WO2007048552A1 - 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

Info

Publication number
WO2007048552A1
WO2007048552A1 PCT/EP2006/010181 EP2006010181W WO2007048552A1 WO 2007048552 A1 WO2007048552 A1 WO 2007048552A1 EP 2006010181 W EP2006010181 W EP 2006010181W WO 2007048552 A1 WO2007048552 A1 WO 2007048552A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder dispersions
groups
dispersions according
particles
organic solvents
Prior art date
Application number
PCT/EP2006/010181
Other languages
German (de)
English (en)
Inventor
Michael Tecklenborg
Bianca Giesen
Marco Deyda
Hubert Baumgart
Ulrike RÖCKRATH
Silke Böhnke
Original Assignee
Basf Coatings Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Coatings Ag filed Critical Basf Coatings Ag
Publication of WO2007048552A1 publication Critical patent/WO2007048552A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to novel, 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.
  • binder slurries or “slurries” for short.
  • slurries here and below refers to pseudoplastic, aqueous solvent dispersions free of organic solvents. If the slurries contain no opaque constituents, they are also referred to below as “clearcoat slurries”.
  • Clearcoat slurries which contain solid and / or highly viscous particles which are dimensionally stable under storage and use conditions are known, for example, from German patent application DE 101 35 998 A1. They may contain thermally curable reactive diluents in their aqueous phase, such as the hyperbranched compounds or dendrimers known from German patent application DE 198 40 605 A1.
  • the known clearcoat slurries generally have good filterability and good gear pump handling. In addition, they have a low wetting limit, d. h., They already wet at a wet film thickness, corresponding to a dry film thickness of 24 microns, to be coated electrocoats completely and at a
  • wet film thickness corresponding to a dry film thickness of 28 ⁇ m basecoats completely. They provide clearcoats that have a very good flow, very good optical properties (appearance) and a high chemical resistance, scratch resistance and
  • European patent application EP 1 070 748 A1 discloses powder coatings containing dendrimers.
  • the dendrimers improve the chemical resistance, solvent resistance, adhesion and impact resistance of the coatings produced from the known powder coatings.
  • solvent-borne basecoats and clearcoats containing star polymers are known. They are quick-drying and deliver coatings that have good adhesion, moisture resistance, chemical resistance and stone chip resistance.
  • the object of the present invention is to provide novel, pseudoplastic, substantially completely or completely free from organic solvents, aqueous powder dispersions, ie new slurries, which have good filterability and good gear pump performance.
  • they should have a low wetting limit, ie they should already wet at a wet film thickness, corresponding to a dry film thickness of 16 microns, the substrates to be coated.
  • the new slurries are said to be ideally suited for the production of thermoset materials.
  • the coating materials should be used as primers, fillers, primers, basecoats, solid-color topcoats and clearcoats for the production of primer coatings, surfacer coats, antistonechip primers, basecoats,
  • Solid topcoats and clearcoats are suitable.
  • the clearcoat slurries are said to be outstandingly suitable for the production of clearcoats of colored and / or effect multicoat paint systems, in particular multicoat paint systems which are prepared by wet-on-wet processes.
  • the clearcoats are to have a very good flow, very good optical properties (appearance) and a high chemical resistance, scratch resistance and
  • the novel, structurally viscous, substantially completely or completely free of aqueous solvents, aqueous powder dispersions are referred to as "slurries" according to the invention.
  • the slurries according to the invention had good filterability and good gear pump handling. In addition, they had a low wetting limit, d. h., They already wet at a wet film thickness, corresponding to a dry film thickness of 16 microns, the substrates to be coated completely.
  • 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 from new primer coatings, surfacer coats, antistonechip primers, base coats, 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 clearcoats of the invention showed a very good flow, very good optical properties (appearance) and a high chemical resistance,
  • Lacquer disorders such as noses, specks, pinholes, micro disorders (starry sky), pimples and cloudiness. Overall, their tendency to form edge and surface cookers was significantly reduced at very high layer thicknesses. Their ability to wet substrates, especially precoated substrates, was significantly improved.
  • 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.
  • D (v, 0.5) 1.5 to 2.5 ⁇ m, preferably 1.6 to 2.4 ⁇ m and in particular 1.7 to 2.3 ⁇ m;
  • D (v, 0.9) 2.5 to 3.6 microns, preferably 2.6 to 3.5 microns and especially 2.7 to 3.5 microns and
  • the laser diffraction method is a customary and known method for measuring particle sizes and their distribution and can be carried out, for example, with the aid of 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 Slurriy invention is substantially or completely free of organic solvents.
  • Substantially free means that the slurry according to the invention has a solvent content of ⁇ 3% by weight, preferably ⁇ 1% by weight and in particular ⁇ 0.1% by weight. “Completely free” means that the solvent content is below the usual and known detection limits for organic solvents.
  • 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 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 of the invention preferably its particles (A), activatable with actinic radiation bonds which are activated by the irradiation and with other activated bonds of their kind undergo polymerization and / or crosslinking reactions, the radical and / or ionic mechanisms expire.
  • electromagnetic radiation such as near infrared (NIR), visible light, UV radiation, X-rays 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 at least one, in particular one, star polymer (A1) as a constituent essential to the invention.
  • Star polymers is the name given to polymers in which 3 and more chains start from one center.
  • the center can be a single atom or an atomic group.
  • Star polymers are preferably accessible by polyaddition, for example of epoxides to polyhydric alcohols.
  • Star polymers belong in principle to the branched polymers. They are sometimes called radial polymers, starburst polymers or dendrimers. Of the latter, however, the star polymers should be strictly distinguished, since these - in contrast to the star polymers - themselves have branched side arms.
  • star polymers consist of repeating linear and fully branched structural units.
  • the number average molecular weight of the star polymers (A1) can vary very widely. Preferably, it is from 1,000 to 100,000 daltons, preferably from 2,000 to 50,000 daltons, more preferably from 2,500 to 40,000 daltons.
  • They can be prepared by the polymerization of olefinically unsaturated monomers with polyfunctional initiators as initiators, by reaction of monofunctional
  • Macromolecules eg, living polymers
  • Macromolecules with low molecular weight polyfunctional
  • Compounds and are prepared by polyaddition or polycondensation. Preferably, they are prepared by polyaddition or polycondensation, in particular polyaddition.
  • the star polymer (A1) contains terminal or terminal reactive functional groups which can be activated thermally and / or with actinic radiation.
  • Suitable reactive functional groups of this type are the reactive functional groups described below, in particular carboxyl groups, hydroxyl groups, amino groups and (meth) acrylate groups, in particular hydroxyl groups.
  • terminal reactive functional groups can be introduced after preparation of a star polymer by polymer analogous reactions.
  • terminal hydroxyl groups or amino groups can be reacted with olefinically unsaturated isocyanates such as vinyl isocyanate, terminal carboxyl groups with olefinically unsaturated epoxides such as glycidyl acrylate or terminal isocyanate groups with hydroxyl-containing olefinically unsaturated compounds such as 2-hydroxyethyl acrylate, whereby a star polymer (A1) having terminal olefinically unsaturated groups, in particular Acrylate groups, results.
  • olefinically unsaturated isocyanates such as vinyl isocyanate
  • terminal carboxyl groups with olefinically unsaturated epoxides such as glycidyl acrylate
  • terminal isocyanate groups with hydroxyl-containing olefinically unsaturated compounds such as 2-hydroxyethyl acrylate
  • the content of the star polymer (A1) on terminal reactive functional groups can vary widely.
  • the content is 0.9 to 10 meq / g, preferably 1, 2 to 8 meq / g, more preferably 1, 4 to 6.5 meq / g and especially 1, 6 to 5.5 meq / g.
  • the star polymer is a polyester (A1) which can be prepared by the reaction of polyols with carboxylic acids or carboxylic anhydrides to form a polyamide obtained by reacting polyamines with carboxylic acids or
  • Carboxylic anhydrides can be produced, a polyurethane, by reaction of
  • Polyisocyanates and polyols can be produced, or to a polyurea, by the
  • the polyamines are in
  • polyester (A1) particularly preferably polyester (A1) having aliphatic and / or cycloaliphatic structural units, very particularly preferably polyesters having terminal hydroxyl groups.
  • the OH number of polyesters (A1) having terminal hydroxyl groups can vary widely. Preferably, they have an OH number of 50 to 550 mg KOH / g, preferably 70 to 450 mg KOH / g, more preferably 80 to 350 mg KOH / g and in particular 90 to 300 mg KOH / g.
  • the acid number is ⁇ 10 mg KOH / g, in particular ⁇ 5 mg KOH / g.
  • Suitable starting compounds for the preparation of the star polymers (A1) and suitable preparation processes are described in international patent application WO 2005/061574 A1, page 2, paragraph [0009], to page 8, paragraph [0023], and page 14, paragraph [0044], to page 17, paragraph [0057], or the American patent application US 2003/0161961 A1, page 2, paragraph [0022], to page 5, [0067], and page 7, paragraph [0104], to page 8, paragraph [ 0126], known.
  • A1 An example of a particularly well-suited star polymer (A1) is the polyester, which consists of
  • (a3) at least one, in particular one, monoalcohol, in particular Versatic® acid glycidyl ester (Cardura® E 10) (cf., for this, Rompp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Versatic® Acids” )
  • the content of the particles (A) on the star polymer or the star polymers (A1) can vary very widely and depends on the requirements of the individual case.
  • the content is preferably from 0.1 to 30% by weight, preferably from 1 to 25% by weight, particularly preferably from 2 to 20% by weight and in particular from 2.5 to 15% by weight, based in each case on the film-forming agent Solid body of the slurry according to the invention.
  • film-forming solid is understood to mean the sum of all constituents of the slurry according to the invention, which after application and curing of the According to the invention slurry build the solid state of the thermoset materials of the invention. In general, all or almost all of the film-forming ingredients are concentrated in the dimensionally stable particles (A).
  • the slurries of the invention may otherwise be of different composition.
  • the slurries of the invention may otherwise be of different composition.
  • the clearcoat slurries prepared by the secondary dispersion method which contain the special methacrylate copolymers (A2) described below as binders in the dimensionally stable particles (A).
  • 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 are used.
  • the neutralizing agent (A3) in particular low molecular weight organic acids such as formic acid, acetic acid, dimethylolpropionic acid or lactic acid are used.
  • 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).
  • anionic binders (A2) generally have a better resistance to yellowing than the class of cationic binders (US Pat. A2).
  • cationic binders (A2) 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 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 polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition” and “polyaddition resins (polyadducts)", and pages 463 and 464, “polycondensates”, “polycondensation” and “Polykondensationsharze”, as well as pages 73 and 74, "binder", referenced.
  • 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.
  • Suitable reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tubular reactors,
  • the (meth) acrylate comonomers containing potentially ionic groups are preferably acrylic acid, beta-carboxyethyl acrylate and / or methacrylic acid, in particular methacrylic acid.
  • the (meth) acrylate comonomers containing potentially ionic groups are copolymerized into the methacrylate copolymers (A2) in an amount such that the above-described content of the particles (A) of potentially ionic groups can be easily adjusted.
  • 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.
  • the soft 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 ° 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 the thermal crosslinking described below and / or autoreactive functional groups which are "self-reactive", ie 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 compulsorily contained in the methacrylate copolymers (A2) of the 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.
  • the selection of the respective complementary reactive functional groups depends on the fact that in the production of the binders (A2) and in the preparation, storage, application and melting of the slurries according to the invention no undesired reactions, in particular no formation of polyelectrolyte complexes or premature crosslinking, received and / or curing with actinic radiation should not disturb or inhibit, and secondly thereafter, in which temperature range the crosslinking should take place.
  • crosslinking temperatures of 60 to 180 ° C. are used in the slurries according to the invention.
  • 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 up to 20
  • Esters e.g. epsilon-caprolactone and these hydroxyalkyl methacrylates
  • Reaction products of methacrylic acid with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid or instead of the reaction product, an equivalent amount of methacrylic acid, which then during or after the Polymerization reaction with the glycidyl ester of an alpha-branched 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.
  • 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 particular 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 well-known continuous polymer-analogous reactions such as the reaction of pendant glycidyl groups with olefinically unsaturated comonomers containing a Contain acid group of pendant hydroxyl groups with the halides of these comonomers, of hydroxyl groups with double bonds containing isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® the CYTEC company) or of pendant isocyanate groups with the hydroxyl-containing comonomers described above.
  • TMI® the CYTEC company
  • 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. It is preferably from 5 to 80, preferably from 6 to 75, particularly preferably from 7 to 70, very particularly preferably from 8 to 65 and in particular from 9 to 60,% by weight, based in each case on the film-forming solid of the slurry according to 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
  • 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,
  • Tris (alkoxycarbonylamino) triazines as described in the patents US 4,939,213 A, US Pat. No. 5,084,541 A, US Pat. No. 5,288,865 A or the patent application EP 0 604 922 A1,
  • beta-hydroxyalkylamides such as N, N, N ', N 1 -tetrakis (2-hydroxyethyl) adipamide or N, N, N', 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
  • 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], 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
  • 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 available on the market in a wide variety of choices. 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), from to set the desired, pseudo-conductive 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 on 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 commercially available compounds and are described, for example, by BASF Aktiengesellschaft under the trademark Lutensol®
  • Lutensol® TO 1 AT 25 (25 ethylene oxide groups in the molecule) and AT 50 (50 ethylene oxide groups in the molecule) or Lutensol® TO 1 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), distributed.
  • 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 ° C. Preferably, the decomposition of the salt at 250 ° 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 act.
  • 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. Preference is given to choosing 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 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 star polymers (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 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.
  • they may be added to the organic solution of components of the slurry of the invention.
  • 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 from 6O 0 C and in particular does not exceed 50 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.
  • Examples of 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 to the devices described above with the aid of suitable devices, such as pumps, in particular gear pumps, and driven over it in a circle until the desired particle size has been 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.
  • Mesh size of the filter can vary widely and depends primarily on the
  • 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 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 invention applied as a wet layer releases 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.
  • the wet layer is dried in a circulating air oven at 23 to 150 0 C, preferably 30 to 12O 0 C and especially 50 to 100 ° 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. In some cases, it may be advantageous to run the leveling process and the curing or crosslinking reaction with a time lag by running a step heating program or a so-called heat ramp.
  • the crosslinking temperature is between 120 and 16O 0 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 and moldings and films according to the invention used.
  • 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
  • Water or air such as bicycles, trolleys, rowboats, sailboats,
  • Hollow glass body industrial small parts such as screws, nut, hubcaps or rims,
  • Containers such as CoNs 1 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.
  • 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 car 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, Rockfall protection primers, surfacer coatings, basecoats,
  • 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 original finish of passenger cars (OEM) 1, in particular coatings of passenger cars of the upper class.
  • the multicoat color and / or effect coating 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 fully conform to the appearance of a Class A surface. 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. Their ability to wet substrates, especially precoated substrates, is significantly improved.
  • the polyester had an OH number of 131 mg KOH / g solids and a viscosity at 23 ° C of 0.85 dPas.
  • 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.
  • A3 a blocked polyisocyanate (A3) based on hexamethylene diisocyanate 534 parts by weight Desmodur® N 3300 (commercial isocyanurate of hexamethylene diisocyanate from Bayer AG) and 200 parts by weight of methyl ethyl ketone were placed in a reaction vessel and heated to 40 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 mixture slowly warmed to 8O 0 C. It was held at this temperature until its isocyanate content had dropped below 0.1%. Thereafter, the reaction mixture was cooled and discharged.
  • Desmodur® N 3300 commercial isocyanurate of
  • 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 ° C).
  • 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, 3.12 parts by weight of 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
  • the resulting aqueous emulsion was diluted with 1188 parts by weight of deionized water.
  • she was on a rotary evaporator under vacuum 560th Parts by weight of a mixture of volatile organic solvents and water removed.
  • Viscalex® HV commercial anionic thickener (A3) based on polyacrylate
  • Associative thickener (A3) from Rohm & Haas), 0.4 parts by weight of dimethylethanolamine
  • Clearcoat slurry 1 exhibited pronounced pseudoplastic behavior, excellent filterability, and excellent gear pump performance.
  • test panels steel sheets were used, which had been coated with a conventional and known, cathodically deposited and baked electrocoating.
  • a layer of a customary and known water filler from BASF Coatings AG and a layer of a customary and known black water-based coating from BASF Coatings AG were applied wet-on-wet to the electrodeposition coatings. After their application, the layers were each predried at 80 ° C. for 10 minutes.
  • 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 clearcoat 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.
  • edge cookers appeared.
  • Surface cookers only appeared from a layer thickness> 70 ⁇ m.
  • the wetting limit was only 16 ⁇ m both on the electrodeposition coating and on the basecoat.
  • test panels were prepared in the manner described above, except that the clearcoat 1 was not wedge-shaped but was applied in a practical dry film thickness of 40 microns.
  • Wave Scan (measuring device: Byk / Gardner company - Wave scan plus): Long Wave / Short Wave 4/20.
  • the clearcoat 1 had excellent scratch resistance, chemical resistance, weather resistance, intercoat adhesion, and condensation resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)

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 un polymère en étoile (A1) ; contenant des groupes fonctionnels réactifs, terminaux, pouvant être activés par rayonnement actinique et/ou thermiquement. L'invention concerne également des procédés de production et d'utilisation desdites dispersions.
PCT/EP2006/010181 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 WO2007048552A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005050822.7 2005-10-24
DE200510050822 DE102005050822A1 (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

Publications (1)

Publication Number Publication Date
WO2007048552A1 true WO2007048552A1 (fr) 2007-05-03

Family

ID=37635764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/010181 WO2007048552A1 (fr) 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

Country Status (2)

Country Link
DE (1) DE102005050822A1 (fr)
WO (1) WO2007048552A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251647A (zh) * 2018-08-02 2019-01-22 雅图高新材料有限公司 用于纤维增强环氧树脂复合材料的水性底漆及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109796578A (zh) * 2019-01-22 2019-05-24 华大化学(安徽)有限公司 一种耐刮耐磨、宽发泡温度的粗羊巴树脂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19840605A1 (de) * 1998-09-05 2000-03-09 Basf Coatings Ag Hyperverzweigte Verbindungen mit einer tetrafunktionellen Zentralgruppe und ihre Verwendung
WO2003010247A1 (fr) * 2001-07-24 2003-02-06 Basf Coatings Ag Vernis incolore a viscosite intrinseque se presentant sous la forme d'une pate, son procede de production et son utilisation
US20050020763A1 (en) * 2003-07-22 2005-01-27 Richard Milic Aqueous coating composition
US20050131146A1 (en) * 2003-12-16 2005-06-16 Retsch William H.Jr. Polymer additives for powder coatings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19840605A1 (de) * 1998-09-05 2000-03-09 Basf Coatings Ag Hyperverzweigte Verbindungen mit einer tetrafunktionellen Zentralgruppe und ihre Verwendung
WO2003010247A1 (fr) * 2001-07-24 2003-02-06 Basf Coatings Ag Vernis incolore a viscosite intrinseque se presentant sous la forme d'une pate, son procede de production et son utilisation
US20050020763A1 (en) * 2003-07-22 2005-01-27 Richard Milic Aqueous coating composition
US20050131146A1 (en) * 2003-12-16 2005-06-16 Retsch William H.Jr. Polymer additives for powder coatings

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251647A (zh) * 2018-08-02 2019-01-22 雅图高新材料有限公司 用于纤维增强环氧树脂复合材料的水性底漆及其制备方法
CN109251647B (zh) * 2018-08-02 2020-09-01 雅图高新材料股份有限公司 用于纤维增强环氧树脂复合材料的水性底漆及其制备方法

Also Published As

Publication number Publication date
DE102005050822A1 (de) 2007-04-26

Similar Documents

Publication Publication Date Title
DE19843581C2 (de) Verfahren zur Herstellung lackierter Substrate sowie entsprechend lackierte Substrate und deren Verwendung
EP1165702B1 (fr) Poudre en suspension durcissable thermiquement ou par rayonnement actinique, son procede de production et son utilisation
EP0947557B1 (fr) Dispersions de copolymères, combinaisons de liant à base de dispersions de copolymères, procédé de leur fabrication et leur utilisation
DE19841408C2 (de) Pulverklarlack und wäßrige Pulverklarlack-Slurry sowie deren Verwendung
WO2000044839A1 (fr) Agent de revetement comprenant au moins quatre composants, son procede de fabrication et son utilisation
WO2000050518A1 (fr) Poudre en suspension durcissable par rayonnement actinique et eventuellement par voie thermique, son procede de production et son utilisation
DE10055464B4 (de) Strukturviskose, von organischen Lösemitteln und externen Emulgatoren freie Pulverklarlack-Slurry und ihre Verwendung
EP1412436B1 (fr) Vernis incolore a viscosite intrinseque se presentant sous la forme d'une pate, son procede de production et son utilisation
WO1999003595A2 (fr) Procede de production de revetements multicouches
WO2007048552A1 (fr) Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes
WO2007025722A2 (fr) Utilisation d'alcools gras alcoxyles dans des suspensions de vernis clair a viscosite intrinseque, suspension de vernis clair a viscosite intrinseque, et procede de production et utilisation de cette suspension de vernis clair a viscosite intrinseque
EP1554323B1 (fr) Dispersion de microgel modifiee par acide phosphonique
EP1412442B1 (fr) Suspension de vernis clair de viscose de constitution, son procede d'obtention et son utilisation
EP1409434B1 (fr) Vernis incolore a viscosite intrinseque se presentant sous la forme d'une pate, son procede de production et son utilisation
WO2007048554A2 (fr) Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes
WO2007048551A2 (fr) Dispersions aqueuses sous forme de poudre, a viscosite intrinseque, exemptes ou partiellement exemptes de solvants organiques, procedes de production et d'utilisation associes
EP1525241B1 (fr) Suspension de vernis clair a viscosite intrinseque, procede pour la produire et son utilisation
DE19839453A1 (de) Oligomere und hochmolekulare Umsetzungsprodukte von Allophansäureestern mit nucleophilen Verbindungen und niedermolekulare, oligomere und hochmolekulare Verbindungen mit Allophanatseiten- und/oder -endgruppen sowie ihre Verwendung
DE29924932U1 (de) Copolymerisatdispersionen, Bindemittelkombinationen auf Basis der Copolymerisatdispersionen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06806458

Country of ref document: EP

Kind code of ref document: A1