WO2002046321A2 - Produit de revetement aqueux a effet, son procede de production et son utilisation - Google Patents

Produit de revetement aqueux a effet, son procede de production et son utilisation Download PDF

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Publication number
WO2002046321A2
WO2002046321A2 PCT/EP2001/014019 EP0114019W WO0246321A2 WO 2002046321 A2 WO2002046321 A2 WO 2002046321A2 EP 0114019 W EP0114019 W EP 0114019W WO 0246321 A2 WO0246321 A2 WO 0246321A2
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WIPO (PCT)
Prior art keywords
water
effect
dispersion
coating
pigments
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PCT/EP2001/014019
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German (de)
English (en)
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WO2002046321A3 (fr
Inventor
Karl-Heinz Josten
Harry Libutzki
Celina Budzinski
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Basf Coatings Ag
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Priority to AU2002233219A priority Critical patent/AU2002233219A1/en
Publication of WO2002046321A2 publication Critical patent/WO2002046321A2/fr
Publication of WO2002046321A3 publication Critical patent/WO2002046321A3/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
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients

Definitions

  • the present invention relates to a new, aqueous, effect-providing coating, in particular a metallic water-based paint.
  • the present invention also relates to a process for the production of the new, aqueous, effect-imparting coating material.
  • the present invention relates to the use of the new, aqueous, effect-imparting coating material for the production of single- or multi-layer, effect-imparting coatings.
  • Aqueous, effect-imparting coating materials in particular metallic water-based paints, especially metallic water-based paints based on polyurethane, are known, for example, from patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A 1, EP 0 593 454 A 1, DE-A-43 28 092 A 1, EP 0 299 148 A 1, EP 0 394 737 A 1, EP 0 590 484 A 1, EP 0 234 362 A 1, EP 0 234 361 A 1, EP 0 543 817 A 1, WO 95/14721, EP 0 521 928 A 1, EP 0 522420 A 1, EP 0 5224
  • the static viscosity of the aqueous coating material the kinematic viscosity of its droplets, its surface tension, - the surface tension of the substrate, the coating of the surface of the effect pigments, the evaporation properties of the solvents or cosolvents, the flight speed and kinetic energy of the droplets of the aqueous coating material, the diameter of the droplets or - the distribution of the droplet diameters.
  • Coating materials and the new, single-layer and multi-layer, effect coatings which are produced therefrom furthermore, if not exceed, the advantageous property profile of the known, aqueous, effect coating materials and the single-layer and multi-layer, effect coatings which are produced therefrom.
  • the new, aqueous, effect-imparting coating materials are to be obtainable in a simple manner with the aid of customary and known starting products with as little material modification of the known coating materials as possible, so that they can be produced, handled, applied and cured in existing devices.
  • the new, aqueous, effect-imparting coating material comprising at least one water-soluble or dispersible binder and at least one effect pigment, which can be prepared by:
  • the dispersions (I) and (II) are combined with the aqueous solution or dispersion of at least one water-soluble or dispersible binder.
  • coating material according to the invention The new aqueous, effect-imparting coating material is referred to below as "coating material according to the invention".
  • coating material according to the invention The new process for producing the coating material of the invention was found, in which
  • At least one water-miscible organic solvent and an aqueous solution or dispersion of at least one water-soluble or dispersible binder.
  • the dispersions (I) and (II) are combined with the aqueous solution or dispersion of at least one water-soluble or dispersible binder.
  • the new process for producing the coating material of the invention is referred to below as the "process of the invention”.
  • optical effects caused by the coating material according to the invention are preferably metallic effects and / or dichroic optical effects, but in particular metallic effects (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, pages 176, » Effect Pigments «and pages 380 and 381» Metal Oxide Mica Pigments «to» Metal Pigments «).
  • suitable effect pigments are metallic effect pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which is a shade of pink to brownish red, liquid crystalline effect pigments or fluorescent pigments (daylight pigments) such as bis (azomethine) pigments.
  • metallic effect pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1
  • non-metallic effect pigments such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which is a shade of pink to brownish red
  • liquid crystalline effect pigments or fluorescent pigments (daylight pigments) such as bis (azomethine) pigments.
  • fluorescent pigments such as bis (azomethine) pigments.
  • Römpp Lexikon Lacquers and Printing Inks Georg Thi
  • Metallic effect pigments are preferably used, in particular aluminum effect pigments (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, pages 24 and 25, “aluminum pigments”).
  • the aluminum effect pigments are leafing pigments (see Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 351, "Leafing-Pigments”) or non-leafing pigments (see Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 , Page 412, »Non-Leafing Pigments «). They are of a platelet-shaped, essentially round shape (silver dollar type) or of a platelet-i-shaped, essentially elongated shape.
  • a first part of it is dispersed in a mixture of at least one water-miscible organic solvent and an aqueous solution or dispersion of at least one water-soluble or dispersible binder (dispersion I).
  • the dispersion (I) can also contain part of the second effect pigment (cf. below).
  • water-miscible organic solvents are to be understood as paint-typical solvents which are miscible with water in any ratio, such as ethylene glycol, propylene glycol, butyl glycol and their methyl, ethyl or propyl ether, ketones such as acetone or diacetone alcohol, cyclic ethers such as tetrahydrofuran or Dioxane or amides such as N, N-dimethylformamide or N-methylpyrrolidone (see Paints Coatings and Solvent, edit. Dieter Stoye and Werner Freitag, second edition, Wiley-VCH, and Weinheim, New York, 1998, pages 329 and 330).
  • water-soluble or dispersible binders examples include those described below.
  • Water-soluble or dispersible polyesters are preferably used.
  • the content of the effect pigment or effect pigments in the dispersion (I) can vary very widely and depends, on the one hand, on the coverage of the effect pigment and on the intensity of the optical effect which it is desired to achieve.
  • the dispersions (I) preferably contain, based on their total amount, 10 to 80, preferably 12 to 75, particularly preferably 14 to 70, very particularly preferably 16 to 65 and in particular 18 to 60% by weight of effect pigment or pigments.
  • the content of the dispersion (I) in water-soluble or dispersible binders can also vary very widely and depends primarily on the dispersibility of the effect pigments on the one hand and the dispersibility of the binders on the other.
  • the binders are preferably used in an amount of, based on the total amount of dispersion (I), 10 to 60, preferably 11 to 55, particularly preferably 12 to 50, very particularly preferably 13 to 45 and in particular 14 to 40% by weight. % used.
  • the preparation of the dispersion (I) offers no special features in terms of method, but instead takes place by mixing the starting products, using the customary and known methods and devices for mixing liquid and solid products, such as stirred kettles, dissolvers or Ultraturrax. The mixing is carried out so gently that the effect pigments used are not damaged. If only one effect pigment is used for the production of the coating material according to the invention, the second part thereof is dispersed in a mixture of at least one water-miscible organic solvent and at least one water-immiscible or to a small extent solvent (dispersion II).
  • At least two different effect pigments are used to produce the coating material of the invention, at least one of them is used to produce the dispersion (II) (second effect pigment).
  • Suitable water-miscible organic solvents are those described above.
  • the organic solvents which are immiscible or only slightly miscible in water, take up at 20 ° C., based on water and solvent, preferably less than 10, preferably less than 9 and in particular less than 8% by weight of water. Conversely, water takes up at 20 ° C., based on water and solvent, preferably less than 6, preferably less than 5 and in particular less than 4% by weight.
  • suitable organic solvents which are immiscible or only slightly miscible in water are ketones such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone or trimethylcyclohexanone, ethers such as dibutyl ether, esters such as isopropyl acetate, butyl acetate, ethyl glycol acetate or butyl glycol acetate or higher alcohols such as hexanol or trimethyl, cyclohexanol alcohol 1-hexanol (isooctanol) (see Paints Coatings and Solvente, Edit.
  • ketones such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone or trimethylcyclohexanone
  • ethers such as dibutyl ether
  • esters such as isopropyl acetate, butyl acetate, ethyl glycol
  • the content of the effect pigment in the dispersion (II) can vary very widely and is also based on the parameters described above for the dispersion (I).
  • the dispersion (II) preferably contains, based on its total amount, 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight of effect pigment or pigments.
  • the content of the dispersion (II) in organic solvents which are immiscible or only slightly miscible with water can vary very widely.
  • the upper limit is the amount of solvent which just does not cause any separation phenomena in the coating material of the invention.
  • 1 to 80, preferably 2 to 75, particularly preferably 3 to 70, very particularly preferably 4 to 65 and in particular 5 to 60% by weight are preferably used.
  • Dispersion (II) is prepared in the same way as dispersion (I), except that no binder is used.
  • the dispersions (I) and (II) described above are combined with the aqueous solution or the dispersion (III) of at least one water-soluble or dispersible binder.
  • the dispersion (II) is preferably combined with the dispersion (III) before the dispersion (I).
  • the dispersion (III) contains at least one water-soluble or water-dispersible binder.
  • the binders can be curable physically, thermally or thermally and with actinic radiation. The latter is also referred to by experts as "dual cure”.
  • the term “physical hardening” means the hardening of a layer of a coating material by filming by release of solvent from the coating material, the connection within the coating via loop formation of the polymer molecules of the binders (for the term cf. Römpp Lexicon lacquers and printing inks , Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74. Or the filming takes place via the coalescence of binder particles (cf.
  • the binders are thermally curable, they can be thermally externally crosslinking or self-crosslinking, in particular externally crosslinking.
  • self-crosslinking denotes the property of a binder to undergo crosslinking reactions with itself.
  • binders already contain both types of complementary reactive functional groups which are necessary for thermal crosslinking, or reactive functional groups which are necessary for thermal crosslinking, or reactive functional groups which are necessary for thermal crosslinking.
  • Designated binder which is a kind of complementary reactive
  • actinic radiation means electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UN radiation, and corpuscular radiation such as electron beams.
  • NIR near infrared
  • the binders are oligomeric and polymeric resins. Oligomers are understood to mean resins which contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomere«, page 425.
  • Suitable binders are random, alternating and / or block-like linear and / or branched and / or crest-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyadditionharze (polyadducts)", and pages 463 and 464, "Polycondensates”, “Polycondensation” and “Polycondensation Resins", as well as pages 73 and 74, "Binders”.
  • suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers, especially polyurethane-modified (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, polyunides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyesters and polyurethanes.
  • the self-crosslinking thermally curable or dual-cure binders contain reactive unfunctional groups, with groups of their kind or with complementary reactive -functional groups can undergo crosslinking reactions.
  • the externally crosslinking thermally curable or dual-cure binders contain reactive functional groups which can undergo crosslinking reactions with complementary reactive functional groups which are present in the crosslinking agent. Examples of suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview.
  • the variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
  • the selection of the respective complementary groups depends on the one hand on the fact that they are involved in the manufacture, storage and application of the coating materials according to the invention do not undergo any undesirable reactions, in particular no premature crosslinking, and / or, if appropriate, must not interfere with or inhibit curing with actinic radiation and, secondly, according to the temperature range in which the crosslinking is to take place.
  • Crosslinking temperatures of 60 to 180 ° C. are preferably used in the coating materials of the invention.
  • crosslinking temperatures of 60 to 100 ° C. are used. Binders with thio, hydroxyl, primary and secondary amino groups and the imino groups and crosslinking agents with free isocyanate groups are preferably used.
  • crosslinking temperatures above 100 ° C. are preferably used.
  • A-koxyme ylaminogmppen on the other hand applied.
  • binders especially methylol, methylol ether and / or N-alkoxymethylamino groups are used.
  • the binders contain uni functional grappes which make them water-dispersible and / or water-soluble. These are either
  • Suitable functional groups (fl) which can be converted into cations by neutralizing agents and / or quaternizing agents are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, in particular tertiary amino groups or secondary sulfide groups.
  • Suitable catalytic groups (fl) are primary, secondary, tertiary or quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or tertiary sulfonium groups, but especially tertiary sulfonium groups.
  • Suitable functional grappes (12) which can be converted into anions by neutralizing agents are carboxylic acid, sulfonic acid or phosphonic acid groups, in particular carboxylic acid groups.
  • Suitable anionic groups (f2) are carboxylate, sulfonate or phosphonate groups, in particular carboxylate groups.
  • suitable neutralizing agents for functional grappes (fl) which can be converted into cations are inorganic and organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid or citric acid.
  • Suitable neutralizing agents for functional groups (f2) which can be converted into anions are ammonia or A ⁇ -ine, e.g. Trimemylamine, triethylamine, tributylarnine, dimethylaniline, diethylaniline, triphenylamine, diethylethanolamine, diethylethanolamine, methyldiethanolamine, 2- aminomethylpropanol, dimethylisopropylamine, thin ethylisopropanolamine or triethanolamine.
  • D-methylethanolamine and / or triethylamine is preferably used as the neutralizing agent.
  • the complementary reactive functional groups described above can be incorporated into the binders by the customary and known methods of polymer chemistry. This can be done, for example, by incorporating monomers which carry the corresponding reactive functional groups and / or using polymer-analogous reactions.
  • Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid, which are derived from an alkylene glycol which is esterified with the acid, or by reaction of the alpha, beta-olefinically unsaturated Carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-
  • hydroxyethyl 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indene-dimethanol or
  • olefinically unsaturated alcohols such as allyl alcohol
  • Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • (Meth) acrylic acid amides such as (meth) ac-ylic acid amide, N-methyl, N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl) -, N-ethoxymethyl and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide;
  • Acrylic acid methacrylic acid, ethacrylic acid, crotonic acid, maleic acid,
  • Fumaric acid or itaconic acid or allyl glycidyl ether Fumaric acid or itaconic acid or allyl glycidyl ether.
  • Invention is to be understood by subordinate amounts of high-functional monomers which do not lead to the crosslinking or gelling of the copolymers, in particular the (meth) acrylate copolymers, unless one wishes to produce crosslinked polymeric microparticles in a targeted manner.
  • suitable monomers for the introduction of reactive functional groups in polyester or polyester polyurethanes are 2,2-dimethylolethyl or propylamine, which are blocked with a ketone, the resulting ketoxime group being incorporated is hydrolyzed again; or compounds which contain two hydroxyl groups or two primary and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or at least one sulfonic acid group, such as dihydroxypropionic acid, dihydroxy succinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid , 2,2-dimethylolbutyric acid, 2,2-dimenthylolpentanoic acid, 3,4-
  • Diaminobenzoic acid 2,4-diaminotoluenesulfonic acid or 2,4-diamino-diphenyl ether sulfonic acid.
  • the dual-cure binders contain on average at least one, preferably at least two, grappa (s) with at least one bond (s) per molecule which can be activated with actinic radiation.
  • a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its kind which take place according to radical and / or ionic mechanisms.
  • suitable bonds are single carbon-hydrogen bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon-egg-individual bonds or double bonds.
  • the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".
  • the Grappe preferred according to the invention contains a double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually in the end, in the Grappe in question. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
  • the grapples are structurally different from one another or of the same structure. If they are structurally different from one another, this means in the context of the present invention that two, three, four or more, but in particular two grapples which can be activated with actinic radiation and which differ from two, three, four or more, but in particular two, are used. Derive monomer classes.
  • Suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.
  • the groups are preferably bound to the respective basic structures of the binders via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups.
  • This is usually done by customary and known polymer-analogous reactions, such as the reaction of pendant glycidyl groups with the above-described olefinically unsaturated monomers containing an acid group, of side hydroxyl groups with the halides of these monomers, of hydroxyl groups with double bonds containing isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or l- (l-isocyanato-l-methylethyl) - 3- (l-methylethenyl) benzene (TMI® from CYTEC) or of isocyanate groups with the above-described monomers containing hydroxyl groups.
  • the grappes can be used with the aid of compounds which contain at least one, in particular one, of the isocyanate-reactive or acid-reactive functional groups described above and at least one, in particular one, bond which can be activated with actinic radiation. Be stirred.
  • suitable compounds of this type are 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane, neopentylglycol, diethylene glycol, dipropylene glycol, dibutylene glycol,
  • EP 0 256 540 A1 EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A 1, EP 0 574417 A 1, EP 0 531 510 A 1, EP 0 581 211 A 1, EP 0 708 788 A 1, EP 0 593 454 A 1, DE-A-43 28 092 A 1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521
  • the content of the dispersion (III) in the binders described above can vary very widely.
  • the content is preferably 1 to 80, preferably 2 to 70, 3 to 60, particularly preferably 4 to 50, very particularly preferably 5 to 40 and in particular 6 to 30, by weight, based in each case on the total amount of the dispersion (III). %.
  • the dispersion (III) can contain customary and known color-imparting, electrically conductive or magnetically shielding pigments, soluble dyes and / or fillers.
  • Suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black; Colored pigments such as chromium oxide, Cl-romoxide hydrate green, cobalt green or ulframarin green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ulframarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
  • white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone
  • Black pigments such as carbon black, iron-manganese black or spinel black
  • Suitable organic color pigments are monoazo pigments,
  • Bisazo pigments antoquinone pigments, benzine azidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments,
  • Dioxazine pigments indanthrone pigments, isoindoline pigments, Isoindolinone pigments, azomethine pigments, thioindigo pigments,
  • Metal complex pigments perinone pigments, perylene pigments,
  • Phmalocyanine pigments or aniline black Phmalocyanine pigments or aniline black.
  • Suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.
  • suitable magnetically shielding pigments are pigments based on iron oxides or chromium dioxide.
  • Suitable soluble organic dyes are lightfast organic dyes with little or no tendency to migrate from the coating materials according to the invention and the coatings produced therefrom.
  • the person skilled in the art can estimate the tendency to migrate on the basis of his general specialist knowledge and / or determine it with the aid of simple preliminary tests, for example in the context of sound tests.
  • Suitable organic and inorganic fillers are chalk,
  • Calcium sulfate barium sulfate, silicates such as talc, mica or kaolin,
  • Silicic acids oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polylamide or Polyacrylonitrile.
  • organic fillers such as plastic powder, in particular made of polylamide or Polyacrylonitrile.
  • platelet-shaped inorganic fillers such as talc or mica
  • non-platelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfate or barium sulfate
  • the pigments, dyes and fillers described above can be in finely divided, non-opaque form.
  • the dispersion (III) can also contain additives such as nanoparticles, thermally or with actinic radiation reactive diluents, the above-described water-miscible and / or water-miscible organic solvents, UV absorbers, light stabilizers, radical scavengers, thermolabile radical initiators , Photoinitiators and co-initiators, crosslinking agents, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming aids, rheology-controlling additives (thickeners), flame retardants, skin additives, drying agents Containing agents, corrosion inhibitors, waxes and / or matting agents.
  • additives such as nanoparticles, thermally or with actinic radiation reactive diluents, the above-described water-miscible and / or water-
  • Suitable nanoparticles are, in particular, those based on silicon dioxide, aluminum oxide and zirconium oxide with a particle size ⁇ 50 nm, which have no matting effect.
  • suitable nanoparticles based on silicon dioxide are pyrogenic silicon dioxides, which are sold under the trade name Aerosil® VP8200, VP721 or R972 by Degussa or the trade name Gab O Sil® TS 610, CT 1110F or CT 1110G by the company CABOT are distributed.
  • these nanoparticles are sold in the form of dispersions in actinic radiation curable monomers such as the reactive diluents described below.
  • Suitable monomers which are particularly suitable for the present use are alkoxylated pentaerythritol tetra- or triacrylate, ditrimethylolpropane tetra- or triacrylate, dineopentylglycol diacrylate, trimethylolpropane triacrylate, trishydroxyethyl isocyanurate triacrylate,
  • these dispersions contain the nanoparticles in an amount of, based on the dispersions, 10 to 80% by weight, preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight and in particular 25 to 50% by weight .-%.
  • An example of a particularly suitable dispersion of nanoparticles is the dispersion, which is marketed by Clariant Hoechst under the trade name High Link® OG 103-31.
  • thermally stable reactive diluents are position-isomeric diethyloctanediols or hydroxyl groups containing hyperbranched compounds or dendrimers, as described, for example, in German patent applications DE 198 05 421 A1, DE 198 09 643 A1 or DE 198 40 405 A1.
  • Suitable reactive thinners curable with actinic radiation are those in Römpp Lexikon Lacke und Drackmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword, "Reaktiwer Printerner", or in column 7, lines 1 to 26, der DE 198 18 715 A1 or reactive diluents with at least 5, in particular 5, bonds which can be activated with actinic radiation in the molecule, such as, for example, dipentaerythritol pentaacrylate.
  • thermolabile free radical initiators examples include organic peroxides, organic azo compounds or CC-cleaving initiators such as Dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
  • Suitable catalysts for the crosslinking are dibutyltin dilaurate, 5 dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts such as bismuth lactate or dimethylol propionate.
  • Suitable crosslinking agents such as those used in multicomponent systems and which are usually added to the dispersions (III) subsequently, are polyisocyanates with an average of at least 15 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule how
  • Ethyl ethylene diisocyanate, trimemyl hexane diisocyanate, Heptamethylene diisocyanate or diisocyanates derived from dimer fatty acids, as described by the Henkel company under the trade name DDI 1410 xmd, are described in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl ) -l-pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-
  • Polyisocyanates containing urea carbodiimide and / or uretdione groups which are prepared in a customary and known manner from the diisocyanates described above;
  • suitable production processes and polyisocyanates are, for example, from the patents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0
  • Dual-cure polyisocyanates which are prepared from the above-described polyisocyanates and the above-described compounds which contain at least one, in particular one, of the above-described isocyanate-reactive or acid-reactive functional groups and at least one, in particular one, bond which can be activated with actinic sfrahhing ( see, for example, the European patent application EP 0 928 800 A1).
  • Suitable crosslinking agents such as are used in one-component systems, are aminoplast resins, such as are found, for example, in Römpp 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 ff, the book “Paints, Coatings and Solvente”, second completely revised edition, edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A or EP 0 245 700 A1 and in the article by B.
  • suitable deaerating agents are diazadicycloundecane or benzoin.
  • suitable emulsifiers are nonionic emulsifiers, such as alkoxylated alkanols, polyols, phenols and alkylphenols, or anionic emulsifiers, such as alkali metal salts or Ammom 'umsalze of alkanecarboxylic acids, alkanesulfonic acids, and sulphonic acids of alkoxylated alkanols, polyols, phenols and alkylphenols.
  • Suitable wetting agents are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.
  • An example of a suitable adhesion promoter is tricyclodecanedimethanol.
  • Suitable film-forming aids are cellulose derivatives such as cellulose acetobutyrate (GAB).
  • rheology-controlling additives examples include those known from patent applications WO 94/22968, EP 0 276 501 A1, EP 0 249201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aliiminixim magnesium silicates, sodium magnesium and
  • Sodium magnesium fluorine lithium layered silicates of the montmorillonite type Silicas such as aerosils; or synthetic polymers with ionic and / or associative grapples such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or polyacrylates; or associative thickeners based on polyurethane, as described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Thickeners", pages 599 to 600, and in the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 51 to 59 and 65; especially combinations of ionic and non-ionic thickeners, as described in patent application DE 198 41 842 A 1 for setting a structure-viscous behavior; or the
  • An example of a suitable matting agent is magnesium stearate.
  • UV absorbers examples include UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin retarding agents, corrosion inhibitors and waxes (B) are described in the textbook “Varnish Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York , 1998, described in detail.
  • the preparation of the dispersion (III) offers no special features in terms of method, but instead takes place as described above for the dispersions (I) and (II).
  • the ratio of dispersion (I) to dispersion (II) can vary very widely and depends primarily on the particular effect pigments present, their concentration and the optical effect that is to be set.
  • the ratio (I): (II) is preferably 1:10 to 10: 1, preferably 1: 8 to 8: 1, particularly preferably 1: 6 to 6: 1, very particularly preferably 1: 4 to 4: 1 and especially 1: 2 to 2: 1.
  • the coating material of the invention is for numerous applications in the fields of automotive OEM painting, automotive refinishing, the Painting of buildings indoors and outdoors, the painting of furniture, doors and windows as well as industrial painting, including container coating and coil coating and the coating of electrical components.
  • the coating material of the invention can be used as a filler, waterborne basecoat or solid-color topcoat, but in particular as a waterborne basecoat.
  • a waterborne basecoat it is used to produce multi-layer finishes according to the invention using the wet-on-wet process.
  • Suitable substrates consist of metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials such as gypsum and cement boards or roof tiles, as well as composites of these materials.
  • primers can be used which are produced in a customary and known manner from electrocoat materials. Both anodic and cathodic electrocoat materials, but especially cathodic ones, are suitable for this.
  • filler paint or stone scarf protection primer made from a conventional and known filler.
  • Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, GAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DEM 7728T1) can be painted.
  • non-functionalized and / or non-polar substrate surfaces these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a primer in a known manner before the coating.
  • Suitable clearcoats for the wet-on-wet process are single- or multi-component clearcoats, powder clearcoats, powder slurry clearcoats, UV-curable clearcoats or sealers, as described in patent applications, patent specifications and publications DE 42 04 518 A1, EP 0 594 068 A1 , EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A 1, US 5,356,669 A 1 or US 5,605,965 A 1, DE 42 22 194 A 1, the product information from BASF Lacke + Maschinen AG, "P
  • the coating materials of the invention can be applied by all customary application methods, such as spraying, knife coating, brushing, pouring, dipping, soaking, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.
  • Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application, such as hot air hot spraying.
  • the applications can be used at temperatures of max. 70 to 80.degree. C.
  • hot spraying can be designed in such a way that the coating material is heated only very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the respective applied coating material itself is operated.
  • the application is preferably carried out under illumination with visible light of a wavelength of over 550 nm or with exclusion of light. This avoids material changes or damage to the dual-cure coating material according to the invention and the overspray.
  • the water-based lacquer layer and the clear lacquer layer according to the invention are applied in a wet layer thickness in the production of the effect-imparting multi-layer lacquers according to the invention, so that after they have hardened, layers result with the layer thicknesses necessary and advantageous for their functions; in the case of the basecoat they are 5 to 50, preferably 6 to 40, particularly preferably 7 to 30 and in particular 8 to 25 ⁇ m, and in the case of the clearcoats they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 ⁇ m.
  • electrocoat layers xmd filler coats are used, their layer thicknesses in the case of electrocoating are 5 to 50, preferably 6 to 45, particularly preferably 7 to 40 and in particular 8 to 35 ⁇ m and in the case of filler coating 10 to 150, preferably 15 to 120 ⁇ m particularly preferably 20 to 100 and in particular 25 to 90 ⁇ m.
  • the hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h ⁇ md, in particular 1 min to 30 min.
  • the rest period is used, for example, for the course and degassing of the applied layers or for the evaporation of volatile constituents such as solvents or water.
  • the rest period can be supported and / or shortened by using elevated temperatures up to 80 ° C, provided that there is no damage or changes to the applied layers, such as premature complete crosslinking.
  • the thermal hardening has no special features in terms of method, but takes place according to the customary and known methods such as heating in a forced air oven or irradiation with IR lamps.
  • the hardening can also be carried out in stages. According to the invention, it takes place at temperatures from 60 to 180 ° C., preferably for a time of 1 minute to 2 hours, particularly preferably 2 minutes to 1 hour and in particular 3 minutes to 30 minutes.
  • UV radiation is preferably used.
  • work is preferably carried out under an inert gas atmosphere. This can be done, for example, by adding carbon dioxide and / or Nitrogen can be guaranteed directly to the surface of the applied layers.
  • inert gas atmosphere for example, by adding carbon dioxide and / or Nitrogen can be guaranteed directly to the surface of the applied layers.
  • inert gas it is also possible to work under inert gas in order to avoid the formation of ozone.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • suitable radiation sources are high-pressure or low-pressure mercury vapor lamps, which may be doped with lead in order to open a radiation window up to 405 nm, or electron beam sources.
  • Further examples of suitable radiation sources are described in German patent application DE 198 18 735 A1, column 10, lines 31 to 61. Their arrangement is known in principle and can be adapted to the conditions of the workpiece xmd of the process parameters.
  • the areas (shadow areas) which are not directly accessible to radiation, such as ceilings, folds and other undercuts caused by contraction, can be cured with point, single-surface or all-round jets combined with an automatic movement device for irradiating cavities or edges ,
  • the hardening can take place in stages, i. H. by multiple exposure or irradiation with actinic radiation. This can also take place alternately, i. that is, for example, alternately hardened with UN radiation and electron radiation.
  • Thermal curing and curing with actinic radiation can be used simultaneously or alternately. Will the two hardening methods Used alternately, curing with actinic radiation can begin, for example, and end with thermal curing. In other cases, it may prove advantageous to start and end the curing with actinic radiation.
  • the person skilled in the art can determine the hardening method which is most advantageous for the individual case on the basis of his general specialist knowledge, if necessary with the aid of simple standard tests.
  • the single-layer and multi-layer effect coatings according to the invention produced from the coating materials according to the invention, in particular the effect multi-layer coatings according to the invention, have the overall quality required for use in automotive OEM coating. So are yours
  • optical properties such as
  • a condensation product (number average molecular weight: 1410) from 1.81 mol of a polymeric fatty acid (dimer content at least 98% by weight, trimers content at most 2.0% by weight, monomer content at most traces), 0.82 mol of isophthalic acid, 0.61 mol of hexanediol and 0.61 mol of neopentyl glycol, 61 parts by weight of dimethylolpropionic acid, 10.6 parts by weight of neopentyl glycol, 365 parts by weight of methyl ethyl ketone and 308.3 parts by weight of m-tetramethylxylylidene diisocyanate were placed in a suitable reaction vessel heated to 80 ° C while stirring under a nitrogen atmosphere.
  • the reaction was continued up to an isocyanate content of 1.1% by weight, based on the total amount of the reaction mixture. Then 52.6 parts by weight of trimethylolpropane --------- were added, after which the resulting reaction mixture was stirred at 80 ° C. until no free isocyanate groups were detectable. Then 33 parts by weight of D-mernyleth-molamine, 255 parts by weight of butylglycol xmd and then 2153 parts by weight of deionized water were slowly stirred in. The methyl ethyl ketone was distilled off under vacuum. The result was a finely divided dispersion, the pH of which was adjusted to 7.4 with dimethylethanolamine and the non-volatile content of which was adjusted to 31% by weight with deionized water.
  • a condensation product (number average molecular weight: 1423) from 1.0 mol of a polymeric fatty acid (dimer content at least 98% by weight, dimer content at most 2.0% by weight, monomer content of the highest traces), 1.5 mol of isophthalic acid, 1, 6 moles of neopentyl glycol and 1.7 moles of hexanediol, 31.2 parts by weight of neopentyl glycol, 185 parts by weight of methyl ethyl ketone, 201.7 parts by weight of m-tetramethylxylylidene diisocyanate and 0.7 parts by weight of dibutyltin dilaxxate were heated to 80 ° C.
  • a solution of 1.17 parts by weight of t-butyl perethylhexanoate in 3.5 parts by weight of butyl glycol was then added uniformly at a rate such that the addition was complete after 1.5 hours.
  • a mixture of 5.85 parts by weight of acrylic acid and 4.65 parts by weight of n-butyl methacrylate, 2.94 parts by weight of methyl methacrylate, 5.90 parts by weight of lauryl methacrylate, 1.25 parts by weight of hydroxypropyl acrylate and 2.94 Parts by weight of styrene started.
  • the monomer mixture was added uniformly at such a rate that the addition was completed within one hour.
  • the temperature of the reaction mixture was then kept at 110 ° C.
  • the resulting resin solution was concentrated by distillation under vacuum to 80% by weight solids content and neutralized with dimernyleth-molamine at this temperature within 30 minutes to a degree of neutralization of 80%.
  • the resin solution was cooled to 60 ° C, after which the heating was switched off. Water was then slowly added until the solids content of the dispersion was 40% by weight.
  • the dispersion had an acid number of 36.7 mg KOH / g and a pH of 7.6.
  • the production of a dispersion containing effect pigments (I) was prepared by mixing 3.0 parts by weight of the commercially available aluminum mix effect pigment Alu-Stapa Hydrolux® VP 51284 / G6, 1.8 parts by weight of the commercial Alxmi effect effect pigment Alu-Stapa Hydrolux® 2154 (both from Eckart), 4. 8 parts by weight of butylglycol, 1.0 part by weight of l-propoxy-2-propanol and 2.4 parts by weight of the polyester resin solution according to Preparation Example 2.
  • the dispersion (I) was mixed by mixing 0.6 parts by weight of the commercially available aluminum effect pigment Alu-Stapa Hydrolux® VP 51284 / G6, 1.8 parts by weight of the commercial aluminum effect pigment Alu-Stapa Hydrolxix® 2154 (both from Eckart), 2.9 Parts by weight of butyl glycol and 2.4 parts by weight of the polyester resin solution prepared according to Preparation Example 2.
  • the dispersion (II) was prepared by mixing 2.4 parts by weight of the commercially available aluminum effect pigment Alu-Stapa Hydrolux® VP 51284 / G6, 1.9 parts by weight of butylglycol, 1.0 part by weight of 1 -propoxy-2-propanol xmd 0.5 part by weight of 2- Ethyl-l-hexanol produced.
  • the waterborne basecoats were adjusted to a viscosity of 70 to 90 mPas in a shear field of 1,000 s "1 .
  • the waterborne basecoat from example 1 was used.
  • test boards measuring 30 x 70 cm were used in a customary and known manner manufactured.
  • steel panels which had been coated with a customary and known, cathodically deposited and baked electro-dip coating were coated with a commercially available filler from BASF Coatings AG, after which the resulting filler layer was kept at 20 ° C. and a relative air humidity of 65 for five minutes % flashed off and baked in a forced air oven at 140 ° C for 30 minutes.
  • the waterborne basecoats were applied in two spray passes.
  • the first order is made using ESTA (bell speed: 45,000 rpm; steering air: 120 V ⁇ -i ---- voltage: 65KV; distance: 0.25 m; paint discharge: 170 ml / min), corresponding to a dry film thickness of 8 to 2 ⁇ m.
  • the second application was pneumatic (distance: 0.32 m; paint discharge: 540 mt / min; atomizing air - quantity: 300 Nt / min; atomizing air - pressure: 4.8 bar; horn air - pressure: 5.2 bar; horn air - Quantity: 395 Nl / min), corresponding to a dry film thickness of 4 to 6 ⁇ m.
  • the waterborne basecoats were each flashed off for two minutes after the first and second application.
  • the water-based lacquer layers were dried at 80 ° C. for 15 minutes, cooled and covered with a commercially available two-component clear lacquer from BASF Coatings AG.
  • the water-based lacquer layers and the clear lacquer layers were then baked at 130 ° C. for 30 minutes, resulting in the multi-layer coating of Example 2 according to the invention and the multi-layer coating of Comparative Experiment V 2 not according to the invention.
  • test panels were visually assessed and graded under diffuse light from a distance of 2 to 3 m in top view (80 °) and in oblique view (40 °) with regard to light-dark shading (clouds) (grade 1: no clouds visible; to Grade 5: Clouds very clearly visible).
  • clouds light-dark shading
  • Example 2 Clouds (supervision): 2; Clouds (oblique view): 3
  • Clouds (supervision): 3; Clouds (oblique view): 5
  • Example 2 showed significantly fewer light-dark shades than the waterborne basecoat of Comparative Experiment V 2.

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Abstract

L'invention concerne un produit de revêtement aqueux à effet contenant au moins un liant soluble ou dispersible dans l'eau et au moins un pigment à effet. Pour obtenir ce produit, on (I) disperse une première fraction du pigment à effet ou au moins un premier pigment à effet dans un mélange, composé au moins d'un solvant organique miscible à l'eau et d'une solution aqueuse ou d'une dispersion au moins liant soluble ou dispersible dans l'eau, et on (II) disperse une deuxième fraction du pigment à effet ou au moins un deuxième pigment à effet dans un mélange, composé au moins d'un solvant organique miscible à l'eau et au moins d'un solvant pas ou peu miscible à l'eau, ensuite on (III) ajoute les dispersions (I) et (II) à la solution aqueuse ou à la dispersion d'un liant soluble ou dispersible dans l'eau. L'invention concerne son procédé de production et son utilisation dans la peinture en série d'automobiles, la réparation de peinture automobile, la peinture de constructions à l'intérieur et à l'extérieur, la peinture de portes, fenêtres et meubles ainsi que la peinture industrielle, y compris l'enduction en continu de bandes et le revêtement de composants électrotechniques.
PCT/EP2001/014019 2000-12-05 2001-11-30 Produit de revetement aqueux a effet, son procede de production et son utilisation WO2002046321A2 (fr)

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Cited By (4)

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WO2012004075A1 (fr) * 2010-07-07 2012-01-12 Basf Coatings Gmbh Procédé de fabrication d'une peinture multicouche colorante et/ou à effet, la composition du revêtement produisant une coloration contenant un cyclohexanol substitué pour réduire le nombre de piqûres
WO2014202724A1 (fr) 2013-06-19 2014-12-24 Igp Pulvertechnik Ag Procédé de revêtement d'une surface d'un substrat électriquement non conducteur au moyen de peintures en poudre
EP2886570A1 (fr) * 2013-12-18 2015-06-24 BASF Coatings GmbH Agent de revêtement en base aqueuse et fabrication de peintures multicouches à l'aide de l'agent de revêtement
WO2015090807A1 (fr) * 2013-12-18 2015-06-25 Basf Coatings Gmbh Agent de revêtement aqueux et production de laquages multicouches en utilisant l'agent de revêtement

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EP0608773A1 (fr) * 1993-01-26 1994-08-03 Herberts Gesellschaft mit beschränkter Haftung Procédé pour la préparation de revêtements aqueux en utilisant des systèmes modulaires

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ATE158608T1 (de) * 1990-07-13 1997-10-15 Basf Corp Wässerige metallic-grundierungszusammensetzung auf basis von acryl-latex-harzen unter verwendung eines wasserverdünnbaren harzes als medium für das aluminium und hectorit-ton zur rheologie- regelung

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DE4110520A1 (de) * 1991-03-30 1992-10-01 Basf Lacke & Farben Mischsystem zur herstellung wasserverduennbarer ueberzugsmittel
EP0608773A1 (fr) * 1993-01-26 1994-08-03 Herberts Gesellschaft mit beschränkter Haftung Procédé pour la préparation de revêtements aqueux en utilisant des systèmes modulaires

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012004075A1 (fr) * 2010-07-07 2012-01-12 Basf Coatings Gmbh Procédé de fabrication d'une peinture multicouche colorante et/ou à effet, la composition du revêtement produisant une coloration contenant un cyclohexanol substitué pour réduire le nombre de piqûres
CN102892841A (zh) * 2010-07-07 2013-01-23 巴斯夫涂料有限公司 生产赋予色彩和/或效果的多层涂漆的方法，其中形成色彩的涂料组合物包含取代的环己醇以减少针孔数量
WO2014202724A1 (fr) 2013-06-19 2014-12-24 Igp Pulvertechnik Ag Procédé de revêtement d'une surface d'un substrat électriquement non conducteur au moyen de peintures en poudre
US10010908B2 (en) 2013-06-19 2018-07-03 Igp Pulvertechnik Ag Method for coating a surface of an electrically non-conductive substrate with powder coatings
CN105829381A (zh) * 2013-12-18 2016-08-03 巴斯夫涂料有限公司 水性涂料组合物和使用所述涂料组合物制备多涂层油漆体系
WO2015091194A1 (fr) * 2013-12-18 2015-06-25 Basf Coatings Gmbh Agent de revêtement aqueux et production de laques multicouches en utilisant l'agent de revêtement
WO2015090807A1 (fr) * 2013-12-18 2015-06-25 Basf Coatings Gmbh Agent de revêtement aqueux et production de laquages multicouches en utilisant l'agent de revêtement
CN105940031A (zh) * 2013-12-18 2016-09-14 巴斯夫涂料有限公司 水性涂料组合物和使用所述涂料组合物制备多涂层油漆体系
JP2017507201A (ja) * 2013-12-18 2017-03-16 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 水性塗料組成物および前記塗料組成物を使用した多層塗装系の製造
JP2017509725A (ja) * 2013-12-18 2017-04-06 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 水性塗料組成物および前記塗料組成物を使用した多層塗装系の製造
US9976052B2 (en) 2013-12-18 2018-05-22 Basf Coatings Gmbh Aqueous coating composition and production of multicoat paint systems using said coating composition
EP2886570A1 (fr) * 2013-12-18 2015-06-24 BASF Coatings GmbH Agent de revêtement en base aqueuse et fabrication de peintures multicouches à l'aide de l'agent de revêtement
CN105940031B (zh) * 2013-12-18 2019-03-01 巴斯夫涂料有限公司 水性涂料组合物和使用所述涂料组合物制备多涂层油漆体系
US10344181B2 (en) 2013-12-18 2019-07-09 Basf Coatings Gmbh Aqueous coating composition and production of multicoat paint systems using said coating composition
CN105829381B (zh) * 2013-12-18 2020-01-14 巴斯夫涂料有限公司 水性涂料组合物和使用所述涂料组合物制备多涂层油漆体系

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