • the storage-stable, water-dilutable coating compositions prepared according to the invention are particularly suitable for the preparation of water-dilutable basecoats, in particular metallic pigments, for example aluminum paste, in combination with clearcoat for wet-on-wet - Processes are suitable and lead to multi-layer coatings with very good properties, in particular with regard to quick drying or the possibility of overpainting with clear lacquer and excellent metallic appearance and water resistance.
  • Thermosetting, solvent-containing, water-dilutable or powdered coating compositions for example based on hydroxyl-containing acrylate resins and / or hydroxyl-containing polyesters, in particular aromatics-free and / or low-aromatics, and aminoplasts, in particular, can be used as the clearcoat Melamine-formaldehyde resins, and / or polyisocyanates, in particular based on aliphatic or cycloaliphatic polyisocyanates, for example hexamethylene diisocyanate, isophorone diisocyanate, or on the basis of epoxy resins, in particular cycloaliphatic epoxy resins.
  • the remaining 80% of the monomer mixture consisting of 204 g styrene, 298 g butyl methacrylate, 124 g 2-hydroxyethyl acrylate, 30 g methacrylic acid and 5 g tert-butyl peroctoate are uniformly introduced into this solution over a metering dropping funnel within 2 hours. After a further hour, a mixture of 2 g of tert-butyl peroctoate and 34 g of butyl glycol is added dropwise within 30 minutes and polymerization is continued for a further 2 hours at 120 ° C.
  • a clear, highly viscous acrylic resin solution with a solids content of 66%, acid number 30 (based on solid resin) and a viscosity (DIN 53 211) of 70 seconds is measured, measured after dilution to 30% by weight solids with butyl glycol.
  • a homogeneous milky white acrylic resin solution is obtained.
  • the solids content of the solution is 60%, the acid number is 30 and the viscosity according to DIN 53211 (4 mm nozzle) at 20 "C is 75 sec (30% in butyl glycol).
  • neopentyl glycol 100.1 g of trimethylolpropane, 287.6 g of dimethyl terephthalate and 0.6 g are placed in a 2-liter four-necked round-bottomed flask equipped with a thermometer, stirrer, gas inlet tube, intercooler, water separator, reflux condenser and heating Dibutytin oxide heated to 160 ° C and stirred at this temperature for 1 hour.
  • the temperature is then increased by 10 ° C every hour until 200 ° C is reached. After a further hour, 246.1 g of isophthalic acid, 216.5 g of adipic acid and 12 g of xylene are added and the temperature is increased again by 10 ° C. to 220 ° C. every hour. At this temperature, stirring is continued until an acid number of ⁇ 5 is reached. The mixture is then cooled to 190 ° C. and the acid number is adjusted to 33-35 with 95 g of trimellitic anhydride. After the acid number has been reached, the mixture is diluted with butyl glycol to a solids content of 75%. The finished polyester resin solution has a viscosity (DIN 53 211, 4 mm nozzle, 20 oC) of 30 sec, 40% in butyl glycol.
  • Example 1 Example 1:
  • a white, highly viscous chemical solution with a solids content of 28%, a pH of 8.9 and a viscosity (DIN 53 211; 4 mm nozzle; 20 ° C.) of the solution diluted with butyl glycol to 20% for 60 seconds is obtained.
  • the coating agent obtained in this way is a storage-stable, aqueous dispersion.
  • Example 1 In the apparatus described in Example 1, a mixture of 337.5 g of the acrylic resin according to Reference Example 3, 96.3 g of the melamine-formaldehyde resin solution used in Example 1, 4 g of dimethylaminoethanol and 100 g of fully demineralized water are carefully heated to 60 ° C. and stirred for 2 hours this temperature. Then 3.2 g of dimethylaminoethanol and 459 g of demineralized water preheated to 60 ° C. are added and the mixture is stirred at this temperature for a further 2.5 h.
  • a white, highly viscous binder solution having a solids content of 27%, a pH of 8.9 and a viscosity (DIN 53 211; 4 mm nozzle, 20 ° C.) of the solution diluted with butyl glycol to 20% for 40 seconds is obtained.
  • the coating agent obtained in this way is a storage-stable, aqueous dispersion.
  • Example 3 In the apparatus described in Example 1, a mixture of 375 g of acrylic resin solution according to Reference Example C, 107 g of the melamine-formaldehyde resin solution used in Example 1, 3 g of dimethylaminoethanol and 100 g of fully demineralized water is carefully heated to 60 ° C. and stirred for 2 hours Temperature.
  • a cream-colored 3-solvent solution with a solids content of 30%, a pH of 7.5 and a viscosity (DIN 53 211; 4 mm nozzle, 20 ° C.) of the undiluted 30% solution of 30 seconds is obtained.
  • the coating agent obtained in this way is a storage-stable, aqueous dispersion.
  • Example 4 is a storage-stable, aqueous dispersion.
  • Example 1 In an apparatus according to Example 1, 375 g of the acrylic resin solution from Reference Example D, 107 g of the melamine-formaldehyde resin solution used in Example 1, 3 g of dimethylaminoethanol and 100 g of fully demineralized water are carefully heated to 60 ° C. and stirred at this temperature for 2 hours.
  • a cream-colored, binder solution having a solids content of 30%, a pH of 7.6 and a viscosity (DIN 53 211; 4 mm nozzle, 20 ° C.) of the undiluted 30% solution of 50 seconds is obtained.
  • the coating agent obtained in this way is a storage-stable, aqueous dispersion.
  • Example 1 In an apparatus according to Example 1, 276.2 g of the acrylic resin solution from Reference Example A, 26.7 g of butyl glycol, 20.3 g of a commercially available triol based on caprolactone (MW: 900, viscosity: 270 cSt / 55 ° C.) are heated. , 96.3 g of the melamine-formaldehyde resin solution used in Example 1, 5 g of dimethylaminoethanol and 144.7 g of fully demineralized water carefully at 60 ° C. and stirred at this temperature for 2 h.
  • a commercially available triol based on caprolactone MW: 900, viscosity: 270 cSt / 55 ° C.
  • the coating agent obtained in this way is a storage-stable, aqueous dispersion.
  • a white, highly viscous binder solution having a solids content of 27%, a pH of 8.9 and a viscosity (DIN 53 211; 4 mm nozzle, 20 ° C.) of 45 seconds is obtained, diluted with butyl glycol to a solids content of 20%.
  • This mixture tends to separate after only a few hours of storage and, after 48 hours of storage at 20 ° C., has a separation into two phases, so that it can practically not be used as a coating agent.
  • Aquacer 840 polyethylene copolymer 11.31 parts from Cera-Chemie 30% in water
  • Viscosity 30 sec (DIN 53 211, 4 mm nozzle 20 ° C)
  • Viscosity 30 sec (DIN 53 211, 4 mm nozzle 20 ° C)
  • Latekoll D-Lsg (acrylic acid-based thickener from
  • Viscosity 30 sec (DIN 53 211, 4 mm nozzle 20 oC)
  • Latekoll 2 solution / 8% in distilled water 3.10 parts
  • Viscosity 30 sec (DIN 53 211, 4 mm nozzle 20 oC)
  • Application example 5 (comparison)
  • a basecoat was prepared analogously to Application Example 1, but with the difference that the coating composition according to Comparative Example II was used instead of the coating composition according to Example 1.
  • Viscosity 28.sec (DIN 53 211, 4 mm nozzle 20 ° C)
  • the basecoats prepared according to use examples 1 to 5 were each applied in a customary manner to steel sheets coated with zinc phosphating, cathodic electrocoating primer and spray filler, as are usually used for test purposes in the automotive industry, by means of a spray gun, so that a dry film layer thickness of 12 to 15 ⁇ m was achieved.
  • the test sheets coated in this way were pre-dried for 5 minutes at a circulating air temperature of 80 ° C. and then in the usual way with a commercially available baking clear varnish based on hydroxyl-containing acrylate resin and melamine formaldehyde resin, as is used for automotive painting, in a dry film layer thickness of 35-40 ⁇ m overpainted and baked for 30 minutes at 130 ° C.
  • the resulting multi-layer coatings have a high gloss, brilliant appearance and are extremely resistant to the effects of water, light and weather.
  • a refinish coating was applied to the test sheets with the multi-layer coating as described above, the procedure being as above, but with the exception that instead of the above baking clearcoat, a two-component automotive repair clearcoat based on a hydroxyl-containing acrylate resin and an aliphatic polyisocyanate based on Hexamethylene diisocyanate was used and at 45 min
  • a metallic base layer was applied in a customary manner to the basecoat according to application example 1 on a bumper made of polycarbonate primed with a commercially available 2-component primer based on hydroxyacrylate / polyisocyanate and, after a predrying of 5 minutes at 80 ° C. ambient air temperature, then with a commercially available high flexible 2-component clearcoat based on hydroxyacrylate / polyisocyanate overcoated, after which it was baked for 40 min at 80 ° C. The following tests were carried out with this plastic part painted in this way:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour fabriquer des matériaux de revêtement diluables à l'eau et stables au stockage, à base de résines acryliques renfermant des groupes carboxyle et hydroxyle et/ou leurs copolymérisats, produits par polymérisation en solution, d'aminoplastes diluables à l'eau totalement ou partiellement étherifiés, de solvants organiques miscibles dans l'eau, d'amines et d'eau, caractérisé en ce que des aminoplastes non diluables à l'eau, totalement ou partiellement étherifiés sont utilisés et en ce que le matériau de revêtement obtenu est précondensé dans le domaine alcalin à haute température. L'emploi de ces matériaux de revêtement est également décrit.
PCT/EP1989/000962 1988-08-18 1989-08-16 Procede pour fabriquer des materiaux de revetement diluables a l'eau et stables au stockage, ainsi que leur emploi WO1990002159A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900700792A KR900701950A (ko) 1988-08-18 1990-04-18 저장하기에 안정한 수성 피복조성물의 제조방법 및 이의 용도

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3828051.5 1988-08-18
DE3828051A DE3828051C3 (de) 1988-08-18 1988-08-18 Verfahren zur Herstellung von lagerstabilen, wasserverdünnbaren Überzugsmitteln und Verwendung

Publications (1)

Publication Number Publication Date
WO1990002159A1 true WO1990002159A1 (fr) 1990-03-08

Family

ID=6361117

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1989/000962 WO1990002159A1 (fr) 1988-08-18 1989-08-16 Procede pour fabriquer des materiaux de revetement diluables a l'eau et stables au stockage, ainsi que leur emploi

Country Status (5)

Country Link
KR (1) KR900701950A (fr)
AU (1) AU4061589A (fr)
DE (1) DE3828051C3 (fr)
WO (1) WO1990002159A1 (fr)
ZA (1) ZA896220B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007195A1 (fr) * 1991-09-28 1993-04-15 Basf Lacke + Farben Aktiengesellschaft Peintures aqueuses et procede pour la fabrication de vernis de finition pour automobiles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58147467A (ja) * 1982-02-26 1983-09-02 Toray Ind Inc 電着被覆用組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1519046B2 (de) * 1965-08-04 1973-04-05 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Einbrennlacke
DE1519068C3 (de) * 1965-08-05 1981-01-15 Hoechst Ag, 6000 Frankfurt Wäßrige Lacklösungen zur elektrophoretischen Lackierung
AT291571B (de) * 1969-07-29 1971-07-26 Vianova Kunstharz Ag Verfahren zur Herstellung von nach Neutralisation wasserverdünnbaren, wärmehärtbaren, selbstvernetzenden Copolymerisaten
GB1454405A (en) * 1972-12-04 1976-11-03 Ppg Industries Inc Sprayable water-dispersed acrylic interpolymer compositions
JPS59105064A (ja) * 1982-12-07 1984-06-18 Kansai Paint Co Ltd 熱硬化性メタリツク塗料
US4579888A (en) * 1984-04-10 1986-04-01 Toyo Ink Manufacturing Co., Ltd. Aqueous resin dispersion

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58147467A (ja) * 1982-02-26 1983-09-02 Toray Ind Inc 電着被覆用組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 86, Nr. 16, 18. April 1977 (Columbus, Ohio, US), seiten 81, 82* Zusammenfassung Nr. 108121e, & JP-A-51136729 (Nippon Paint Corp.) 26. November 1976* *
PATENT ABSTRACTS OF JAPAN, Band 7, Nr. 263 (C-196)(1408), 24. November 1986; & JP-A-58147467 (Toray K.K.) 2. September 1983 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993007195A1 (fr) * 1991-09-28 1993-04-15 Basf Lacke + Farben Aktiengesellschaft Peintures aqueuses et procede pour la fabrication de vernis de finition pour automobiles
CN1042136C (zh) * 1991-09-28 1999-02-17 巴斯福涂料股份公司 水基涂料和制造汽车罩面漆的方法及其用途

Also Published As

Publication number Publication date
KR900701950A (ko) 1990-12-05
AU4061589A (en) 1990-03-23
DE3828051A1 (de) 1990-03-08
DE3828051C2 (fr) 1990-08-23
DE3828051C3 (de) 1994-04-14
ZA896220B (en) 1990-05-30

Similar Documents

Publication Publication Date Title
EP0579193B1 (fr) Composition de revêtement aqueuse thermodurcissable, sa préparation et utilisation
EP0391271B1 (fr) Composition de revêtement aqueuse et thermodurcissable à base de polyester et d'acrylate, son procédé de préparation et son utilisation
EP0036975B1 (fr) Procédé de fabrication de vernissages à effet métallique et objets plans présentant des vernissages multi-couches à effet métallique résistant aux intempéries
DE4009858C2 (de) Wäßriger pigmentierter Basislack enthaltend als Bindemittel ein wasserverdünnbares Polyacrylatharz und Verwendung eines solchen Basislacks
EP0674672B1 (fr) Dispersions aqueuses de polymeres pour laques transparentes
EP0871552B1 (fr) Procede d'obtention de revetements multicouches
EP0598280B1 (fr) Composition de liant, revêtement la contenant, leur préparation et utilisation
EP0902731A1 (fr) Procede de production de revetements multicouches
EP0071071B2 (fr) Procédé de préparation d'une dispersion aqueuse d'un copolymère et usage de celle-ci
EP0505469B1 (fr) Procede de fabrication d'un revetement multicouche de protection et/ou de decoration
DE19604911A1 (de) Bindemittel für Lacke auf Polyurethanbasis
DE19712940A1 (de) Wäßriges Beschichtungsmittel
DE3832826A1 (de) Verfahren zur herstellung eines mehrschichtigen ueberzugs, waessrige beschichtungszusammensetzungen, wasserverduennbare polyacrylatharze und verfahren zur herstellung von wasserverduennbaren polyacrylatharzen
DE19730890A1 (de) Verfahren zur Herstellung mehrschichtiger Überzüge
DE4223183C1 (en) Emulsifier-free thermo-curable coating as aq. emulsion - comprises self-emulsifying ester-based copolymers, polyester oligomers, water-(in)soluble amine resin crosslinking agents and capped poly:isocyanate(s)
EP1590385A1 (fr) Substances de recouvrement, leur procede de production et leur utilisation
EP0812867B1 (fr) Procédé pour le revêtement de substrats
DE3828051C2 (fr)
DE3832142A1 (de) Verfahren zur herstellung eines mehrschichtigen, schuetzenden und/oder dekorativen ueberzugs und wasserverduennbare beschichtungszusammensetzungen
EP3227349B1 (fr) Agent de revêtement pigmenté et revêtements fabriqués à partir de celui-ci
EP3227350B1 (fr) Agent de revêtement pigmenté et revêtements fabriqués à partir de celui-ci
WO1995033011A1 (fr) Agents de revetement aqueux
EP3227351B1 (fr) Copolymère et agent de revêtement pigmenté contenant le copolymère

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR DK FI HU JP KR NO RO SU US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE