WO2020099151A1 - Structure de peinture à effets multicouche - Google Patents

Structure de peinture à effets multicouche Download PDF

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Publication number
WO2020099151A1
WO2020099151A1 PCT/EP2019/079964 EP2019079964W WO2020099151A1 WO 2020099151 A1 WO2020099151 A1 WO 2020099151A1 EP 2019079964 W EP2019079964 W EP 2019079964W WO 2020099151 A1 WO2020099151 A1 WO 2020099151A1
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Prior art keywords
layer
lacquer
effect
component
weight
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PCT/EP2019/079964
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German (de)
English (en)
Inventor
Marco CAPIZZI
Christoph Martin Schumacher
Original Assignee
Karl Bubenhofer Ag
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Publication of WO2020099151A1 publication Critical patent/WO2020099151A1/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
    • C09D5/03—Powdery paints
    • C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B05D5/063—Reflective effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • 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
    • 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
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/036—Stabilisers
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines

Definitions

  • the present invention relates to a multi-layer lacquer structure and lacquers for such structures and methods for producing such structures.
  • Stable, inexpensive effect surfaces are provided, which have a mirror-like look similar to polished metal surfaces or electroplated parts.
  • the proposed paint structure provides very weather-stable surfaces that meet the requirements of various automotive standards and various quality labels from the architectural field.
  • Metallically reflecting components of all kinds are mainly produced by means of chrome plating or by polishing metallic or rivet-coated materials.
  • chrome plating or by polishing metallic or rivet-coated materials.
  • the generation of uniform reflective properties is difficult, cost-intensive and under certain circumstances not possible at all (by polishing).
  • a multi-layer coating which comprises a base coating and a top coating, and is formed on an object such as a chemically treated steel plate by the object with a
  • a basecoat composition is coated which contains (a) a crosslinking agent which does not interfere with the hydrosilylation of a topcoat composition, and (b) a functional resin reactive with the crosslinking agent and then a topcoat composition which (c) (i) a mixture of a hydrosilyl group-containing compound and an alkenyl group-containing compound and / or (ii) a self-crosslinkable resin and (d) a catalytic amount of a hydrosilylation catalyst, followed by separate or simultaneous heat curing.
  • the top layer composition can contain functional groups (phosphorus and / or alkoxysilyl groups) or a compound containing functional groups. The proportion of effect pigment in this document is always at least 12 percent by weight.
  • US2015284585 describes a coating composition containing a carboxy-containing compound (A), a polyepoxide (B) and a specific polyol (C) having a number average molecular weight of 300 to 1,500, and a method for forming a multilayer coating film using the coating composition as a clear coating composition, the method comprising sequentially applying an aqueous first colored coating composition, an aqueous second colored coating composition and the clear coating composition to a substrate and simultaneously thermosetting the resulting coating films form the multilayer coating film.
  • A carboxy-containing compound
  • B polyepoxide
  • C specific polyol
  • W003033172 describes a two-part powder coating system in which the first part contains at least one film-forming polymer, at least one chromatic pigment and at least one metallic effect pigment and the second part is essentially free of chromatic pigment.
  • the first portion When the first portion is applied to at least one surface of a substrate to form a base powder coating and cured in the absence of the second portion, it can reflect incident white light in a color that is substantially independent of the color of the chromatic pigment.
  • the second portion can reflect incident white light in a color that is a function of the combined colors of the chromatic pigment and the metallic effect pigment.
  • At least a two-layer structure comprising the paint containing the effect agent and a protective top coat / protective coating is required.
  • the primary purpose of this is to avoid corrosion of the effect pigment, which lies essentially on the surface of the effect lacquer without protection, and secondly also to protect the lacquer matrix of this layer, which itself is sensitive or more sensitive to weather influences.
  • the use of top coats allows a great diversification in terms of color (combination with the mirror effect).
  • Effect pigments are based on metal platelets, preferably aluminum platelets, preferably in the order of magnitude (length) of 200 nm, 300 nm or 400 nm to approximately 5 micrometers, which have a form factor between 5: 1 and 1000: 1 (diameter: thickness). These particles are usually produced by special grinding processes (ball mills), which process the starting material (aluminum grit) into very fine particles with a plate-like geometry. The effect particles can be surface-modified with a material which causes or at least promotes the surface leafing effects from the paint during the drying or hardening process. Long-chain, aliphatic carboxylic acids such as stearic acid are often used.
  • the coating can be done relatively quickly.
  • toxic substances such as chromium (VI) acid (galvanic chrome plating) are eliminated and time-consuming post-treatment steps (such as polishing) are completely eliminated.
  • chromium (VI) acid galvanic chrome plating
  • time-consuming post-treatment steps such as polishing
  • almost all aluminum effect pigments used in the paint and varnish industry have been surface-modified in order to achieve inerting. This can be achieved by applying special oxide layers or inertizing organic components. In the present case, however, such a treatment would not allow nearly as brilliant, polish-like mirror properties. Only very thin
  • Coatings such as stearic acid, which are on a molecular scale, allow the described brilliance of the coating results.
  • oligomeric binder units based on acrylates, polyesters, polyurethanes or combinations thereof.
  • binders are made crosslinkable by adding a hardener (HA), which can itself be in the form of oligomeric binder units.
  • HA hardener
  • Systems such as 1, 12-dodecanedicarboxylic acid, (methylated) imino-melamine hardeners, isocyanate hardeners such as uretdione-blocked isocyanate hardeners, e-caprolactam-blocked isocyanate hardeners, epoxides such as bis (2,3-epoxypropyl) terephthalate,
  • the crosslinked (baked) lacquers have a polymer content (binder crosslinked with hardener) between 50 and 99% by weight.
  • This basic formulation principle can be used for powder coatings as well as liquid coatings.
  • Effect pigments are also added.
  • the addition takes place only after the extrusion by the Effect pigments are bound to the powder coating grains under a slight temperature influence (bonding process).
  • the direct extrusion of effect pigments would destroy them due to the strong shear forces.
  • the proportion of the effect pigments, based on the coating formulation is between 0.1 and 4% by weight. Particularly preferably between 0.5 and 1.2%.
  • the coating system can contain UV absorbers and / or HALS (hindering amine light stabilizer) to stabilize it against light and weather influences.
  • HALS and / or UV absorbers preferably in combination, range between 0.5 and 5% by weight, preferably 1-4% by weight.
  • the ratio of UV to HALS is in the range from 1: 10-5: 1, preferably in the range from 1: 3-l: l.
  • composition of a protective topcoat essentially consists of oligomeric binder units based on acrylates, polyesters, polyurethanes or combinations thereof.
  • binders are made crosslinkable by adding a hardener, which can also be in the form of oligomeric binder units.
  • a hardener which can also be in the form of oligomeric binder units.
  • Systems such as 1,12-dodecanedicarboxylic acid, (methylated) imino-melamine hardeners, isocyanate hardeners such as uretdione-blocked isocyanate hardeners, e-caprolactam-blocked isocyanate hardeners, epoxides such as bis (2,3-epoxypropyl) terephthalate, tris (oxiranylmethyl) benzene can be used as hardeners.
  • the crosslinked (burned-in) topcoats usually have a polymer content (binder crosslinked with hardener) of between 95 and 99%.
  • This basic formulation can be used for powder coatings as well as liquid coatings.
  • UV absorbers and HALS hindered amine light stabilizer
  • HALS hindered amine light stabilizer
  • the sensible additions for HALS and UV absorbers range between 0.5% and 6% by weight, preferably between 1 and 5% by weight. This addition protects both the topcoat itself and the underlying paint layers from harmful light effects. The way it works is like sunglasses, which is placed over this lacquer. Harmful UV radiation is absorbed by the UV absorber.
  • the HALS absorber on the other hand, can only work in the paint itself, since it can neutralize the radicals that come into contact with it.
  • the ratio of UV to HALS is in the range from 1: 10-5: 1, preferably in the range from 1: 3-1: 1.
  • surface-active substances which are usually based on acrylates, can be added to the system as additives. These enable a uniform surface tension which leads to a perfect surface (no craters and other wetting problems). Furthermore, certain pigments or dyes can be added to the paint in a deeply concentrated amount, these give the paint structure a color nuance. Micronized waxes can also be used as additives to improve the surface of the lacquer. Among other things, these make the paint less sensitive to the effects of scratching.
  • the task of a primer essentially includes the appropriate preparation of a substrate for the subsequent painting steps.
  • the primer often has better adhesive properties on the metal workpiece, for example, smoothes its surface and also compensates for imperfections (unevenness, protruding metal pimples, etc.).
  • the primer should offer good adhesion conditions for layers of paint applied to it.
  • the primer often protects the metal workpiece, for example, against corrosion. The following is described a possible powder coating primer.
  • primers have a polymer component (hardened paint film, i.e. the binder cross-linked with hardener) between 50 and 80%.
  • oligomeric bisphenol A-based resins with glass transition temperatures of 40 to 75 ° C. are used. These can have epoxy equivalent weights between 500 g / eq and 1400 g / eq.
  • the lacquer is typically cured using cyanamides such as dicyandiamide, guanidines such as l - (o-tolyl) biguanide or, more rarely, phenolic hardeners.
  • cyanamides such as dicyandiamide
  • guanidines such as l - (o-tolyl) biguanide or, more rarely, phenolic hardeners.
  • a crosslinking of the epoxy resin with itself is also conceivable, often not practical in practice due to the longer curing times.
  • the curing reaction can be accelerated if necessary using catalysts, for example from the group of imidazoles.
  • additives or fillers can be added to the formulation, e.g. Pigments, fillers such as chalk, barium sulfate or aluminum hydroxide.
  • the primer should not contain excessive amounts of polyolefin waxes ( ⁇ 0.5%). These are added to the system for resistance to scratching and to improve extrusion performance.
  • Epoxy primers as described above offer excellent adhesion conditions for subsequent layers of paint. The protective effect of the effect varnish works particularly well under the following conditions:
  • Topcoat and effect paint should work well together. Good interlayer adhesion is important. Experience has shown that this is particularly good when an epoxy-polyester hardener / binder combination (base of the effect lacquer) meets a polyester-containing acrylate topcoat that is cross-linked with an imino-melamine hardener. Acrylates per se have very good light and weather stability and can be significantly improved again by adding UV and HALS absorbers. It is primarily about preventing the light-related and weather-related degradation of the top coat, because this leads to a massive increase in the water permeability of the paint. Water vapor is very aggressive towards the effect pigment and can lead to graying and delamination of the layers of paint.
  • the topcoat should therefore be applied in a sufficient layer thickness in the range of 0.01-0.2 mm, preferably 0.02-0.1 mm, in order to keep the diffusion barrier high and on the other hand, to enhance the effect of the UV absorber.
  • Another basic requirement is the overall high diffusion barrier of the top coat against water vapor. This can be increased by a comparatively high cross-linking density. However, the physical properties of the binder are decisive here.
  • the present invention thus relates to a multilayer paint structure, at least indirectly on a substrate (ie directly on the substrate or indirectly, ie with one or more layers, for example primer layers, between the substrate and the effect lacquer layer), at least one effect lacquer layer and on top of that Side facing away from the substrate at least one cover layer,
  • oligomeric binder selected from the group consisting of:
  • (BE) 0.1-4 wt .-% effect pigment based on metal flakes, which are not inert, and in particular without an oxide layer;
  • cover layer (14, 16, 17) consists of the following components:
  • oligomeric binder selected from the group consisting of:
  • component (AD) - (ED) add up to 100 percent by weight of the formulation of the top layer.
  • component (AE) of the effect lacquer layer acrylate resins containing glycidyl groups (e.g.
  • Methacrylate-based hydroxylated acrylate resins, carboxylated polyester resins, hydroxylated polyester resins.
  • the systems of component (AE) typically have a glass transition temperature of less than 75 ° C, preferably in the range of 40-70 ° C.
  • the systems of component (AE) further preferably have an OH value in the range of 20-40 mg KOH / g when they are hydroxylated and an acid number in the range of 10-180 mgKOH / g when they are carboxylated.
  • component (AD) of the cover layer glycidyl group-containing acrylate resins (e.g. methacrylate-based), hydroxylated acrylate resins, carboxylated polyester resins, hydroxylated polyester resins, polyester-containing acrylate resins.
  • glycidyl group-containing acrylate resins e.g. methacrylate-based
  • hydroxylated acrylate resins carboxylated polyester resins
  • hydroxylated polyester resins hydroxylated polyester resins
  • polyester-containing acrylate resins glycidyl group-containing acrylate resins (e.g. methacrylate-based), hydroxylated acrylate resins, carboxylated polyester resins, hydroxylated polyester resins, polyester-containing acrylate resins.
  • the systems of component (AD) typically have a glass transition temperature of less than 75 ° C, preferably in the range of 40-70 ° C.
  • the systems of component (AD) further preferably have an OH value in the range of 20-200 mg KOH / g when they are hydroxylated or in the form of polyester-containing acrylate resin, and when they are carboxylated an acid number in the range of 10-180 mgKOH / G.
  • a first preferred embodiment of such a lacquer structure is characterized in that component (AE) of the effect lacquer layer contains polyester as the oligomeric binder or is formed exclusively from polyester, and contains an epoxy resin based in particular on bisphenol-A, preferably as the only hardener, as hardener,
  • that component (AD) of the top layer contains polyester-containing acrylate as the oligomeric binder or is formed exclusively from polyester-containing acrylate, and contains a preferably methylated imino-melamine hardener, preferably as the only hardener, as the hardener.
  • the effect lacquer layer and the top layer can be arranged directly adjacent to one another, and the top layer can form the exposed surface.
  • a primer layer can be arranged between the substrate and the effect lacquer layer.
  • Another preferred embodiment is characterized in that the preferably single effect lacquer layer has a thickness in the range of 0.01-0.3 mm, preferably in the range of 0.05-0.2 mm.
  • a further preferred embodiment is characterized in that the preferably single cover layer has a thickness in the range from 0.01 to 0.2 mm, preferably in the range from 0.02 to 0.1 mm.
  • a further preferred embodiment is characterized in that an optionally present primer layer has a thickness in the range from 0.03 to 0.3 mm, preferably in the range from 0.06 to 0.2 mm.
  • the hardener within component (AE) of the effect lacquer layer and / or within component (AD) of the top layer can be selected from the following group: 1,12-dodecanedicarboxylic acid, (methylated) imino-melamine hardener, isocyanate hardener such as uretdione-blocked isocyanate hardener, e -Caprolactam-blocked isocyanate hardener, epoxides such as bis (2,3-epoxypropyl) terephthalate, tris (oxiranylmethyl) benzene-l, 2,4-tricarboxylate, l, 3,5-tris (oxiran-2-ylmethyl) -l, 3 , 5-triazinan-2,4,6-trione, bisphenol-A based, or combinations thereof.
  • the inorganic fillers within component (DE) of the effect lacquer layer and / or within component (DD) of the top layer can be selected from the group consisting of: fillers, in surface-treated or untreated form, selected from the group consisting of: talc, mica , Silicate, such as in particular iron aluminum silicate and / or sodium aluminum silicate particles, aluminum hydroxide, quartz, quartz powder, titanium dioxide, wollastonite, kaolin, silicas, in particular amorphous silicas, ground or precipitated calcium carbonate, magnesium carbonate, magnesium hydroxide, chalk, lime, feldspar, mica, ground or precipitated barium sulfate, barium titanate, zinc sulfide, glass spheres, in particular solid or hollow glass spheres, ground glass, in particular ground glass fibers, glass flakes, glass flakes, permanently magnetic or magnetizable metal compounds and / or alloys, inorganic pigments, such as in particular iron oxide, iron manganese oxide, metal powder he, in particular iron
  • the additives within the component (EE) of the effect lacquer layer and / or within the Component (ED) of the cover layer can be selected from the following group: surface-active substances, in particular based on acrylates; Waxes, in particular micronized waxes, pigments other than effect pigments, antistatic agents or combinations thereof.
  • the stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer as HALS can be selected from the following group: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, or combinations thereof, and / or selected as a UV stabilizer from the following group: 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -
  • the stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer can be formed as a mixture of an HALS and a UV stabilizer, the ratio of UV to HALS stabilizer preferably being in the range of 1:10. 5: 1, preferably in the range of 1: 3-l: 1.
  • the effect pigment of component (BE) can consist of aluminum flakes free of oxide layer, optionally coated with a saturated fatty acid, preferably stearic acid, these having an average order of magnitude of 200 nm, 300 nm or 400 nm to about 5 micrometers, and preferably a form factor between 5: 1 and 1000: 1 (diameter: thickness).
  • a saturated fatty acid preferably stearic acid
  • the proportion of component (CD) in the cover layer can be in the range of 1-4.5% by weight, preferably in the range of 2-4.5% by weight.
  • the proportion of component (CE) in the effect lacquer layer can be in the range from 0.5-4.5% by weight, preferably in the range from 1-4.5% by weight.
  • the top layer and / or the effect lacquer layer can have been produced on the basis of a powder lacquer.
  • the present invention further relates to a component with a lacquer structure as described above, preferably a metallic component, particularly preferably from the automotive sector, including body components, rims, moldings, switches, transitions, holders, handles, closures, covers, mirrors and combinations of such components .
  • a kit-of-parts of an effect lacquer and an effect lacquer for producing a lacquer structure as described above particularly preferably as a liquid lacquer or powder lacquer.
  • the present invention relates to a method for producing a lacquer structure as described above, which is characterized in that the effect lacquer is applied and cured in a first step, if appropriate after previously producing a primer layer, and in a second step the top layer is applied and cured, the curing, in the case of powder coating, particularly preferably at a temperature of more than 100 ° C. and over a period of at least 10 minutes.
  • Fig. 1 is a schematic representation of the generation of a paint surface
  • Powder coating (top left), which is mixed with a special effect pigment, or a liquid coating (top right) with the same effect pigment is applied to a substrate and melts / hardens or dries / hardens thereon; with a suitable amount of effect pigment, a metal-polished surface is formed (bottom left), while the polish effect is not properly pronounced with the wrong amount of effect pigment (bottom right);
  • FIG. 2 shows a schematic representation of a paint structure with a primer, which may or may not necessarily be present, the effect paint layer with the floating effect pigment and a protective cover layer;
  • Top coats (examples 5 - 7 from left to right, absorber quantity varies) on the same effect lacquer after 3000 hours of rapid weathering test in accordance with DIN EN ISO 16474-2; there are massive differences in the protective effect against the pigment and also clear differences in the degree of gloss of the topcoat;
  • Fig. 6 Results of three different varnishes in a cross-cut test with subsequent tape tear according to DIN EN ISO 2409 after 1000 hours of rapid weathering according to DIN EN ISO 16474-2; the oxidation of the effect pigment leads, in addition to visual losses, to strong detoxification phenomena; and
  • FIG. 7 shows a lacquer structure which is particularly important for multi-colored metal rims; priming can, but does not necessarily have to be done; a further protective clear coat, transparent or colored, is applied to the effect paint with floating or non-floating pigments; this is in turn covered with a colored or opaque lacquer layer; For design reasons, this can be removed in places (by twisting, laser etching or other processes); at the end the painting is done with a protective top coat, transparent or colored.
  • FIG. 1 shows schematically how a multilayer structure comprising an effect lacquer layer and a top layer arranged above it can be formed on a substrate 5.
  • the left branch shows at the top how a raw powder coating 1, which has particles 2 with effect coating particles 3 arranged on the surface, is applied to the substrate 5.
  • the raw powder coating layer 4 on the substrate is shown below. If this layer is exposed to a suitable elevated temperature for a suitable time period t. H. If heat is supplied, the hardening process 9 shown in the middle begins. As a rule, the flake-like effect paint particles migrate to the surface of the corresponding layer.
  • a high-gloss layer forms, as shown at the bottom left.
  • the particles 3 are oriented on the surface and form an effect lacquer layer 10 with a metallic polished effect, because the particles are arranged next to one another parallel to the surface plane.
  • oxidizable metal particles are used as the effect lacquer layer particles, there is a risk if no further layer is arranged on them that the particles arranged on the surface oxidize and the gloss effect is gradually lost.
  • a situation is schematically shown at the bottom right, in which too much effect paint pigment was contained in the formulation.
  • the particles then also migrate to the surface, but prevent each other from adopting a plane-parallel position, so that a sufficient gloss effect cannot occur.
  • FIG. 1 shows above how a liquid lacquer 6 is applied to a substrate 5, so that a raw liquid lacquer layer 8 is formed.
  • the layer is hardened either by drying or by drying and applying heat.
  • a further cover layer is applied to such a layer.
  • FIG. 1 Another possible multilayer structure is shown schematically in FIG.
  • a primer layer 12 is initially arranged on the substrate 5.
  • the effect lacquer layer 10 is then arranged on this primer layer 12.
  • the primer layer 12 is particularly advantageous if the substrate consists of metal and the adhesion between the effect lacquer layer and the substrate is to be improved.
  • a top layer 14 is now additionally arranged on the effect lacquer layer 10, on the surface of which the effect lacquer particles are to a certain extent concentrated and aligned in a layer 13.
  • the cover layer then exposes the exposed surface 15 of the final component.
  • Figure 7 shows an alternative layer structure.
  • a primer 12 is initially provided on the substrate 5, followed by the effect lacquer layer 10, in which this time the pigments are not concentrated and oriented to the same extent on the surface, but nevertheless have a metallic surface. Appearance is guaranteed.
  • a first top layer in the form of a clear lacquer layer 16 another top layer in the form of an opaque lacquer layer 17, which can be pigmented, for example, and then at the end is the final covering layer 14.
  • the pigmented lacquer layer 17 can have cutouts 18 in order to provide certain optical effects.
  • epoxy resin BM bisphenol-A based, glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals
  • 70g epoxy resin leveling agent masterbatch AD contains an acrylate-based, surface-active additive, epoxide equivalent weight approx. 800g / eq, Jana ) were mixed with a stoichiometric amount of epoxy hardener HA (l- (o-tolyl) biguanide, AlzChem).
  • epoxy hardener HA l- (o-tolyl) biguanide, AlzChem
  • the homogeneously mixed mixture was extruded at about 110 ° C. using a single-screw extruder (PLK-46, Buss).
  • the extrudate was then ground with an impact mill with sifter (Hosokawa Alpine) to form an applicable powder coating.
  • Polyolefin wax mixed in AD (dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.
  • the homogeneously mixed mixture was extruded with a single-shaft extruder (PLK-46, Buss) at approx. 120 ° C and then with an impact mill with classifier (Hosokawa Alpine) ground to powder.
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5pm, Sun Chemical) under the influence of light heat (just above the glass transition temperature of the powder), which leads to the effect pigment particles sticking to the powder grains (so-called bonding process, see 3) to prevent subsequent separation of the effect pigment, the proportion of the amount of the effect pigment based on the 1000 g specified above being 0.666% by weight.
  • the result was an applicable powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • Tris oxiranylmethyl
  • 2,4-tricarboxylate HA Heuntsman
  • 10 g of acrylate-based leveling agent AD on silicate carrier, Altana
  • 3 g of micronized polyolefin wax AD dropping point approx. 110 ° C., Clariant
  • 7 g of pearl black PI Oprion Engineered Carbons
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • Polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) added. In total, this resulted in a mass of 1000 g.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.5% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.8% by weight.
  • the result was an applicable powder coating that forms mirror-like surfaces during the stoving process.
  • acrylate-based leveling agent AD on silicate carrier, Altana
  • 5g 2,2 '- (6-anilino- [1,3,5] triazine-2,4-diyl) -bis-phenol UV Clariant
  • 3g micronized polyolefin wax mixed in AD Drop point approx. 110 ° C, Clariant
  • the homogeneously mixed mixture was extruded at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the above-mentioned 1000 g being 0.7% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • hydroxylated polyester resin BM (TG approx. 51 ° C, OH value 85 mg KOH / g, DSM) was mixed with a stoichiometric amount of uretdione-blocked isocyanate hardener HA (TG approx. 48 ° C, NCO content approx. 13.5% , Covestro) mixed.
  • the homogeneously mixed mixture was extruded with a single-screw extruder (PLK-46, Buss) at approx. 130 ° C and then ground to powder with an impact mill with sifter (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 m 2, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g given above being 0.6% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • DSM was based on 239g epoxy resin HA (bisphenol-A,
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 m 2, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g given above being 0.7% by weight.
  • the result was an application-like powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment being 0.5% by weight based on the abovementioned 1000 g.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 ml, Sun Chemical) under the influence of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.6% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • DSM was based on 580g epoxy resin HA (bisphenol-A,
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of ⁇ 5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.666% by weight.
  • the result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.
  • the homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). In total, this resulted in a mass of 1000 g.
  • polyester resin leveling agent masterbatch AD contains an acrylate-based, surface-active additive, OH value 45 mg KOH / g, Allnex) with a stoichiometric amount of e-caprolactam-blocked isocyanate hardener HA (TG approx. 49 ° C, NCO content approx. 10.5%, Evonik) mixed.
  • the homogeneously mixed mixture was extruded twice at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and was then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • the baking process after application gives smooth-running coatings with high transparency, good weather resistance, a glossy surface (> 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties.
  • polyester resin adhesive masterbatch AD (contains an acrylate-based, surface-active additive, acid number 35 mg KOH / g, Allnex), 20 g bis (2,2,6,6- tetramethyl-4-piperidyl) sebacate HALS (BASF), 10g 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF), 3g micronized polyolefin wax AD (dropping point approx . 1 10 ° C, Clariant) and 0.02g pearl black PI (Orion Engineered Carbons) mixed. In total, this resulted in a mass of 1000 g.
  • BASF bis (2,2,6,6- tetramethyl-4-piperidyl) sebacate HALS
  • BASF 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol UV
  • BASF 2-tert-butyl-6- (5-ch
  • the homogeneously mixed mixture was extruded twice at approx. 120 ° C. using a single-screw extruder (PLK-46, Buss) and was then ground to powder using an impact mill with classifier (Hosokawa Alpine).
  • a single-screw extruder PK-46, Buss
  • an impact mill with classifier Hesokawa Alpine
  • slightly dark tinted, smooth-running coatings with good weather resistance a glossy surface (> 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties are obtained.
  • the homogeneously mixed mixture was extruded twice at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with sifter (Hosokawa Alpine).
  • the baking process after application gives smooth-running coatings with high transparency, very good weather resistance, a glossy surface (> 95 gloss units at a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties.
  • the homogeneously mixed mixture was extruded twice at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with sifter (Hosokawa Alpine).
  • the baking process after application gives smooth-running coatings with high transparency, very good weather resistance, a glossy surface (> 95 gloss units at a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties.
  • polyester-containing acrylate resin in butyl acetate BM (77%, OH value 150mg KOH / g, Synthopol) was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 155g White Spirit LM (Exxon Mobil) mixed using a dissolver.
  • polyester-containing acrylate resin in butyl acetate BM (77%, OH value 150mg KOH / g, Synthopol) was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 150g White Spirit LM (Exxon Mobil) mixed using a dissolver.
  • KOH / g, Synthopol was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 120g White Spirit LM (Exxon Mobil) using a dissolver.
  • the resistance to weathering (degree of gloss, cloudiness of the top coat and integrity of the mirror effect) is checked using the accelerated process of the xenon arc lamp test (in accordance with DIN EN ISO 16474-2 or similar to various automotive standards).
  • the entire paint structure is applied to sample panels or directly to coated components.
  • the structure is then artificially weathered for a period to be defined. Alternatively, outdoor exposure can also be carried out.
  • With a suitable choice and layer thickness of the topcoat 3000 hours and more can be achieved in the xenon arc lamp test according to DIN EN ISO 16474-2 without loss of gloss and corrosion of the effect pigments (Fig. 5).
  • the adhesion of the top coat to the effect paint is also important. This can be checked before and after weathering by means of a cross cut with adhesive tape tear off according to DIN EN ISO 2409. A suitable top coat in sufficient layer thickness shows good adhesion to the substrate even after advanced weathering (Fig. 6 right).
  • the layers were each applied to a metal substrate (aluminum) with the following layer thicknesses:
  • Top layer 0.03 mm.
  • the lacquers were applied in the form of powder lacquers and in each case cured at a temperature of 180 ° C. over a period of 15 minutes. Liquid topcoats were cured at 120 ° C. for 10 minutes.
  • binder effect paint particles can functional groups

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  • Engineering & Computer Science (AREA)
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Abstract

Structure de peinture multicouche comprenant, au moins indirectement sur un substrat (5), une couche de peinture à effets (10) et sur le côté de celle-ci opposé au substrat (5) une couche de revêtement (14, 16, 17), la couche de peinture à effets étant composée des composants suivants : (AE) 50 à 99,9 % en poids d'agent liant oligomère choisi dans le groupe composé de : acrylate, polyester, polyuréthane ou une combinaison de ces systèmes avec un agent durcissant ; (BE) 0,1 à 4 % en poids de pigment à effets basé sur des flocons métalliques ; (CE) 0 à 5 % en poids de stabilisation aux UV et/ou stabilisation HALS ; (DE) 0 à 30 % en poids de charges particulaires inorganiques ; (EE) 0 à 10 % en poids d'additifs, les composants (AE) à (EE) se complétant à 100 % en poids de la formulation de la couche de peinture à effets ; et la couche de revêtement se composant des composants suivants : (AD) 90 à 99,5 % en poids d'agent liant oligomère choisi dans le groupe composé de : acrylate, polyester, polyuréthane ou une combinaison de ces systèmes avec un agent durcissant ; (CD) 0,5 à 5 % en poids de stabilisation aux UV et/ou stabilisation HALS ; (DD) 0 à 5 % en poids de charges particulaires inorganiques ; (ED) 0 à 10 % en poids d'additifs, les composants (AD) à (ED) se complétant à 100 % en poids de la formulation de la couche de revêtement.
PCT/EP2019/079964 2018-11-16 2019-11-01 Structure de peinture à effets multicouche WO2020099151A1 (fr)

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CN112246569A (zh) * 2020-09-07 2021-01-22 江苏信轮美合金发展有限公司 一种自行车铝圈表面处理方法
WO2021030197A1 (fr) * 2019-08-09 2021-02-18 Ppg Industries Ohio, Inc. Compositions, couches et systèmes de revêtement pour transmission radar et leurs procédés de fabrication et d'utilisation
CN116376438A (zh) * 2023-02-28 2023-07-04 滁州金桥德克新材料有限公司 一种应用于镀锌板的uv固化涂层组合物
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US11809933B2 (en) 2018-11-13 2023-11-07 Ppg Industries Ohio, Inc. Method of detecting a concealed pattern
US11932928B2 (en) 2018-05-15 2024-03-19 Novelis Inc. High strength 6xxx and 7xxx aluminum alloys and methods of making the same
US12001034B2 (en) 2019-01-07 2024-06-04 Ppg Industries Ohio, Inc. Near infrared control coating, articles formed therefrom, and methods of making the same
US12050950B2 (en) 2023-07-28 2024-07-30 Ppg Industries Ohio, Inc. Method of detecting a concealed pattern

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CN112246569B (zh) * 2020-09-07 2023-03-21 江苏信轮美合金发展有限公司 一种自行车铝圈表面处理方法
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