EP3004253A1 - Pigments à effet métallique résistant à la corrosion, procédé pour les fabriquer et leur utilisation - Google Patents

Pigments à effet métallique résistant à la corrosion, procédé pour les fabriquer et leur utilisation

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Publication number
EP3004253A1
EP3004253A1 EP14730798.7A EP14730798A EP3004253A1 EP 3004253 A1 EP3004253 A1 EP 3004253A1 EP 14730798 A EP14730798 A EP 14730798A EP 3004253 A1 EP3004253 A1 EP 3004253A1
Authority
EP
European Patent Office
Prior art keywords
component
metallic effect
polymer layer
metallic
effect pigment
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP14730798.7A
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German (de)
English (en)
Inventor
Ulrich-Andreas HIRTH
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Individual
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Individual
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Filing date
Publication date
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Publication of EP3004253A1 publication Critical patent/EP3004253A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/035—Coloring agents, e.g. pigments
    • 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
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C09C2200/1058—Interference pigments characterized by the core material the core consisting of a metal comprising a protective coating on the metallic layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2210/00—Special effects or uses of interference pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation

Definitions

  • the present invention relates to chemical and corrosive effects resistant metal effect pigments having a polymeric, organic protective layer.
  • the optical effect of metallic effect pigments is based on the directed reflection of light on ideally plane-parallel aligned platelet-shaped pigment particles.
  • the viewing angle changes the brightness and in some cases the hue.
  • Characteristic for metallic effect pigments are their metallic luster and their excellent hiding power. Important for the visual impression are an optimal distribution, a plane-parallel orientation in the coating film and a sufficient corrosion resistance of the metallic effect pigments in the processing, coating and application medium.
  • metallic effect pigments are only very limitedly stable in aqueous media.
  • aluminum pigments decompose comparatively rapidly in water to form hydrogen and aluminum hydroxide.
  • the metal pigment surfaces are often protected by phosphating, chromating or silanization.
  • metallic effect pigments coated with a polymeric organic protective layer are also becoming increasingly important.
  • EP 0 477 433 B1 describes aluminum-based resin-coated metal pigments, wherein a synthetic resin layer is covalently bound via a siloxane coating applied to the effect pigment surface.
  • the siloxane layer should serve as a bonding agent for a good connection of the synthetic resin coating on the effect pigment surface.
  • it has been shown that it can come under the action of shear forces to a partial detachment of the resin layer. These pigments are therefore not reliable gas stable and corrosion resistant.
  • EP 0 280 749 B1 discloses resin-coated metal pigments, wherein an ethylenically unsaturated carboxylic acid and / or a phosphoric acid mono- or diester is arranged as adhesion promoter between the pigment surface and the synthetic resin layer.
  • the carboxyl group of the carboxylic acid monomer or the phosphoric acid groups of the phosphate monomer bind to the metal pigment surface. With the thus arranged on the metal pigment surface ethylenic double bonds further monomers are reacted to form a highly crosslinked resin layer.
  • the gassing stability of these metal pigments in aqueous media is at the same time low.
  • WO2005 / 063897 discloses chemically stable metallic effect pigments which are coated with oligomeric and / or polymeric binders which can be crosslinked thermally and / or under UV or IR radiation.
  • the metallic effect pigments can thus be embedded in a polymeric paint film.
  • the binders are still thermally curable and polymerizable after the coating of the metallic effect pigments, which is why these metallic effect pigments are used in powder coatings. While coating the metallic effect pigments or removing the solvents, the pigments can easily polymerize, but they do not harden out. Precoating the pigment surface with functionalized silanes, polymers or organophosphorus compounds improves the adhesion of the pigment coating.
  • EP 1 084 198 B1 discloses metal effect pigments whose surface has been modified with orientation aids.
  • the orientation aid present in monomeric or polymeric form carries at least two different functional groups, which are separated from one another by a spacer.
  • One of the functional groups is chemically bound to the metal effect pigment, the other can be linked to the binder of the surrounding paint in a crosslinking reaction and thus make an additional contribution to the stabilization of the metallic effect pigment.
  • metallic effect pigments are to be obtained which are to be readily wettable, to be excellently oriented in the liquid coating film and, after film drying, to form an intimate bond with the surrounding binder matrix. This should significantly improve the condensation resistance of a hardened lacquer.
  • No. 4,213,886 discloses a coated aluminum pigment, wherein a silane having a monoethylene group and subsequently an acrylate resin layer are applied in a first layer. It has been found that this two-layer structure of silane layer and subsequent acrylate resin layer is not sufficiently dense against ingress of water and chemicals.
  • DE 10 2005 037 61 1 A1 describes metallic effect pigments with an inorganic / organic mixed layer which, in addition to high mechanical stability, should also have good gassing stability in water-based paints.
  • organic oligomers and / or polymers with an inorganic network consisting of inorganic oxide components should be at least partially covalently bonded via network formers such as, for example, organofunctional silanes.
  • DE 10 2004 006 145 A1 describes platelet-shaped substrates with a functional multilayer structure consisting of one or more layers of a polymer and one or more layers of a silane. The layers of one or more silanes are intended to exert a barrier function, while the layers of one or more polymers to stabilize the pigments mechanically and against a tendency to agglomerate.
  • US 4,434,009 describes a polymer coating of metal pigments composed of monomers having a polymerizable double bond and an epoxy group.
  • JP 56-161470 Another polymer coating of metal pigments is described in JP 56-161470.
  • the coating is carried out by monomers of the type styrene, (meth) acrylonitrile or
  • DE 102 09 359 A1 discloses platelet-shaped effect pigments coated with hardened melamine-formaldehyde resin.
  • WO 2004/029160 describes effect pigments enveloped with LCST and / or UCST polymers which are said to be stable in aqueous solution in a pH range of 3 to 9.
  • No. 6,192,248 B1 discloses a coating formulation in which metal pigments are mixed with alicyclic isocyanates and alicyclic polyurea ketimines. However, this is not a coating of individual metal flakes but already a finished coating formulation.
  • the described polymer coatings have in common that the polymeric network wholly or partly generated by free-radical polymerization.
  • Radical starters are used whose decomposition products are toxic and extremely harmful to health.
  • the radical starter AIBN azo-bis- (isobutyrodinitrile)
  • the radical starter AIBN which is used very frequently in the free-radical polymerization to coat the metal pigments, forms the toxic decomposition product tetramethylsuccinonitrile, which is found in significant amounts on the corresponding polymer-coated metallic effect pigments.
  • AIBN azo-bis- (isobutyrodinitrile)
  • the use of polymer-coated metallic effect pigments in which AIBN is used in the free radical polymerization process is therefore limited to applications in which a health risk for users and consumers can be ruled out.
  • radical polymerizations are rather uncontrolled and therefore do not lead to a homogeneous, completely closed polymer coating of the metallic effect pigment.
  • the polymer shells with adhesion promoters prove to be in part not resistant to increased mechanical forces, as they act, for example, in a bonding process in the powder coating on the coated metallic effect pigments.
  • the object of the present invention is to provide metallic effect pigments which are resistant to corrosive chemicals and media.
  • the metallic effect pigments should have good compatibility with the application medium, in particular with powder coatings.
  • the object is achieved according to the invention by providing metallic effect pigments with a platelet-shaped, metallic core and a platelet-shaped metal core enveloping homogeneous, polyurea-like polymer layer, wherein the polymer layer is obtained by an addition reaction of a component A with a component B, wherein the component A has molecules containing 1 - 20 primary and / or secondary amino groups and the component B has molecules which 1 to 20 isocyanate groups.
  • an enveloping, homogeneous, polyurea-like polymer layer is understood to mean that the polymer layer coats the individual metallic effect pigment particles.
  • the coating is applied in a separate step before the thus coated metallic effect pigments are converted into a formulation such as e.g. a lacquer or a printing ink are incorporated.
  • a formulation such as e.g. a lacquer or a printing ink are incorporated.
  • the coating of the enveloping homogeneous, polyurea-like layer is thus not carried out in the finished paint.
  • the metallic effect pigments are not coated during the application of the coating composition.
  • the polymer layer enveloping the metallic core is characterized in that it is constructed by means of an addition reaction of two different components, components A and components B.
  • Component A has molecules containing 1 to 20, preferably 2 to 15 primary and / or secondary amino groups.
  • Component B has molecules containing 1 to 20, preferably 2 to 15, isocyanate groups.
  • component A has from 1 to 20, preferably from 2 to 15, more preferably from 3 to 10, primary and / or secondary amino groups.
  • component B has from 1 to 20, preferably from 2 to 15, more preferably from 3 to 10, isocyanate groups.
  • the polyurea-like polymer layer is formed by formation of a polymeric network enveloping the metallic effect pigment core by addition of the NH function of component A to the NCO functions of component B. This reaction proceeds very rapidly even at room temperature in anhydrous organic solvents without side reaction.
  • a polyurea-like polymer layer on which the invention is based adheres extremely firmly and reliably to the metal pigment surface and is also exceptionally stable with respect to mechanical shear forces.
  • the polyurea-like polymer layer is the sensitive metal core permanently protects against aggressive and corrosive chemicals and media, so that their optical properties such as gloss and color are not impaired.
  • Another advantage of the present invention is that the coating reaction occurs at room temperature. Previous methods of the prior art always take place at temperatures around 80 ° C or above. Performing the coating reaction at room temperature saves time and energy.
  • the metallic effect pigments according to the invention are further distinguished by the fact that the homogeneous, urea-like polymer layer can be relatively thin, whereby on the one hand the production costs can be reduced due to the low material consumption and, on the other hand, an influence of gloss and color of the metallic effect pigments largely by the polyurea-like polymer layer applied in an enveloping manner is eliminated.
  • the thickness of the homogeneous, urea-like polymer layer is preferably selected from a range of 5 to 1000 nm, more preferably from a range of 10 to 150 nm, and most preferably from a range of 30 to 70 nm.
  • the weight of the polyurea-like polymer layer is preferably in a range of 0.5 to 80 wt .-%, based on the total weight of the metallic effect pigment according to the invention.
  • the weight of the polyurea-like polymer layer is in a range of 5 to 70 wt .-%, and most preferably in a range of 15 to 60 wt .-%, each based on the total weight of the metallic effect pigment according to the invention. In individual cases, the amount of weight to be chosen will depend on the fineness and thickness of the metallic, platelet-shaped core.
  • the polymer coating no longer has sufficient corrosion resistance.
  • the hiding power that is to say the area covered by pigment per unit area of pigment, of the metallic effect pigments according to the invention decreases too much and the corrosion-protecting properties no longer improve significantly.
  • the polyurea-like polymer layer can be applied in a single-stage process, which manifests itself cost-effectively on the production costs.
  • the polyurea-like polymer layer also contain other other chemical building blocks.
  • the proportion of the polyurea-like polymer layer is preferably at least 50% by weight of the weight of the coating of the metallic effect pigments.
  • These other chemical building blocks may be additives, such as corrosion inhibitors, colored pigments, dyes, UV stabilizers, etc., or mixtures thereof.
  • the polyurea-like polymer layer preferably contains from 70 to 100% by weight of polyurea, based on the total weight of the enveloping polymer layer. More preferably, the enveloping polymer layer contains 80-100% by weight of polyurea and most preferably 90-100% by weight of polyurea, based in each case on the total weight of the enveloping polymer layer.
  • the molar ratio of the isocyanate groups of component B to the amino groups of component A is preferably in a range of 0.9 to 1.1; more preferably in a range of 0.95 to 1, 07, and most preferably in a range of 1, 00 to 1, 05.
  • the isocyanate groups usually react substantially completely, preferably completely, with the amino groups to form a urea group. However, it may be advantageous for the polyurea layer to have a slight excess of isocyanate groups in order to use these functionalities for attaching surface modifiers.
  • Such surface modifiers are preferably aminosilicones or fatty amines.
  • Such compounds upon formation of an enveloping polyurea layer on the metallic effect pigments, will react with excess isocyanate groups of the polyurea coating due to their amino groups and thus become bound to the surface of the coated metallic effect pigment. Because of their hydrophobic radical, they give the thus modified metallic effect pigments a particularly high stability against agglomeration and lead to an improved pigment orientation in the application medium. This manifests itself in an increased hiding power and a stronger light-dark flop, compared with metal pigments according to the invention which do not have such a surface modification.
  • embodiments it is advantageous to have some excess of amino groups in the polymer coating, since excess amino groups can bind both to the metallic effect pigment surface to allow good adhesion to the surface of the metallic effect pigment, as well as to the surface of the polymer layer as functional groups are available for surface modification.
  • embodiments having a molar ratio of the isocyanate groups of component B to the amino groups of component A are also in the range of 0.9 to 0.99 preferably and more preferably from a range of 0.95 to 0.98.
  • the components on which components A are based preferably comprise primary and / or secondary mono, di-, polyamines and / or polyamidoamines having 1-20 amino groups.
  • the components underlying components A particularly preferably have 2 to 4 amino groups.
  • Monoamines are used only in very small amounts, since they essentially allow a termination of an addition polymerization, but no further polymerization. Monoamines are therefore preferably used only in amounts of 0 to 15 wt .-%, based on the total weight of component A.
  • the component A compared to the number of amino groups only 10 mol%, more preferably only 5mol% and most preferably 0 mol% of hydroxyl groups on. It has been found that the presence of hydroxyl groups which react with isocyanate groups to form a urethane group, the stability of the polymer layer is not conducive.
  • preferred embodiments have no toxic constituents in the coating of the metallic effect pigments according to the invention.
  • Suitable monoamines are stearylamine, palmitoleinamine, caprylamine, cyclohexylamine or butylamine.
  • di-amines examples include isophoronediamine, 2,2,4-trimethylhexanediamine, 2,4-toluenediamine, ethylenediamine, propylenediamine, hexamethylenediamine or tetramethylenediamine.
  • Suitable higher-functional amines or polyamines and / or polyamidoamines are PAMAM CeTePox 1950 H, triethylenetetramine, N, N'-bis (3-aminopropyl) ethylenediamine, N, N-dimethyldipropylenetriamine, diethylenetriamine or polyethyleneimines (available, for example, under the name Luprasol ® (BASF)).
  • component A comprises a mixture of an isophorone diamine and an aliphatic diamine.
  • the weight ratio of isophoronediamine to aliphatic diamine is preferably 3: 1 to 1: 2 and more preferably 2: 1 to 1: 1.
  • the components on which components B are based preferably comprise mono, di- and / or polyisocyanates and / or isocyanate-containing prepolymers having 1-20 isocyanate groups.
  • the components underlying components B preferably have 2 to 6 isocyanate groups (per monomer molecule).
  • Monoisocyanates are, analogously to monoamines in the component A, used only in very small amounts as component B, since they essentially allow termination of an addition polymerization, but no further polymerization. Monoisocyanates are therefore preferably used only in amounts of 0 to 15 wt .-%, based on the total amount of component B.
  • Suitable mono-isocyanates are stearyl isocyanate, palmitole isocyanate, caprylic acid, cyclohexyl isocyanate or butyl isocyanate.
  • di-isocyanates examples include isophorone diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate or tetramethylene diisocyanate.
  • di-isocyanates examples include Desmodur Z 4470 BA, Desmodur XP 2489, Desmodur N 75, Desmodur XP 2406 or Desmodur E 305 (all commercially available from Bayer Material Science).
  • both component A and component B have isophorone groups. It has surprisingly been found that the polymerization proceeds well with such groups and particularly corrosion-resistant coatings of the metallic effect pigments are obtained.
  • component A is isophorone-containing diamines and component B is isophorone-containing diisocyanates.
  • the isophorone-containing diamines or di-isocyanates have a particularly high affinity for the surfaces of the metallic effect pigments. Therefore, they are at least partially adsorbed on the surface of the metallic effect pigments before the start of the addition polymerization, and thereby the polymerization preferably takes place on the surface of the metallic effect pigments. This results in a dense polymer layer which uniformly envelopes the metallic, platelet-shaped cores and has a very low content of secondary precipitations.
  • the platelet-shaped metallic cores are preferably selected from at least one metal which comprises or consists of aluminum, copper, tin, zinc, iron, chromium, nickel, silver, gold, gold bronze, brass or steel or their mixtures or alloys.
  • the platelet-shaped metallic core comprises or consists of aluminum, copper, iron or gold bronze.
  • the platelet-shaped metallic core comprises or consists of aluminum.
  • the proportion of aluminum in a range of 90 to 100 wt .-%, more preferably from 98 to 99.99 wt .-%, each based on the total weight of the aluminum pigment.
  • the platelet-shaped metal pigments preferably have an average diameter of 1 to 200 ⁇ m, more preferably of 3 to 140 ⁇ m, even more preferably of 5 to 95 ⁇ m.
  • the average thickness of the platelet-shaped metal pigments is preferably in a range from 20 nm to 1 ⁇ m, more preferably from 30 nm to 750 nm, even more preferably from 40 nm to 600 nm.
  • the shape factor ie, the ratio of average diameter (D 50 ) to average thickness (h 50 ), is preferably in a range from 1000: 1 to 5: 1, more preferably from 500: 1 to 10: 1, still more preferably from 300: 1 to 100: 1.
  • the platelet-shaped metal pigments may be metal pigments obtained by milling, preferably aluminum pigments, or pigments obtained by physical vapor deposition (PVD), preferably PVD pigments.
  • the invention further relates to the use of the metallic effect pigments of the invention in paints, printing inks, paints, powder coatings, plastics and cosmetics.
  • the metallic effect pigments according to the invention are preferably used in powder coatings. Very particular preference is given to powder coating applications for the interior.
  • the invention furthermore relates to a coating system comprising the metallic effect pigments according to the invention.
  • the coating system may in this case preferably consist of at least one material selected from the group of paints, printing inks, lacquers, powder coatings, plastics and / or cosmetics.
  • the subject of the invention is a coated article, which contains appropriate metallic effect pigments or which contains a coating system containing at least one inventive metallic effect pigment.
  • the metallic effect pigments according to the invention are distinguished by exceptional resistance to aggressive and corrosive substances and media, which is demonstrated by the following examples.
  • the examples are merely illustrative of the invention and do not limit the scope of the invention.
  • the coating was carried out analogously to Example 7, except that 8.66 g of Desmodur Z 4470 BA in 20 g of butyl acetate were used as component B. 4 h after the addition of the amine components, 0.1 g of rofamine KD (Ecogreen Oleochemicals DHW Deutsche Hydrierwerke) was added to the reaction mixture for surface modification and stirred at room temperature for a further 2 hours.
  • rofamine KD Green Oleochemicals DHW Deutsche Hydrierwerke
  • the coating was carried out analogously to Example 7, except that 8.66 g of Desmodur Z 4470 BA in 20 g of butyl acetate were used as component B. 4 h after the addition of the amine components, 0.1 g of amino silicone Wacker L656 (non-reactive, amino-functional polydimethylsiloxane, Wacker Chemie, Germany) was added to the reaction mixture for surface modification and the mixture was stirred at room temperature for a further 2 hours.
  • amino silicone Wacker L656 non-reactive, amino-functional polydimethylsiloxane, Wacker Chemie, Germany
  • the PMMA plates were in each case dripped with 1 M sodium hydroxide solution, the drop sizes having a diameter of 12-15 mm. After application of the drops at room temperature (22 ° C) was allowed The soda lye drops act on the painted surfaces of the PMMA sheets for 14 hours, 1 hour, 2 hours, 4 hours and 8 hours. Thereafter, the drops were rinsed under running water and the PMMA plates were dried in air at room temperature (22 ° C) for 4 hours. Then, a visual evaluation of the drop areas on the painted PMMA plates was carried out according to the degree of graying.
  • the metallic effect pigments according to the invention also have a very good weather resistance and a very good dispersing behavior. Because of their excellent resistance to aggressive and corrosive substances and media, and not least because of their exceptional resistance to shear forces, the metallic effect pigments of the invention are very well suited for a wide variety of applications and paint or dyeing and coating systems.
  • the metallic effect pigments according to the invention of Examples 1 to 9 and Comparative Example 7 were mixed at a pigmentation level of 2.0% by weight with the powder coating 89/00060 (epoxy / polyester powder coating for interior applications of the company Tiger; Austria) were weighed into a ThermoMix 2 (Vorwerck). Added to this was 0.2% AluOxide C. The batch was then mixed at the parameters 4 min - stage 4. The dry-blend obtained was applied to thin iron sheets with a powder coating applicator (GEMA EasySelect at 100 kV and 100 ⁇ ) and then the sheets were baked at 180 ° C. for 10 min.
  • GEMA EasySelect at 100 kV and 100 ⁇
  • the pigment applications of Examples 6 to 9 according to the invention show a very good corrosion resistance in this powder coating system for interior applications. Compared to PCU 2000, this is all the more surprising since this pigment has a double protective coating of Si0 2 and a polyacrylate.
  • the pigments of Inventive Examples 6 to 9 showed excellent compatibility with the powder coating system used, which should also contribute to high chemical stability in addition to very good optical properties.

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

Abstract

L'invention concerne un pigment à effet métallique qui présente un noyau métallique en forme de lamelle recouvert d'au moins une couche polymère, caractérise en ce que la couche polymère est homogène et de type polyurée. Selon l'invention, la couche polymère est obtenue par une réaction d'addition entre un composant A et un composant B, le composant A contenant des molécules qui portent 1 à 20 groupes amino primaires et/ou secondaires et le composant B contenant des molécules qui portent 1 à 20 groupes isocyanate.
EP14730798.7A 2013-05-31 2014-06-02 Pigments à effet métallique résistant à la corrosion, procédé pour les fabriquer et leur utilisation Withdrawn EP3004253A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013009692 2013-05-31
PCT/EP2014/061402 WO2014191583A1 (fr) 2013-05-31 2014-06-02 Pigments à effet métallique résistant à la corrosion, procédé pour les fabriquer et leur utilisation

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EP3004253A1 true EP3004253A1 (fr) 2016-04-13

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US (1) US20160108245A1 (fr)
EP (1) EP3004253A1 (fr)
CN (1) CN105264020A (fr)
WO (1) WO2014191583A1 (fr)

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US4594271A (en) * 1984-12-24 1986-06-10 U.S. Philips Corporation Process for coating inorganic particles with condensating polymers
JPH07258581A (ja) * 1994-03-18 1995-10-09 Nippon Paint Co Ltd フォトクロミック性光輝顔料及びそれを含むコーティング組成物
US6191248B1 (en) * 1996-12-19 2001-02-20 The Boeing Company Coating
US7241502B2 (en) * 2001-09-14 2007-07-10 Merck Patentgesellschaft Moulded bodies consisting of core-shell particles
DE102004026955A1 (de) * 2004-06-01 2005-12-29 Eckart Gmbh & Co. Kg Wässrige Beschichtungszusammensetzung mit korrosionsstabilen dünnen deckenden Aluminiumpigmenten, Verfahren zu deren Herstellung und Verwendung derselben
MX2007002429A (es) * 2004-09-02 2007-05-04 Ppg Ind Ohio Inc Revestimiento de varios componentes que incluye una capa de revestimiento de poliurea.
DE102005037611A1 (de) * 2005-08-05 2007-02-15 Eckart Gmbh & Co. Kg Metalleffektpigmente mit anorganisch/organischer Mischschicht, Verfahren zur Herstellung solcher Metalleffektpigmente und deren Verwendung
CN101191023B (zh) * 2006-11-30 2012-06-27 中国石油化工股份有限公司 表面改性的固体微粒及其制备方法和应用
DE102007006820A1 (de) * 2007-02-07 2008-08-14 Eckart Gmbh & Co.Kg Chemikalienbeständige Metalleffektpigmente, Verfahren zu deren Herstellung und Verwendung derselben
JP2011216582A (ja) * 2010-03-31 2011-10-27 Fujifilm Corp 研磨方法、および研磨液
DE102011103882A1 (de) * 2011-03-25 2012-09-27 Eckart Gmbh Kupferhaltige Metallpigmente mit Metalloxidschicht und Kunststoffschicht, Verfahren zu deren Herstellung, Beschichtungsmittel und beschichteter Gegenstand

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Publication number Publication date
CN105264020A (zh) 2016-01-20
WO2014191583A1 (fr) 2014-12-04
US20160108245A1 (en) 2016-04-21

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