WO2007048554A2 - Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes - Google Patents

Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes Download PDF

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Publication number
WO2007048554A2
WO2007048554A2 PCT/EP2006/010183 EP2006010183W WO2007048554A2 WO 2007048554 A2 WO2007048554 A2 WO 2007048554A2 EP 2006010183 W EP2006010183 W EP 2006010183W WO 2007048554 A2 WO2007048554 A2 WO 2007048554A2
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WIPO (PCT)
Prior art keywords
powder dispersions
organic solvents
coatings
particles
melamine
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PCT/EP2006/010183
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German (de)
English (en)
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WO2007048554A3 (fr
Inventor
Michael Tecklenborg
Bianca Giesen
Marco Deyda
Hubert Baumgart
Veronika Tomanek
Petra Wagner
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Basf Coatings Ag
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Publication of WO2007048554A2 publication Critical patent/WO2007048554A2/fr
Publication of WO2007048554A3 publication Critical patent/WO2007048554A3/fr

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    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D5/03—Powdery paints
    • C09D5/031—Powdery paints characterised by particle size or shape
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm

Definitions

  • the present invention relates to new, pseudoplastic, of organic solvents substantially or completely free, aqueous powder dispersions. Moreover, the present invention relates to a novel process for the preparation of pseudoplastic, of organic solvents substantially or completely free, aqueous powder dispersions. Furthermore, the present invention relates to the use of the new, pseudoplastic, of organic solvents substantially or completely free, aqueous powder dispersions for the production of thermoset materials.
  • Aqueous powder dispersions in particular aqueous powder coating dispersions, are known to experts as “powder slurries” or “slurries” for short.
  • slurries refers to structurally viscous powder dispersions which are essentially or completely free of organic solvents. If the slurries contain no opaque constituents, they are also referred to below as “clearcoat slurries”.
  • the known clearcoat slurries must therefore be further developed so that they provide clearcoats of primary finishes which have excellent adhesion to the refinishes applied to the clearcoats even without prior sanding.
  • the refinishes may comprise a surfacer, a basecoat and a clearcoat or a basecoat and a clearcoat or only a clearcoat. In all cases, however, liability must be guaranteed.
  • Object of the present invention is novel, pseudoplastic, free from organic solvents, aqueous powder dispersions, d. H. To provide new slurries, which have a good filterability, a good gear pump handling and a good storage stability.
  • thermoset materials are said to be ideally suited for the production of thermoset materials.
  • the coating materials should be suitable as primers, fillers, primers, basecoats, solid-color topcoats and clearcoats for the production of primer coatings, surfacer coats, antistonechip primers, basecoats, solid-color topcoats and clearcoats.
  • the clearcoat slurries should be outstandingly suitable for the production of clearcoats of color and / or effect multicoat paint systems, in particular multicoat paint systems which are prepared by wet-on-wet processes.
  • the new clearcoat slurries are intended to provide new clearcoats of original finishes, in particular of primary finishes on automobile bodies, which, even without prior grinding, have excellent adhesion to the refinishes applied to the clearcoats, in particular to refinishes which are applied as part of the complete repair of automotive bodycoat finishes , exhibit.
  • the refinish coatings are intended to comprise a surfacer coating, a basecoat and a clearcoat or a basecoat and a clearcoat or only a clearcoat. In all cases, however, the liability should be guaranteed.
  • the new clearcoats should have a very good flow, very good optical properties (Appearance) and a high condensation resistance, chemical resistance, scratch resistance and weather resistance. They should be largely or completely free of paint defects, such as noses, specks, pinholes, craters, stoves, micro-disturbances (starry sky), pimples and cloudiness.
  • the new, pseudoplastic, free from organic solvents, aqueous powder dispersions are referred to as "slurries invention.
  • the slurries according to the invention had a good filterability and a good gear pump handling combined with a good storage stability.
  • thermoset materials were outstandingly suitable for the production of new thermoset materials.
  • novel coating materials were outstandingly suitable as novel primers, fillers, primers, basecoats, solid-color topcoats and clearcoats for the production of new primer coatings, surfacer coats, antistonechip primers, basecoats, solid-color topcoats and clearcoats.
  • the clearcoat slurries according to the invention were outstandingly suitable for the production of clearcoats of novel multicoat color and / or effect paint systems, in particular new multicoat systems, which were prepared by wet-in-wet processes.
  • the new clearcoat slurries provided new clearcoats of original finishes, in particular of primary finishes on automobile bodies, which, even without prior sanding, had outstanding adhesion to the refinish coatings applied to the novel clearcoats, in particular to refinishes applied as part of the complete repair of automotive bodywork initial coatings. on.
  • the refinishes comprised a surfacer coating, a basecoat and a clearcoat or a basecoat and a clearcoat or only a clearcoat. In all cases, however, the excellent adhesion was guaranteed even without sanding.
  • the new clearcoats had a very good flow, very good optical properties (Appearance) and a high condensation resistance, chemical resistance, scratch resistance and weather resistance. They were largely or completely free from paint defects, such as noses, specks, pinholes, craters, stoves, micro-disturbances (starry sky), pimples and cloudiness. Surprisingly, they also showed a high stone chip resistance.
  • the slurry according to the invention contains as disperse phase solid and / or highly viscous, dimensionally stable particles (A).
  • Dispossionally stable means that the particles (A) under the usual and known conditions of storage and application of pseudoplastic, aqueous powder dispersions or slurries, if at all, only slightly agglomerate and / or disintegrate into smaller particles, but also under the influence of Shearing forces retain their original shape entirely or substantially.
  • the maximum particle size is preferably 30, preferably 20, particularly preferably 10 and in particular 5 ⁇ m.
  • the dimensionally stable particles (A) preferably have a monomodal particle size distribution measured by the laser diffraction method:
  • D (v, 0.1) 0.8 to 1.2 ⁇ m, preferably 0.9 to 1, 1 ⁇ m and in particular 0.95 to
  • the laser diffraction method is a customary and known method for measuring particle sizes and their distribution and can be carried out, for example, using the Mastersizer® from Malvern Instruments.
  • the particle size distribution can be adjusted in any desired manner, for example by the use of suitable dispersing aids (A3) such as emulsifiers or wetting agents, by mechanical comminution of the dimensionally stable particles (A) and / or by the content of the particles (A) in ionic groups.
  • suitable dispersing aids (A3) such as emulsifiers or wetting agents
  • the particles (A) are dispersed in an aqueous medium (B).
  • the aqueous medium can be water or preferably contain at least one of the additives (A3) described below, in particular dispersing assistant (A3) and rheology aid (A3).
  • the content of the slurry of particles (A) according to the invention can vary very widely and depends on the requirements of the individual case.
  • the content is preferably from 5 to 70, preferably from 10 to 60, more preferably from 15 to 50 and in particular from 15 to 40,% by weight, based on the inventive slurry.
  • the slurry according to the invention is completely or substantially free of organic solvents.
  • Substantially free means that the slurry according to the invention has a solvent content of ⁇ 6% by weight, preferably ⁇ 5% by weight and in particular ⁇ 3% by weight.
  • the slurry according to the invention is structurally viscous.
  • the viscosity behavior describes a state which, on the one hand, takes account of the requirements of storage and settling stability of the slurry according to the invention: in the agitated state, for example when pumping the slurry according to the invention in the ring line of a coating plant and when applied, the slurry of the invention assumes a low-viscosity state, which ensures good processability. Without shear stress, on the other hand, the viscosity increases and in this way ensures that the slurry according to the invention already present on the substrate to be coated has a reduced tendency to run off on vertical surfaces ("run formation").
  • the higher viscosity in the unmoved state prevents sedimentation of the solid particles (A) or ensures that the slurry of the invention which is only slightly deposited and / or agglomerated during the storage time is stirred up again.
  • the pseudoplastic behavior is preferably adjusted by means of suitable rheology auxiliaries (A3), preferably thickener (A3), in particular nonionic and ionic thickeners (A3), which are preferably present in the aqueous phase (B).
  • suitable rheology auxiliaries A3
  • thickener A3
  • nonionic and ionic thickeners A3
  • the slurry according to the invention serves to prepare the thermoset materials according to the invention; it is therefore curable.
  • the inventive slurry may be curable physically, thermally and / or with actinic radiation.
  • the inventive slurry is preferably curable with actinic radiation, thermally or thermally and with actinic radiation (dual cure).
  • the inventive slurry is preferably thermally or thermally curable and curable with actinic radiation; in particular, it is thermally curable.
  • the physical hardening can support the other hardening mechanisms.
  • the term "physical curing” means the hardening of a layer of a coating material by filming
  • the thermal curing can take place via the so-called self-crosslinking of constituents of the slurry according to the invention.
  • the inventive slurry preferably its particles (A) contains complementary reactive functional groups that undergo thermally initiated and sustained reactions with the hydroxyl groups present and / or different complementary reactive functional groups, and / or autoreactive functional groups can react with oneself.
  • the thermal curing can also take place via the so-called foreign crosslinking of constituents of the slurry according to the invention.
  • the slurry according to the invention preferably its particles (A), contains at least two constituents, each containing one type of complementary reactive functional group, which can undergo thermally initiated and sustained reactions with each other.
  • the slurry according to the invention preferably its particles (A) contains activatable bonds with actinic radiation, which are activated by the irradiation and with other activated bonds of their kind Polymerization reactions and / or crosslinking reactions, which proceed by free-radical and / or ionic mechanisms.
  • Actinic radiation here and below includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-radiation or gamma radiation, in particular UV radiation, or corpuscular radiation, such as electron radiation, beta radiation, alpha radiation, proton radiation or neutron radiation, in particular electron radiation , to understand.
  • electromagnetic radiation such as near infrared (NIR), visible light, UV radiation, X-radiation or gamma radiation, in particular UV radiation, or corpuscular radiation, such as electron radiation, beta radiation, alpha radiation, proton radiation or neutron radiation, in particular electron radiation , to understand.
  • the inventive slurry contains as essential ingredient of the invention at least one of organic solvents depleted, reactive, water-insoluble, etherified melamine-formaldehyde resin (A1), preferably in an amount of 1 to 20 wt .-%, preferably 2 to 18 wt .-% and in particular 3 to 15 % By weight, in each case based on the film-forming solids of the slurry according to the invention.
  • organic solvents depleted, reactive, water-insoluble, etherified melamine-formaldehyde resin (A1) preferably in an amount of 1 to 20 wt .-%, preferably 2 to 18 wt .-% and in particular 3 to 15 % By weight, in each case based on the film-forming solids of the slurry according to the invention.
  • film-forming solid is to be understood as meaning the sum of all components of the slurry according to the invention which, after the application and curing of the slurry according to the invention, build up the solids of the thermoset materials according to the invention.
  • all or almost all of the film-forming ingredients are concentrated in the dimensionally stable particles (A).
  • the melamine-formaldehyde resin (A1) is depleted of organic solvents, in particular hydroxyl-containing organic solvents, especially monoalcohols having 1 to 6 carbon atoms in the alkyl radical, especially butanol and / or isobutanol.
  • Depleted means that from a solution of a melamine-formaldehyde resin, the organic solvents are removed so long and in such an amount that there is no danger of damage to the formaldehyde resin, in particular by premature crosslinking.
  • At least 20% by weight, preferably at least 30% by weight, particularly preferably at least 35% by weight and in particular at least 40% by weight of the organic solvent present are removed.
  • the melamine-formaldehyde resin (A1) is reactive. Preferably, the reactivity results from the content of the melamine-formaldehyde resin (A1) in imino groups.
  • the melamine-formaldehyde resin (A1) is etherified. It is preferably etherified with butanol and / or isobutanol.
  • the melamine-formaldehyde resin (A1) can be prepared by the depletion of the organic solvents, preferably by distillation, azeotropic distillation or ultrafiltration, from the solution of a reactive, water-insoluble, etherified melamine-formaldehyde resin.
  • the conditions pressure, temperature should be selected so that no premature crosslinking of the melamine-formaldehyde resin (A1) occurs.
  • the person skilled in the art can therefore select the appropriate conditions based on his general knowledge.
  • the slurries of the invention may otherwise be of different composition.
  • the slurries of the invention may otherwise be of different composition.
  • the slurry according to the invention preferably has a content of potentially ionic groups of from 0.05 to 1, preferably from 0.05 to 0.9, preferably from 0.05 to 0.8, particularly preferably from 0.05 to 0.7 and in particular from 0.05 to Has 0.6 meq / g of solids.
  • these groups are present in the binders (A2).
  • the amount of neutralizing agent (A3) is selected so that the degree of neutralization is 100%, preferably less than 80%, more preferably less than 60% and in particular less than 50%.
  • the chemical nature of the binder (A2) is generally not limitative in this regard, as long as it contains ion-forming groups which can be converted into salt groups by neutralization and can thereby take on ionic stabilization of the particles in water.
  • Suitable anionic groups are acid groups such as carboxylic acid, sulfonic acid or phosphonic acid groups, in particular carboxylic acid groups, into consideration.
  • bases such as alkali metal hydroxides, ammonia or amines are used.
  • Alkali metal hydroxides can be used only to a limited extent, since the alkali metal ions are not volatile during firing and, as a result of their incompatibility with organic substances, can cloud the film and lead to loss of gloss. Therefore, ammonia or amines are preferred. In the case of amines, tertiary amines are preferred. Examples include N, N-dimethylethanolamine or aminomethylpropanolamine (AMP) called.
  • AMP aminomethylpropanolamine
  • Cation-forming groups are primary, secondary or tertiary amines. Accordingly, as the neutralizing agent (A3) in particular low molecular weight organic acids such as formic acid, acetic acid, dimethylolpropionic acid or lactic acid.
  • Binders (A2) having acid groups as ion-forming groups are preferred for the preferred use of the inventive slurry in automotive topcoating as unpigmented clearcoats, since these so-called anionic binders (A2) generally have a better resistance to yellowing than the class of cationic binders (US Pat. A2).
  • cationic binders with groups which can be converted into cations, such as amino groups, can in principle also be used, provided that the field of application can cope with their typical secondary properties, such as their tendency to yellow.
  • Suitable binders (A2) are random, alternating and / or block-structured linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or
  • suitable (co) polymers (A2) are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.
  • suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resins, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes ,
  • the (meth) acrylate copolymers, the polyesters, the alkyd resins, the polyurethanes and / or the acrylated polyurethanes (A2) are advantageous and are therefore used with preference.
  • Highly suitable (meth) acrylate copolymers (A2) and processes for their preparation are described, for example, in German Patent Application DE 199 08 018 A1, page 9, line 44, to page 10, line 53, in European Patent Application EP 0 767 185 A1, den German patents DE 22 14 650 B1 or DE 27 49 576 B1 and the US patents US 4,091,048 A, US 3,781,379 A, US 5,480,493 A, US 5,475,073 A or US 5,534,598 A or in the standard work Houben-Weyl, methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255, 1961 described.
  • Suitable reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tube reactors, loop reactors or Taylor reactors, as described, for example, in the patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Vol. 50, No. 9, 1995, pages 1409-1416.
  • dimensionally stable particles (A) comprise as binders (A2) at least one methacrylate copolymer which, based on a given methacrylate copolymer, comprises at least 90, preferably at least 95 and in particular at least 99% by weight of methacrylate comonomers. including included methacrylate comonomers potentially containing ionic groups, in copolymerized form.
  • the (meth) acrylate comonomers containing potentially ionic groups are preferably acrylic acid, beta-carboxyethyl acrylate and / or
  • Methacrylic acid especially methacrylic acid.
  • Group-containing (meth) acrylate comonomers in an amount in the Copolymerized copolymer of methacrylates (A2) that the above-described content of the particles (A) can be easily adjusted to potentially ionic groups. They are preferably used in an amount of from 0.1 to 3, preferably from 0.2 to 2.8, more preferably from 0.3 to 2.6, very preferably from 0.4 to 2.4 and in particular from 0.5 to 2, 2 wt .-%, in each case based on a given methacrylate copolymer (A2), copolymerized in the methacrylate copolymers (A2).
  • the methacrylate copolymers (A2) preferably have a glass transition temperature Tg of at most 50 ° C.; In this case, the glass transition temperature Tg should preferably not fall below 0, preferably 10 and in particular 20 0 C.
  • the glass transition temperature Tg of the methacrylate copolymers (A2) is adjusted via at least one methacrylate comonomer free of reactive functional groups and of potentially ionic groups.
  • the glass transition temperature Tg is preferably set via at least two, in particular two, methacrylate comonomers free of reactive functional groups and of potentially ionic groups.
  • Suitable methacrylate comonomers free of reactive functional groups and of potentially ionic groups are methyl, ethyl, n-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl, isoamyl, cyclopentyl , n-hexyl and cyclohexyl methacrylate.
  • i-butyl methacrylate glass transition temperature Tg of the homopolymer: 53 0 C
  • n-butyl methacrylate glass transition temperature Tg of the homopolymer: 20 ° C
  • Methacrylate comonomers can vary widely. It is essential that the amount is chosen such that the resulting methacrylate copolymers (A2) are those described above
  • the amount is at least 50, preferably at least 55, more preferably at least 60, most preferably at least 65 and especially at least 70 wt .-%, each based on a given methacrylate copolymer (A2).
  • the weight ratio of the particularly preferred methacrylate comonomer n-butyl methacrylate and i-butyl methacrylate vary widely.
  • the weight ratio n: i is preferably from 10: 1 to 1:10, preferably from 8: 1 to 1: 4, more preferably from 6: 1 to 1: 2, very preferably from 5: 1 to 1: 1, 5 and in particular 4 : 1 to 1: 1.
  • the methacrylate copolymers (A2) contain no or only a small number of reactive functional groups which are insignificant for crosslinking.
  • the methacrylate copolymers (A2) contain the complementary reactive functional groups for thermal crosslinking described below and / or autoreactive functional groups that are "self-reactive", ie. H. Groups of their own kind, can network.
  • the methacrylate copolymers (A2) contain at least one, in particular one, type of the reactive functional groups described below, the complementary reactive functional groups in at least one further constituent, in particular a crosslinking agent (A2). A3).
  • the methacrylate copolymers (A2) may contain reactive functional groups having at least one bond activatable with actinic radiation. These reactive functional groups are compulsorily contained in the methacrylate copolymers (A2) of the actinic-radiation-curable slurries of the invention if the slurries contain no further radiation-curable constituents.
  • the methacrylate copolymers (A2) contain reactive functional groups for the thermal crosslinking and / or reactive functional groups with at least one bond which can be activated with actinic radiation.
  • the reactive functional groups having at least one bond activatable with actinic radiation are in the methacrylate copolymers (A2) of the Compulsory contain dual-cure slurries according to the invention, if the dual-cure slurries contain no further radiation-curable constituents.
  • variable R is an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for identical or different aliphatic radicals or are linked together to form an aliphatic or heteroaliphatic ring.
  • Polyelektrolytkomplexen or premature crosslinking, received and / or the curing with actinic radiation should not disturb or inhibit, and secondly thereafter, in which temperature range the crosslinking should take place.
  • crosslinking temperatures Preferably be used in the slurries of the invention crosslinking temperatures of 60 to 180 0 C.
  • binders with thio, hydroxyl, N-methylolamino, N-alkoxymethylamino, imino, carbamate and / or allophanate groups preferably hydroxyl groups, on the one hand and preferably crosslinking agents with anhydride, epoxy, blocked and unblocked, especially blocked, isocyanate, urethane, methylol, methylol ether, siloxane, carbonate, amino, hydroxy and / or beta hydroxyalkylamide groups, preferably blocked isocyanate, carbamate and / or N-alkoxymethylamino groups, on the other hand applied.
  • the binders (A2) contain, in particular, methylol, methylol ether and / or N-alkoxymethylamino groups.
  • Complementary reactive functional groups which are particularly suitable for use in the thermally externally crosslinking slurries according to the invention and the dual-cure slurries according to the invention are hydroxyl groups on the one hand and blocked isocyanate groups on the other hand.
  • the functionality of the binders (A2) with respect to the above-described reactive functional groups can vary very widely and depends in particular on the crosslinking density which is to be achieved and / or on the functionality of the particular crosslinking agents used.
  • the OH number is preferably 20 to 300, preferably 40 to 250, more preferably 60 to 200, most preferably 80 to 190 and especially 90 to 180 mg KOH / g.
  • the complementary reactive functional groups described above can be incorporated into the binders (A2) by the customary and known methods of polymer chemistry. This can be done, for example, by the incorporation of methacrylate comonomers bearing the corresponding reactive functional groups and / or by means of polymer-analogous reactions.
  • Suitable methacrylate comonomers having reactive functional groups are methacrylate comonomers bearing at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule, such as
  • Hydroxyalkyl esters of methacrylic acid which are derived from an alkylene glycol esterified with the acid, or by reacting the methacrylic acid with a Alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of methacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl or 4-hydroxybutyl methacrylate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monomethacrylate; or reaction products of cyclic esters, such as epsilon-caprolactone and these hydroxyalkyl methacrylates;
  • Monocarboxylic acid having 5 to 18 carbon atoms per molecule in particular a Versatic® acid, is reacted;
  • Aminoethyl methacrylate or N-methylaminoethyl methacrylate which may also serve to introduce potentially ionic groups
  • Methacrylamides such as Methacryl Acidmid, N-methyl, N-methylol, N 1 N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl) -, N-ethoxymethyl and / or N, N-di (ethoxyethyl ) -methacryl Acidmid;
  • Methacryloyloxyethyl, propyl or butyl carbamate or allophanate are described in US Pat. Nos. 3,447,328, 3,674,838, 4,126,747, 4,279,833, or 4,340,497;
  • the reactive functional groups for thermal crosslinking can be introduced via other olefinically unsaturated monomers, such as the corresponding acrylates, allylamine, allyl alcohol or polyols, such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • the binders (A2) of the dual-cure slurries may contain on statistical average at least one, preferably at least two, group (s) having at least one bond (s) activatable with actinic radiation per molecule.
  • a bond which can be activated by actinic radiation is understood to mean a bond which becomes reactive upon irradiation with actinic radiation and undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its type which proceed by free-radical and / or ionic mechanisms.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
  • the carbon-carbon double bonds are particularly advantageous and therefore very particularly preferably used according to the invention. For the sake of brevity, they are referred to below as "double bonds".
  • the preferred group according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds may be conjugated. According to the invention, however, it is advantageous if the double bonds are present in isolation, in particular each terminally, in the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
  • the dual-cure binder (A2) contains, on a statistical average, at least one of the actinic radiation-activatable groups described above.
  • This means that the functionality of the binder in this regard is an integer, i.e. equal to, for example, two, three, four, five or more, or non-integer, i.e., for example equal to 2.1 to 10.5 or more. Which functionality you choose depends on the requirements of the respective dual-cure slurries.
  • the groups are structurally different or of the same structure.
  • Suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.
  • the groups are preferably bonded to the respective basic structures of the binders (A2) via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups.
  • This is usually done by conventional and known continuous polymer-analogous reactions such as the reaction of pendant glycidyl groups with olefinically unsaturated comonomers containing an acid group of pendant hydroxyl groups with the halides of these comonomers, isocyanates containing hydroxyl groups such as vinyl isocyanate, methacryloyl isocyanate and / or 1 - (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or of pendant isocyanate groups with the hydroxyl-containing comonomers described above.
  • the methacrylate copolymers (A2) are particularly preferably prepared under pressure.
  • the content of the dimensionally stable particles (A) on the above-described binders (A2) may vary widely. Preferably, it is 5 to 80, preferably 6 to 75, more preferably 7 to 70, most preferably 8 to 65 and in particular 9 to 65 wt .-%, each based on the film-forming solid of the slurry of the invention.
  • the dimensionally stable particles (A) of the inventive slurries curable thermally or thermally and with actinic radiation may contain crosslinking agents (A3) which have complementary reactive functional groups for thermal crosslinking and / or reactive functional groups having at least one bond activatable with actinic radiation.
  • Suitable crosslinking agents (A3) are all crosslinking agents customary in the field of light-stable clearcoats. Examples of suitable crosslinking agents are
  • aminoplast resins other than the melamine resins described above (A1) as described, for example, in Rompp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 et seq., The book “Paints, Coatings and Solvents", secondly revised edition, Edit. D.
  • Carboxyl-containing compounds or resins as described for example in the patent DE 196 52 813 A1 or 198 41 408 A1, in particular 1, 12-dodecanedioic acid,
  • Epoxy group-containing compounds or resins as described, for example, in patents and patent applications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US Pat. No. 4,091,048 A or US Pat. No. 3,781,379 A,
  • Beta-hydroxyalkylamides such as N, N, N I, N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N 1, N'-tetrakis (2-hydroxypropyl) adipamide.
  • crosslinking agents (A3) described above may be used singly or as a mixture of at least two crosslinking agents.
  • the blocked polyisocyanates and / or tris (alkoxycarbonylamino) triazines, in particular the blocked polyisocyanates have particular advantages and are therefore used with particular preference.
  • the content of the dimensionally stable particles (A) in the crosslinking agents (A3) can also vary widely and depends primarily on the functionality and amount of the star polymers (A1) and binders (A2) to be used according to the invention and the functionality of the crosslinking agents (A). A3) on the other hand.
  • it is 10 to 70, preferably 12 to 65, more preferably 14 to 60, most preferably 16 to 55 and in particular 18 to 50 wt .-%, each based on the film-forming solid of the slurry of the invention.
  • the dimensionally stable particles of the slurry according to the invention may, in addition to the constituents described above, contain additives (A3), as are commonly used in slurries. It is essential that these additives (A3) do not significantly lower the glass transition temperature Tg of the binders (A2).
  • Suitable additives (A3) are polymers other than the binders and crosslinking agents described above, neutralizing agents, catalysts for the
  • Matting agents light stabilizers, corrosion inhibitors, biocides, flame retardants, or
  • the slurry according to the invention can also be colored and / or effect, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powders, organic and inorganic, transparent or opaque fillers and / or nanoparticles and dyes, as described, for example, in German Patent Application DE 101 26 651 A1, page 14, paragraph [0131], to page 16, paragraph [0154], described as additives (A3). If the slurries according to the invention are used as clearcoat slurries, they contain no opaque constituents (A3).
  • the dimensionally stable particles (A) of the above-described binders (A2) may contain different, curable with actinic radiation components as additives (A3), if inventive slurry should be curable thermally and with actinic radiation or with actinic radiation alone. These are for example
  • actinic radiation curable reactive diluents such as those described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the heading "Reactive Thinner”; or to
  • the slurry of the invention may also contain additives in the aqueous phase (B).
  • nonionic and / or ionic thickeners are preferably nonionic and / or ionic thickeners (A3). This effectively counteracts the tendency of the comparatively large particles (A3) to sediment.
  • nonionic thickeners are hydroxyethyl cellulose and polyvinyl alcohols. So-called nonionic associative thickeners are also on the market in a wide variety of choices available. They usually consist of water-dilutable polyurethanes, which are reaction products of water-soluble polyether diols, aliphatic diisocyanates and monofunctional hydroxyl compounds with an organophilic radical.
  • ionic thickeners (A3). These usually contain anionic groups and are based in particular on special polyacrylate resins having acid groups which may be partially or completely neutralized.
  • suitable thickeners (A3) to be used according to the invention are from the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 31 to 65, or the German patent application DE 199 08 018 A1. Page 13, line 18, to page 14, line 48, known.
  • thickener (A3) in particular a nonionic thickener (A3), is sufficient to set the desired, pseudoplastic behavior described above.
  • the amount of thickener (A3) to be added and, if two different thickeners (A3) are used, the ratio of ionic to nonionic thickener (A3) depend on the desired viscosity of the slurry according to the invention, which in turn depends on the settling stability required and the special requirements the spray application can be specified.
  • the person skilled in the art can therefore determine the amount of thickener (A3) and, if appropriate, the ratio of the thickener types (A3) to one another based on simple considerations, if appropriate with the aid of preliminary tests.
  • dispersion aids such as wetting agents and emulsifiers are included.
  • the dispersing aids (A3) are preferably selected from the group consisting of alkoxylated fatty alcohols having 16 to 18 carbon atoms in the alkyl radical and on average at least 20, preferably at least 25, preferably at least 30, more preferably at least 35, very preferably at least 40 and in particular at least 45 oxaalkanediyl groups in the molecule, or alkoxylated fatty alcohols having 8 to 15, preferably 9 to 15, preferably 10 to 14, particularly preferably 5 to 15 and in particular 13 carbon atoms in the alkyl radical and in the statistical average 3 to 19, preferably 5 to 15, preferably 7 to 14, particularly preferably 8 to 12 and in particular 10 oxaalkandiyl groups in the molecule selected.
  • Suitable oxaalkanediyl groups are 1-oxapropane-1, 3-diyl, 1-oxabutane-1, 4-diyl, 1-oxabutane-1,3-diyl, 1-oxapentane-1, 5-diyl or 1-oxapentane-1 , 3-diyl, preferably 1-oxapropane-1, 3-diyl and 1-oxabutane-1, 3-diyl, in particular 1-oxapropane-1, 3-diyl (ethylene oxide group).
  • the wetting agent may contain at least two types of these oxaalkanediyl groups.
  • the oxaalkanediyl chains may be random, alternating or block-like.
  • the wetting agent contains only one type of oxaalkanediyl groups, especially the ethylene oxide groups.
  • the wetting agents (A3) described above are commercial compounds and are described, for example, by BASF Aktiengesellschaft under the trademark Lutensol® AT 25 (25 ethylene oxide groups in the molecule) and AT 50 (50 ethylene oxide groups in the molecule) or the trademark Lutensol® TO , in particular Lutensol® TO 10 [iC 13 H 27 ⁇ - (- CH 2 CH 2 ⁇ -) 1 oH] and Lutensol® 109 (mixture of 85% Lutensol® TO 10 and 15% water).
  • copolymers known from German patent application DE 101 26 651 A1, page 3, paragraphs [0013] to [0015], and page 4, paragraph [0020], to page 7, [0055], are emulsifiers (A3) consideration.
  • the wetting agents and emulsifiers (A3) to be used according to the invention are used in an amount of 0.01 to 2.5, preferably 0.05 to 2.4, particularly preferably 0.1 to 2.2, very particularly preferably 0.15 to 2 and in particular 0.2 to 1, 8 wt .-%, each based on the slurry of the invention used.
  • the aqueous phase of the slurry of the invention may further contain crosslinkable flow control agents (A3) in the film.
  • suitable constituents of this type are thermally curable reactive diluents such as positionally isomeric diethyloctanediols or hydroxylated, hydrogenated metathesis products or hydroxyl-containing dendrimers as described in German patent applications DE 198 05 421 A1, DE 198 09 643 A1 or DE 19840605 A1.
  • the slurry according to the invention may contain in its aqueous phase (B) at least one, in particular one, water-soluble salt (A3), preferably in an amount of from 0.1 to 50 mmol per 1,000 g of water present in the slurry of the invention.
  • the Salt (A3) is residue-free or essentially residue-free decomposable. This means that it does not form any residues or residues in its decomposition in an amount which does not cause any disadvantageous technical effects in the thermoset materials according to the invention.
  • the salt (A3) may be decomposable by means of heat and / or actinic radiation. Preferably, it is thermally decomposable. It is preferably decomposable under the conditions of curing of the clearcoat films of the invention produced from the slurries. According to the invention it is advantageous if the salt (A3) is decomposable at temperatures above 100 0 C. Preferably, the decomposition of the salt at 250 0 C, preferably 200 0 C, more preferably 190 0 C and in particular 180 0 C terminated.
  • the decomposition of the salt (A3) can form a variety of organic, inorganic and organometallic decomposition products.
  • the decomposition products may be volatile elements, neutral organic or inorganic hydrogen compounds, organic and inorganic bases, organic and inorganic acids or oxides.
  • volatile elements are phosphorus, sulfur, nitrogen or oxygen, in particular nitrogen.
  • neutral organic and inorganic hydrogen compounds are water or hydrocarbons, especially water.
  • organic and inorganic bases are ammonia, methylamine, dimethylamine or trimethylamine, especially ammonia.
  • organic and inorganic acids are formic acid, acetic acid, propionic acid, oxalic acid, citric acid, tartaric acid, hydrochloric acid, hydrogen bromide, phosphoric acid, phosphorous acid, amidosulfonic acid, sulfuric acid, sulfurous acid, thiosulfuric acid, HSCN or hydrogen sulfide, especially acetic acid.
  • oxides are carbon dioxide, sulfur dioxide, sulfur trioxide or phosphorus oxides, in particular carbon dioxide.
  • a salt (A3) is selected whose decomposition products are not or only slightly toxic and / or non-corrosive or only slightly corrosive.
  • Prefers is selected in a salt which forms as decomposition products water, nitrogen, carbon dioxide, ammonia and organic acids.
  • the salt (A3) is particularly preferably selected from the group of ammonium salts, very particularly preferably from the group consisting of salts of ammonia and of organic amines with organic and inorganic acids.
  • ammonium salt (A3) is selected from the group consisting of ammonium carbonate, ammonium thiocyanate, ammonium sulfamate, ammonium sulfite monohydrate, ammonium formate, ammonium acetate,
  • Ammonium hydrogen oxalate monohydrate, diammonium oxalate monohydrate, ammonium citrate and ammonium tartrate are very particularly advantageous and are therefore used with very particular preference according to the invention.
  • the slurry of the invention by the German patent DE 198 41 842 C2 or the German patent applications DE 196 17 086 A1, DE 199 08 018 A1, DE 100 01 442 A1, DE 100 55 464 A1, DE 100 40 223 A1 or DE 101 35 998 A1 known secondary dispersion prepared.
  • the melamine-formaldehyde resins (A1) and the binders (A2) and optionally the crosslinking agents (A3) and / or the additives (A3) are mixed in organic solution and dispersed in water together with neutralizing agents (A3). Then it is diluted with water while stirring. It initially forms a water-in-oil emulsion, which turns on further dilution in an oil-in-water emulsion. This point is generally reached at solids contents of ⁇ 50% by weight, based on the emulsion, and is externally evident from a greater decrease in viscosity during dilution.
  • water-miscible solvents are used.
  • these have a high vapor pressure, so that they can be easily removed at low temperatures, preferably by distillation, in particular azeotropic distillation.
  • suitable organic solvents are ethoxyethyl propionate, isopropoxypropanol, isopropanol, acetone, methyl ethyl ketone or methyl isobutyl ketone.
  • the oil-in-water emulsion can also be prepared directly by the melt emulsification of the star polymers (A1) and the binders (A2) and optionally the crosslinking agents (A3) and / or the additives (A3) in water.
  • the wetting agents and emulsifiers (A3) to be used according to the invention are added to the organic solution and / or the water before or during the emulsification. Preferably, they are added to the organic solution.
  • the solvent-containing emulsion thus obtained is subsequently freed of solvents by azeotropic distillation.
  • the removal-solvent at a distillation temperature below 70 0 C, preferably below 50 0 C and are distilled in particular below 4O 0 C.
  • the distillation pressure is chosen so that this temperature range is maintained at higher boiling solvents.
  • the azeotropic distillation can be accomplished by stirring the emulsion at room temperature in an open vessel for several days.
  • the solvent-containing emulsion is freed from the solvents by vacuum distillation.
  • the evaporated or distilled off amount of water and solvents are replaced by water to avoid high viscosities.
  • the addition of the water can be done before, after or during the evaporation or distillation by adding in portions.
  • the glass transition temperature Tg of the dispersed particles increases, and it forms a dispersion instead of the previous solvent-containing emulsion.
  • the rheology aids (A3) are preferably added to the dispersion in this process stage, which is also referred to as completion. This sets the desired pseudoplastic behavior and results in the slurry of the invention.
  • the salts (A3) can be introduced in different ways into the slurries or their precursors according to the invention. For example, they may be added to the organic solution of components of the slurry of the invention. Preferably, they are dissolved in the water before emulsifying the organic solution.
  • the particles (A) of the slurry according to the invention are mechanically comminuted in the wet state, which is also referred to as wet milling.
  • wet milling Preferably conditions are employed here is that the temperature of the grinding stock 70 0 C, preferably 60 0 C and in particular does not exceed 5O 0 C.
  • the specific energy input during the milling process is preferably 10 to 1000, preferably 15 to 750 and in particular 20 to 500 Wh / g.
  • suitable devices which produce low shear fields are customary and known stirred tanks, gap homogenizers, microfluidizers or dissolvers.
  • Examples of suitable devices which produce high shear fields are conventional and known stirred mills or inline dissolvers.
  • the devices that produce high shear fields are used.
  • the agitator mills according to the invention are particularly advantageous and are therefore used with very particular preference.
  • the slurry according to the invention is fed by means of suitable devices, such as pumps, in particular gear pumps, to the devices described above and circulated until the desired particle size is reached.
  • suitable devices such as pumps, in particular gear pumps
  • the slurry of the invention is filtered before use.
  • the usual and known filtration devices and filters are used, as they come into consideration for the filtration of the known clearcoat slurries.
  • the mesh size of the filter can vary widely and depends primarily on the particle size and the particle size distribution of the particles of the slurry according to the invention. The person skilled in the art can therefore easily determine the suitable filters on the basis of this physical parameter. Examples of suitable filters are monofilament surface filters or Bag filter. These are available on the market under the brands Pong® or Cuno®.
  • bag filters are used with the mesh sizes 25 to 50 microns, for example, Pong® 25 to Pong® 50th
  • the slurry according to the invention has good storage stability combined with good gear pump mobility and filterability.
  • the slurry according to the invention can be prepared in an outstanding manner by means of the customary and known methods of applying liquid coating materials, such as e.g. Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling, apply.
  • liquid coating materials such as e.g. Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling, apply.
  • spray application methods are used. If necessary, actinic radiation is excluded.
  • the slurry according to the invention dries without problems and shows filming at the processing temperature, generally at room temperature. That is, the slurry of the present invention applied as a wet layer exhausts at room temperature or slightly elevated temperatures with release of water, whereby the particles (A) contained therein change their original shape, flow together and form a homogeneous film (A).
  • the applied slurry according to the invention can also dry in powder form.
  • the drying may be accelerated by the use of a gaseous, liquid and / or solid hot medium such as hot air, heated oil or heated rolls, or microwave, infrared and / or near infrared (NIR) light.
  • a gaseous, liquid and / or solid hot medium such as hot air, heated oil or heated rolls, or microwave, infrared and / or near infrared (NIR) light.
  • NIR near infrared
  • the wet layer is dried in a circulating air oven at 23 to 150 0 C, preferably 30 to 120 0 C and in particular 50 to 100 0 C dried.
  • the dried layer (A) according to the invention is cured physically, thermally, with actinic radiation or with dual-cure, preferably thermally or with dual-cure, in particular thermally.
  • the thermal curing uses the apparatus and methods described above.
  • the crosslinking temperature is preferably between 120 and 160 ° C.
  • the corresponding burn-in time is between 10 and 60 minutes.
  • the curing with actinic radiation has no special features, but can with the help of the usual and known devices and methods, as described for example in German Patent Application DE 198 18 735 A 1, column 10, lines 31 to 61, the German patent application DE 102 02 565 A1, page 9, paragraph [0092], to page
  • the slurries according to the invention and the thermoset materials according to the invention can be used extremely widely.
  • they are used as coating materials, adhesives and sealants or precursors for moldings and films for the production of coatings according to the invention, adhesive layers and seals as well as moldings and films according to the invention.
  • the coatings, adhesive layers and seals according to the invention can be used for coating, bonding and sealing a wide variety of coated and uncoated substrates.
  • the substrates are um
  • stationary floats such as buoys or parts of docks, indoor and outdoor structures, doors, windows and furniture and hollow glass bodies, - industrial small parts such as screws, nuts, hubcaps or wheel rims,
  • Containers such as coils, containers or packaging, electrotechnical components, such as electronic winding goods, such as coils, optical components, mechanical components and - white goods, such as household appliances, boilers and radiators.
  • the substrates are automobile bodies and parts thereof.
  • the slurry according to the invention is preferably used for the production of the coatings according to the invention.
  • the slurry according to the invention can be used with particular advantage as primer, primer, filler, basecoat, solid-color topcoat and clearcoat for the production of one-coat or multi-coat primer coatings, anticorrosive coatings according to the invention,
  • the slurry according to the invention is used for the production of clearcoats according to the invention in the context of multicoat color and / or effect paint systems, in particular by the customary and known wet-on-wet processes (see German Patent Application DE 100 27 292 A1, page 13, paragraph [0109], to page 14, paragraph [0118]) are prepared from basecoats and the slurry according to the invention.
  • inventive slurries and the clearcoats of the invention produced therefrom are outstandingly suitable for the first-time coating of passenger cars (OEM), in particular coatings of passenger cars of the upper class.
  • the multicoat color and / or effect paint systems according to the invention which comprise at least one clearcoat according to the invention fulfill all the requirements which are imposed on automotive finishes (see European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40) and correspond in appearance (appearance) to a Class A surface in full. In particular, they show a very good flow, very good optical properties (appearance) and high chemical resistance, scratch resistance and weather resistance. They are as far as possible or completely free of paint defects, such as noses, specks, pinholes, micro-disturbances (starry sky), pimples and cloudiness. Overall, their tendency to form edge and surface cookers is significantly reduced at very high layer thicknesses. Surprisingly, they also have a high stone chip resistance.
  • the clearcoats of novel finishes according to the invention in particular of primary finishes on automobile bodies, have excellent adhesion to the refinishes applied to the clearcoats of the invention, in particular without prior grinding
  • the refinish coatings comprise a surfacer coating, a basecoat and a clearcoat or a basecoat and a clearcoat or only a clearcoat. In all cases, however, the excellent liability is guaranteed.
  • the reaction mixture was allowed to react for 3 h at 78 0 C again. Subsequently, the volatiles were removed by vacuum distillation until a solids content of 70 wt .-% was set. Thereafter, the resin solution (A2) was discharged. It had a viscosity of 7.0 to 10.0 dPas (solid resin 60 percent XyIoI at 23 0 C). The acid number was 9.0 to 11.0 and the hydroxyl number was 110 mg KOH / g solid resin.
  • Desmodur® N 3300 commercial isocyanurate of hexamethylene diisocyanate, from Bayer AG
  • 200 parts by weight of methyl ethyl ketone were charged to a reaction vessel and heated to 4O 0 C.
  • To the solution was added, with cooling, 100 parts by weight of 2,5-dimethylpyrazole, waiting for the exothermic reaction to disappear. Thereafter, with continued cooling, 100 parts by weight of 2,5-dimethylpyrazole were added again. After renewed decay of the exothermic reaction, an additional 66 parts by weight of 2,5-dimethylpyrazole were added. Thereafter, the cooling was turned off, causing the reaction slowly heated to 80 0 C.
  • the reaction mixture was cooled and discharged.
  • the resulting solution of the blocked polyisocyanate (A3) had a solids content of 81 wt .-% (1 h at 130 0 C) and a viscosity of 3.4 dPas (70% in methyl ethyl ketone; cone and plate viscometer at 23 0 C ) on.
  • Tinuvin® 400 To the resulting mixture were added 26.17 parts by weight of Tinuvin® 400 and 5.56 parts by weight of Tinuvin® 123 (commercial light stabilizer from Ciba Specialty Chemicals, Inc.) and 15.55 parts by weight Lutensol® AT 50 (ethoxylated alcohol having 16 to 18 carbon atoms in Alkyl radical and on average 50 ethylene oxide groups in the molecule from BASF Aktiengesellschaft), after which the mixture was stirred at room temperature for 30 minutes. Subsequently, 5.28 parts by weight dimethylethanolamine were added. The resulting mixture was stirred for another two hours at room temperature.
  • Tinuvin® 400 To the resulting mixture were added 26.17 parts by weight of Tinuvin® 400 and 5.56 parts by weight of Tinuvin® 123 (commercial light stabilizer from Ciba Specialty Chemicals, Inc.) and 15.55 parts by weight Lutensol® AT 50 (ethoxylated alcohol having 16 to 18 carbon atoms in Alkyl radical and on average 50 ethylene oxide groups in the molecule from
  • the resulting aqueous emulsion was diluted with 1188 parts by weight of deionized water. Thereafter, it was removed on a rotary evaporator under vacuum 581, 5 parts by weight of a mixture of volatile organic solvents and water.
  • the slurry was blended with a mixture of 0.4 parts by weight of Viscalex® HV (commercial anionic thickener (A3) on the polyacrylate basis of the company Allied Colloids) 0.6 parts by weight Acrysol® RM-8W (commercial nonionic associate thickener (A3) Rohm & Haas), 0.4 parts by weight of dimethylethanolamine (10% in water), each 1.0 part by weight of Byk® 333 and 348 (both commercially available additives (A3) from Byk Chemie) and 0.2 parts by weight of deionized water completed. Clearcoat slurry 1 exhibited pronounced pseudoplastic behavior, excellent filterability, and excellent gear pump performance.
  • each of the electrodeposition coatings was coated with a layer of a customary and known water filler from BASF Coatings AG and a layer of a customary and known black aqueous basecoat ("night black”) from BASF Coatings
  • the clearcoat slurry 1 of Example 1 was applied in wedge form to the test panels. Subsequently, the resulting clearcoat slurry wet coating was baked together with the pre-dried water filler layer and the predried aqueous basecoat at 15O 0 C for 23 minutes.
  • the dry film thickness of the resulting wedge-shaped clearcoat 1 was 10 to 80 ⁇ m. Due to the application to the vertical test sheets, an edge bead of a dry layer thickness of 190 ⁇ m was formed at the lower edge of the part.
  • the wetting limit was only 18 ⁇ m both on the electrodeposition coating and on the basecoat.
  • the test panels were prepared in the manner described above, except that the clearcoats 1 were not applied wedge-shaped but in a practical dry film thickness of 40 microns. This resulted in the initial coatings 1 with the clearcoat. 1
  • the gloss and haze of the clearcoat 1 at 20 ° according to DIN 67530 were very good: 84.5 units and 9.2 units.
  • Wave Scan (measuring device: Byk / Gardner company - Wave scan plus): Long Wave / Short Wave 5 / 19.7.
  • the clearcoat 1 had excellent scratch resistance, chemical resistance, weather resistance, intercoat adhesion, and condensation resistance.
  • the first coatings 1 on the test panels of the second series were coated to simulate a full repair with the black aqueous basecoat and the clearcoat slurry 1 wet-on-wet, so that after drying and curing of the resulting basecoat films and clearcoat films 1 secondcoats or refinishes 1 of the same structure as the initial coatings 1 resulted. Before the application of the clearcoat slurry 1, the primary coatings 1 were not ground.
  • the secondary finishes or refinishes 1 had excellent adhesion to the original finishes (cross-cut test: grade GT 0) and a very good resistance to stone chips (VDA: grade 2.5).

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Abstract

L'invention concerne des dispersions aqueuses sous forme de poudre, à viscosité intrinsèque, exemptes ou partiellement exemptes de solvants organiques, contenant en phase aqueuse (B) des particules (A) à dimensions stables dans des conditions de stockage et d'utilisation, solides et/ou très visqueuses en phase dispersée (A). Les particules présentent une taille de particules moyenne mesurée avec la technique de diffraction laser D (v, 0,5) = 1 à 10 µm, lesdites particules (A) à dimensions stables contenant au moins une résine (A1) de mélamine formaldhéhyde éthérifiée, non soluble dans l'eau, réactive et appauvrie en solvants. L'invention concerne également des procédés de production et d'utilisation desdites dispersions.
PCT/EP2006/010183 2005-10-24 2006-10-23 Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes WO2007048554A2 (fr)

Applications Claiming Priority (2)

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DE102005050821.9 2005-10-24
DE102005050821A DE102005050821A1 (de) 2005-10-24 2005-10-24 Strukturviskose, von organischen Lösemitteln im Wesentlichen oder völlig freie, wässrige Pulverdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung

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DE102014116960A1 (de) * 2014-11-19 2016-05-19 Synthopol Chemie Dr. Rer. Pol. Koch Gmbh & Co. Kg Verfahren zur Herstellung einer wässrigen Polymer/Melamin-Dispersion

Citations (5)

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Publication number Priority date Publication date Assignee Title
US5008155A (en) * 1984-03-21 1991-04-16 Hoechst Aktiengesellschaft Aqueous dispersions for the preparation of crosslinkable coatings
WO1999003942A1 (fr) * 1997-07-18 1999-01-28 Basf Coatings Ag Vernis aqueux contenant une dispersion aqueuse a plusieurs constituants
DE10001442A1 (de) * 2000-01-15 2001-10-18 Basf Coatings Ag Strukturviskose, von organischen Lösemitteln freie Pulverklarlack-Slurry, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2003011583A2 (fr) * 2001-07-31 2003-02-13 Ppg Industries Ohio, Inc. Composites multicouches faits de compositions a adherence amelioree, compositions pour revetements, et procedes associes
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