WO2009039842A2 - Substrat en matière plastique comprenant des pigments métalliques, son procédé de production, et pigments métalliques anticorrosion et leur procédé de production - Google Patents

Substrat en matière plastique comprenant des pigments métalliques, son procédé de production, et pigments métalliques anticorrosion et leur procédé de production Download PDF

Info

Publication number
WO2009039842A2
WO2009039842A2 PCT/DE2008/001580 DE2008001580W WO2009039842A2 WO 2009039842 A2 WO2009039842 A2 WO 2009039842A2 DE 2008001580 W DE2008001580 W DE 2008001580W WO 2009039842 A2 WO2009039842 A2 WO 2009039842A2
Authority
WO
WIPO (PCT)
Prior art keywords
metal
component
layer
oxide
pigments
Prior art date
Application number
PCT/DE2008/001580
Other languages
German (de)
English (en)
Other versions
WO2009039842A3 (fr
Inventor
Matthias Koch
Original Assignee
Ropal Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ropal Ag filed Critical Ropal Ag
Publication of WO2009039842A2 publication Critical patent/WO2009039842A2/fr
Publication of WO2009039842A3 publication Critical patent/WO2009039842A3/fr

Links

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
    • C09C1/62—Metallic pigments or fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09C1/62—Metallic pigments or fillers
    • C09C1/627—Copper
    • 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
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • 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
    • C09C1/66—Copper alloys, e.g. bronze
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • Plastic substrate containing metal pigments and process for their preparation and corrosion-protected metal pigments and process for their preparation
  • the present invention relates to plastic substrates containing metal pigments, to processes for their preparation and to corrosion-protected metal pigments and to processes for their preparation.
  • metal pigments for example aluminum pigments
  • a variant of the production of such metal pigments consists of initially vapor-depositing a metal on a support layer, for example made of polyethylene terephthalate (PET), which is provided with a release layer, also called a release coat, by means of physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the thin metal layer freed from the carrier layer with a solvent is then comminuted mechanically or by ultrasound to obtain the metal pigments.
  • PVD pigments are also called PVD pigments for short.
  • PVD pigments are known for their tendency to corrosion.
  • Al pigments can be protected against corrosion by coating aluminum particles with molybdic acid, so that a lasting color effect with permanent resistance to moisture is obtained.
  • Metal pigments are often used in plastic moldings, which are to be equipped with a special metallic gloss effect. In this case, the metal pigments are often already incorporated into the intended for the production of a plastic product granules.
  • plastic moldings reinforced metal components completely or partially displace, even for outdoor applications, such as the automobile, plastic moldings with shiny metallic surfaces to be resistant to external influences, for example, to be weathered.
  • the metallic gloss effect may also be impaired over an extended period of time, not even negligibly, since this would directly and substantially impair the appreciation by the user or purchaser.
  • elaborate topcoat layers are often applied.
  • the invention was based on the object to make available metal pigments, in particular aluminum pigments, are characterized by a very good corrosion protection, which also can be achieved procedurally unaufwendig without raising problems in terms of disposal or environmental protection.
  • Another object of the present invention was to make available plastic moldings with shiny metallic surfaces which are reliably protected against corrosion or other optical impairments due to aging phenomena or external influences.
  • the vapor deposition or application is preferably carried out by means of Physical Vapor Deposition (PVD) coating, vapor deposition by means of an electron beam evaporator, vapor deposition by means of a resistance evaporator, induction evaporation, ARC evaporation and / or sputtering, preferably in a high vacuum.
  • PVD Physical Vapor Deposition
  • the carrier layer preferably represents a carrier film, for example in the form of a plastic carrier film or layer.
  • Suitable plastic carrier films or layers are based, for example, on thermoplastic, thermoset or elastomeric plastics.
  • polytetrafluoroethylene (Teflon), polyethylene terephthalate (PET), polystyrene, vinylaromatic (co) polymers, such as ABS, ASA or SAN, polyphenylene ethers (PPE), polyamides, poly (meth), are suitable materials for the plastic film or layer ) called acrylates, polyoxymethylene and polycarbonates.
  • a release film has ("release coat").
  • the release film can in a suitable embodiment, for example, on polyvinyl chloride, polystyrene, chlorinated rubber, Acrylonitrile-butadiene-styrene copolymers, nitrocellulose, cellophane, methyl methacrylate, acrylic copolymers, fatty acids, waxes, gels, gums and mixtures thereof.
  • the first metal used is preferably aluminum, gold, silver, lead, vanadium, chromium, manganese, magnesium, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, zirconium, stainless steel or Alloys of these metals, in particular brass or bronze.
  • first i. Coating metals brass, bronze, magnesium, titanium or aluminum or magnesium, titanium or aluminum alloys, in particular aluminum or aluminum alloys.
  • the thickness of the metal layer obtained according to method step b) is in the range of 5 nm to 10 .mu.m, preferably in the range of 20 nm to 5 .mu.m and particularly preferably in the range of 30 nm to 1 .mu.m.
  • coating thicknesses in the range of 30 nm to 500 nm or 30 nm to 300 nm are adjustable or available.
  • the compounds of the second metal mentioned are introduced into this layer. Accordingly, these compounds are present in this layer, preferably essentially over the entire thickness and in particular uniformly distributed. It should be understood that compounds of the second metal, as present in the aqueous system, upon contact with the metal layer and / or upon penetration or presence in the metal layer are listed in a compound as above (and also in claim 1) , converts.
  • step c at least one, in particular transparent, cover layer, in particular topcoat layer, and / or at least one glaze layer is / are applied after step c). Furthermore, it can be provided that, after the application of a metal layer according to step b) and / or after step c), the metal layer is subjected to a rinsing step with, in particular demineralized, water.
  • aqueous treatment system there is an acid, an oxide, oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide or salt of the second metal.
  • Zirconium oxides, titanium oxides or hafnium oxides are particularly preferably used here as oxides, zirconium oxyfluorides, titanium oxyfluorides or hafnium oxyfluorides as oxyfluorides, fluoric acid, fluorotitanic acid or fluorophosphonic acid as acids, and fluorozirconates, fluorotanates or fluorohydrides as salts.
  • the aqueous systems may further contain fatty acids, fatty alcohols and / or in particular fatty amines or any mixtures thereof.
  • the fatty amines may also be in the form of their ammonium salts.
  • Fat amines according to the present invention thus also include the corresponding Ammoniumsaize.
  • recourse is preferably made to compounds with saturated fatty alkyl chains.
  • the length of the linear fatty alkyl chains is preferably in the range of C 8 to C 24 .
  • Preferred fatty amines or the corresponding ammonium compounds are based on a C 12 , C 14 , C 16 or C 18 alkyl radical.
  • Suitable fatty acids include, for example, capric acid.
  • suitable aqueous systems may also be treated with polyoxyalkylene ethers, e.g. Polyoxyalkylenglycolethern, in particular polyoxyethylene glycol ethers, polypropylene glycol ethers and mixtures thereof, be added. This can be used on all common, commercially available glycol ethers.
  • polyoxyalkylene ethers e.g. Polyoxyalkylenglycolethern, in particular polyoxyethylene glycol ethers, polypropylene glycol ethers and mixtures thereof. This can be used on all common, commercially available glycol ethers.
  • the detached metal layer is usually comminuted mechanically and / or by means of ultrasound.
  • so-called PVD pigments are well known to the person skilled in the art and can be found, for example, in US Pat. No. 4,321,087, to which reference is expressly made.
  • the metal layer on the carrier layer according to step b) can be made of known vapor deposition and sputtering process.
  • These are, for example, the method of Physical Vapor Deposition (PVD) coating, the vapor deposition by means of an electron beam evaporator, the evaporation by means of a resistance evaporator, the induction evaporation, the ARC evaporation and the sputtering, respectively preferably in a high vacuum.
  • PVD Physical Vapor Deposition
  • a sputtering process Preference is given to using the Physical Vapor Deposition Coating (PVD) process and a sputtering process.
  • PVD Physical Vapor Deposition Coating
  • resistance-heated metal spiral or metal boat evaporators are used, tungsten filaments of the most varied shapes being preferred.
  • an evaporator In the PVD process, in general, an evaporator is equipped with spirals, which can be clamped on mutually insulated evaporator rails. In each helix is preferably given a precisely determined amount of first metal, noble metal or first metal alloy.
  • the evaporation can be started by turning on the power supply, which causes the evaporator bars to anneal the filament. The solid metal begins to melt and completely wets the most twisted coils. By further supply of energy, the liquid metal is transferred into the gas phase, so that it can be deposited on the substrate to be coated.
  • Evaporation from metal boats proceeds in a similar way.
  • the evaporator equipment is in principle identical, but boats are usually used from refractory metal sheets, such as tungsten, tantalum or molybdenum boat.
  • a cathode is arranged in an evacuated container, which is connected to the negative pole of a power supply.
  • the coating material that is sputtered is mounted immediately in front of the cathode and the substrates to be coated are placed opposite to the coating material to be sputtered.
  • argon can be passed as a process gas through the container, which finally also has an anode which is connected to the positive pole of a power supply. is bound. After the container has been pre-evacuated, the cathode and anode are connected to the power supply.
  • the targeted and controlled intake of argon significantly reduces the mean free path of the charge carriers.
  • Argon atoms are ionized in the electric field between the cathode and the anode.
  • the positively charged particles are accelerated with high energy to the negatively charged cathode.
  • this Upon impact and by particle collisions in the coating material, this is converted into the vapor phase, accelerated with high energy in the free space and then condenses on the substrates to be coated.
  • vapor deposition methods which can be used in the method according to the invention are carried out using an electrode beam evaporation, resistance evaporation, induction evaporation and / or evaporation with the aid of a thermal, non-stationary arc (ARC evaporation).
  • ARC evaporation a thermal, non-stationary arc
  • the metal layer Before treating the metal layer according to step c) with an aqueous system containing at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or Salt of a second metal, the metal layer with water, preferably deionized water, wetted or rinsed.
  • the water used for this purpose has a conductance of less than 100 mS / cm, preferably less than 50 mS / cm and particularly preferably less than 35 mS / cm.
  • the aqueous system may e.g. in the form of a solution, a suspension or an emulsion.
  • the aqueous system is used as a solution, i. the abovementioned compounds, salts and / or acids are present substantially dissolved at least before the application.
  • the metallic protective or composite layer particularly preferably contains at least one oxide, double oxide, oxide hydrate and / or oxyhalide, in particular based on one element of group 4 of the Periodic Table, in particular zirconium fluorides, zirconium oxyfluorides and / or zirconium oxides. Zirconia is particularly preferred. Suitable double oxides are, for example, aluminum / zirconium oxides. Furthermore, according to a further embodiment, it is preferable for a second metal or a second metal alloy, in particular based on zirconium, titanium and / or hafnium, to be oxide-bound in the composite layer. Without being bound by any theory, it is presently believed that the compounds of the second metal present in the aqueous system, for example as acid or salt, in the metallic protective layer are converted into an oxide, double oxide, oxide hydrate or oxyhalide ,
  • Suitable acids which are based on a group 4 element include, for example, hydrofluorocarboxylic acid (H 2 ZrF 6 ), fluorotitanic acid (H 2 TiF 6 ) and fluoro hafnic acid (H 2 HfF 6 ). Of course, mixtures of different acids can be used. These fluoric acids can be used both in the pure state and also containing impurities, for example fluoric acid. In the aqueous systems, the acids may be present, for example, in amounts of up to 5% by weight, in particular of up to 3.5% by weight, based on the total weight of the aqueous system.
  • Fluoric acid can be used in the aqueous systems, e.g. in amounts ranging from 0.1 to 3% by weight, may also be present.
  • ammonium zirconium carbonate which is obtainable, for example, from the company Magnesium Electron Inc. under the trade name Bacote 20 ((NH 4 ) 2 [Zr (OH) 2 (COs) 2 ] -n H 2 O)
  • alkali metal and ammonium fluorozirconates for example Na 2 ZrF 6 , KZrF 6 , (NH 4 ) ZrF 6 , as well as zirconium nitrates, zirconium oxynitrates, zirconium carbonates, zirconium fluorides or zirconium sulfate.
  • the compounds based on the 4th group can be used as such or in any mixture with each other.
  • aqueous systems in addition to the compounds mentioned or mixtures thereof further ingredients.
  • Nitric acid, fluoric acid, phosphoric acid, salts of said acids, Ammoniumbiflu- orid and ammonium sulfate into consideration.
  • a suitable titanium salt provides e.g. Ammoniumti- tanfiuorid.
  • the aqueous system preferably contains fluoride ions in free and / or complexed form.
  • Suitable complexed fluoride ions include fluoroborate salts and acids as well as alkali metal and ammonium bifluorides.
  • complex fluorides of titanium, Zirconium, hafium, silicon and / or boron particularly suitable.
  • complexes of fluorides are used as zirconium.
  • the aqueous system comprises hydrofluorocarboxylic acid (H 2 ZrF 6 ), fluorotitanic acid (H 2 TiF 6 ), fluoro hafnic acid (H 2 HfF 6 ) or mixtures thereof.
  • Suitable aqueous systems may preferably in addition to the acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of a second metal, preferably based on a group 4 element of the Periodic Table of the Elements (IUPAC, formerly designated Group IVb or IV-B), in particular zirconium, titanium and / or hafnium, at least one polymeric compound which may be dissolved in the aqueous composition, in emulsion form or in the form of undissolved dispersed particles ,
  • IUPAC Periodic Table of the Elements
  • polymeric compounds may be mentioned in particular the polyacrylic acid and its salts and esters. These acids, esters and salts may be present in the aqueous solution in dissolved or dispersed form.
  • the amount of polymer component can be varied widely and is preferably in the range of 0.1 to 0.5 g per liter.
  • suitable polymeric materials are polymethylvinylmaleic acid and polymethylvinylmaleic anhydride.
  • Suitable polyacrylic acids ideally have a molecular weight of up to 500,000. Preference is often given to mixtures of suitable polymer compounds. Examples which may be mentioned mixtures containing polyacrylic acid, their salts or esters with polyvinyl alcohol.
  • Suitable polymers further include hydroxyethyl ethers of cellulose, ethylene maleic anhydride, polyvinylpyrolidine and polyvinyl methyl ether.
  • Particularly preferred polymeric components in the context of the present invention comprise a cross-linked polyester containing a plurality of carboxylic acid functionalities and a plurality of hydroxyl groups which may have reacted partially or completely with one another.
  • this cross-linked polyester polymer may be the reaction product of a first polymer containing carboxylic acid functionalities with a second polymer containing hydroxyl groups.
  • polyacrylic acid and polymethylvinyl-maleic anhydride may be considered as such first polymers, while polyacrylic acid and polymethylvinyl-maleic anhydride may be considered as such first polymers.
  • vinyl alcohol is a suitable second polymer.
  • both the reaction product of the above-mentioned first and second polymers as well as their mixture is suitable as a constituent of the aqueous system for the treatment by the process according to the invention.
  • such an aqueous solution may additionally preferably contain fluoric acid.
  • Suitable salts of said polyacrylic acid are, for example, ammonium salts.
  • a suitable polymer is 3 - (N -C 1-4 - alkyl-N-2-hydroxethylaminomethyl) -4- hydroxystyrene into consideration, especially if konklare as the compound of Group 4 Hexafluorzir- is used.
  • the homopolymer of the 4-hydroxystyrene may also be present, with an average molecular weight in the range of 3,000 to 6,000. Related details can be found in US 5,089,064.
  • PVD pigments based on aluminum, gold, brass, bronze, silver, lead, vanadium, chromium, manganese, magnesium, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, Zirconium, stainless steel or alloys of these metals are the first metals available, which are also characterized by excellent gloss properties.
  • the invention likewise relates to plastic and paper products containing at least one metal pigment according to the invention.
  • the present invention is directed to aqueous coating compositions comprising at least one metal pigment according to the invention.
  • aqueous coating compositions are regularly used for the application of paint coatings on plastic and metal surfaces, which after drying show the so-called metallic effect.
  • the object on which the invention is based is furthermore achieved by a process for the production of a plastic substrate, at least partially corrosion-protected, in particular shiny, containing metal pigments
  • metal pigments for the process according to the invention it is possible in principle to all metal pigments known to the person skilled in the art and also commercially available, which are suitable for coloring plastic substrates, e.g. AI pigments, to be resorted to.
  • so-called PVD pigments are mentioned.
  • recourse is at least partially, for example also completely, to metal pigments of the invention, in particular Al pigments according to the invention, as described in detail above.
  • aqueous system with compounds of the 4th or 5th group of the Periodic Table of the Elements which is used for the treatment of the plastic substrate surface, corresponds to the aqueous system used for the preparation of the metal pigments according to the invention, both in its general and in the US Pat specific embodiments, so reference is made to the relevant preceding passages of this description in order to avoid repetition.
  • metal pigments preference is given to using aluminum pigments, for example PVD aluminum pigments.
  • Suitable plastic moldings or substrates may be thermosetting, thermoplastic or elastomeric in nature.
  • Suitable thermoplastic molding parts may be, for example, polystyrene, foamed or unfoamed, styrene copolymers such as ABS, SAN and ASA, polyphenylene ethers, polyvinyl chloride, polycarbonate, polyolefins such as polyethylene and polypropylene, polyacrylates, polymethacrylates, polyamides, polyoxymethylenes, Teflon or blends such as ABS / PPE, ASA / PPE, SAN / PPE and ABS / PC.
  • plastic molded parts have proven sen, which have a porous structure, at least in the surface region, in which the aqueous system may optionally penetrate.
  • Suitable thermosetting, thermoplastic or elastomeric plastic substrates are otherwise known to the person skilled in the art as well as commercially available.
  • Elastomeric plastics in the context of the present invention also include thermoplastic elastomers.
  • Plastic substrates according to the invention include e.g. Plastic moldings, for example by injection molding, extrusion, coextrusion, blow molding or other known molding techniques available. Such plastic substrates according to the invention also include plastic granules, such as e.g. used for the production of plastic moldings.
  • the metal pigments are present on, on and / or in the substrate.
  • the metal pigment may have been applied only to the surface, so that it rests on the plastic substrate surface in the sense of a separate layer.
  • the metal pigment may alternatively or additionally be partially embedded in the surface of the plastic substrate and is thus present on the surface.
  • process step b it is optionally possible to subject the substrate surface to a rinsing step with, in particular demineralized, water.
  • the present invention is based on the surprising finding that particularly high-gloss plastic substrates can be obtained which can also be used permanently for outdoor applications without having to accept loss of optical appearance, for example in terms of gloss and flop.
  • extremely corrosion-resistant metal pigments, in particular aluminum pigments are accessible for the first time in a particularly environmentally friendly manner. Without being bound by any theory, it is presently believed that corrosion resistance and gloss are obtained inter alia because the aforementioned second metal compounds are incorporated into the metal layer in the aqueous system treating step.
  • EDX Energy dispersive X-ray microanalyses
  • ESEM Environmental Scanning Microscopy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un procédé de production de pigments métalliques anticorrosion, notamment brillants, procédé comprenant les étapes suivantes : a) production d'une couche support; b) application d'au moins une couche métallique constituée d'un premier métal, d'un premier métal précieux ou d'un premier alliage métallique par dépôt en phase vapeur, ou application de ce premier métal, de ce premier métal précieux ou de ce premier alliage métallique, en particulier sous vide, sur une première surface, recouvrable, de la couche support; et c) addition d'au moins un acide, un oxyde, un oxyde double, un oxydo-hydrate, un sulfure, un halogénure, un nitrure, un carbure, un carbonitrure, un borure, un siliciure, un oxyhalogénure et/ou un sel d'un second métal, dans la couche métallique, par traitement de la couche métallique avec un système aqueux contenant au moins un acide, un oxyde, un oxyde double, un oxydo-hydrate, un sulfure, un halogénure, un carbure, un carbonitrure, un borure, un siliciure, un oxyhalogénure et/ou un sel du second métal, le second métal étant un élément du 4 ème groupe et/ou du 5 ème groupe de la Classification Périodique, ou des mélanges de ces produits; séparation de la couche support, de la couche métallique formée; et e) fragmentation de la couche métallique séparée, tout en conservant les pigments métalliques. L'invention concerne en outre les pigments métalliques obtenus selon ce procédé, ainsi que les produits à base de matière plastique et de papier, et les compositions de revêtement renfermant les pigments métalliques conformes à l'invention. L'invention concerne également un procédé de production de substrats en matière plastique brillants, en particulier anticorrosion, renfermant notamment des pigments métalliques selon l'invention, ainsi que les substrats en matière plastique obtenus suivant ce procédé.
PCT/DE2008/001580 2007-09-28 2008-09-25 Substrat en matière plastique comprenant des pigments métalliques, son procédé de production, et pigments métalliques anticorrosion et leur procédé de production WO2009039842A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007046924.3 2007-09-28
DE200710046924 DE102007046924A1 (de) 2007-09-28 2007-09-28 Kunststoffsubstrat, enthaltend Metallpigmente, und Verfahren zu deren Herstellung sowie korrisionsgeschützte Metallpigmente und Verfahren zu deren Herstellung

Publications (2)

Publication Number Publication Date
WO2009039842A2 true WO2009039842A2 (fr) 2009-04-02
WO2009039842A3 WO2009039842A3 (fr) 2010-04-15

Family

ID=40418012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2008/001580 WO2009039842A2 (fr) 2007-09-28 2008-09-25 Substrat en matière plastique comprenant des pigments métalliques, son procédé de production, et pigments métalliques anticorrosion et leur procédé de production

Country Status (2)

Country Link
DE (1) DE102007046924A1 (fr)
WO (1) WO2009039842A2 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321087A (en) * 1978-12-21 1982-03-23 Revlon, Inc. Process for making metallic leafing pigments
US4338140A (en) * 1978-02-21 1982-07-06 Hooker Chemicals & Plastics Corp. Coating composition and method
GB2165165A (en) * 1984-10-09 1986-04-09 Parker Chemical Co Coating process for aluminium
US5089064A (en) * 1990-11-02 1992-02-18 Henkel Corporation Process for corrosion resisting treatments for aluminum surfaces
US6398999B1 (en) * 1998-10-23 2002-06-04 Avery Dennison Corporation Process for making high aspect ratio reflective metal flakes
US20040020565A1 (en) * 1999-07-08 2004-02-05 Ge Betz, Inc. Non-chromate conversion coating treatment for metals
WO2004026972A1 (fr) * 2002-08-20 2004-04-01 Eckart Gmbh & Co. Kg Flocons metalliques a base de cuivre contenant notamment de l'aluminium et procede de fabrication
EP1455001A1 (fr) * 2001-12-04 2004-09-08 Nippon Steel Corporation Materiau metallique revetu d'un film de revetement d'oxyde metallique et/ou d'hydroxyde metallique et procede de fabrication associe

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3200473B2 (ja) 1992-08-05 2001-08-20 東洋アルミニウム株式会社 アルミニウム顔料

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338140A (en) * 1978-02-21 1982-07-06 Hooker Chemicals & Plastics Corp. Coating composition and method
US4321087A (en) * 1978-12-21 1982-03-23 Revlon, Inc. Process for making metallic leafing pigments
GB2165165A (en) * 1984-10-09 1986-04-09 Parker Chemical Co Coating process for aluminium
US5089064A (en) * 1990-11-02 1992-02-18 Henkel Corporation Process for corrosion resisting treatments for aluminum surfaces
US6398999B1 (en) * 1998-10-23 2002-06-04 Avery Dennison Corporation Process for making high aspect ratio reflective metal flakes
US20040020565A1 (en) * 1999-07-08 2004-02-05 Ge Betz, Inc. Non-chromate conversion coating treatment for metals
EP1455001A1 (fr) * 2001-12-04 2004-09-08 Nippon Steel Corporation Materiau metallique revetu d'un film de revetement d'oxyde metallique et/ou d'hydroxyde metallique et procede de fabrication associe
WO2004026972A1 (fr) * 2002-08-20 2004-04-01 Eckart Gmbh & Co. Kg Flocons metalliques a base de cuivre contenant notamment de l'aluminium et procede de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAVINSÊK B ET AL: "PVD COATINGS AS AN ENVIRONMENTAL CLEAN ALTERNATIVE TO ELECTROPLATING AND ELECTROLESS PROCESSES" SURFACE AND COATINGS TECHNOLOGY, ELSEVIER, AMSTERDAM, NL, Bd. 116-119, 1. September 1999 (1999-09-01), Seiten 476-487, XP002465272 ISSN: 0257-8972 *

Also Published As

Publication number Publication date
DE102007046924A1 (de) 2009-04-09
WO2009039842A3 (fr) 2010-04-15

Similar Documents

Publication Publication Date Title
EP2566997B1 (fr) Procédé de pvd hybride pour déposer des couches de cristal mixte
EP3225717A1 (fr) Procede de fabrication de substrat revetu, substrat revetu et son utilisation
EP0822010B1 (fr) Procédé pour faire un revêtement brillant sur des pièces par exemple de véhicules et notamment des roues, et pièces ainsi revêtues
WO2014108326A1 (fr) Procédé de fabrication d'un substrat métallique ou d'un substrat non métallique muni d'un revêtement métallique, substrat métallique ou substrat non métallique muni d'un revêtement métallique, et utilisation dudit substrat
DE2824319C2 (de) Verfahren zur galvanischen Metallbeschichtung von Gegenständen auf Alumium- oder Magnesiumbasis
EP3117907B1 (fr) Procede de fabrication de substrat revetu
WO2006114429A2 (fr) Objets en plastique pour metallisation, ayant des proprietes de formage ameliorees
DE102007021602A9 (de) Korrosionsschutzsystem für Metalle und Pigment hierfür
EP1652963A1 (fr) Objet à surface améliorée, son procédé de fabrication et utilisation de l'objet
DE102007003766B4 (de) Transparente Barrierefolien für die Verpackungsindustrie
EP2396448B1 (fr) Procédé pour appliquer un revêtement sur des pièces et/ou des matériaux présentant au moins un métal non-ferreux facilement oxydable
EP2591143B1 (fr) Procédé d'enrobage de corps moulés et corps moulés enrobés
DE102005054463B4 (de) Beschichteter Gegenstand, Beschichtungsverfahren sowie Target für ein PVD-Verfahren
EP2463399B1 (fr) Composants de magnésium dotés d'une protection contre la corrosion améliorée
WO2009039842A2 (fr) Substrat en matière plastique comprenant des pigments métalliques, son procédé de production, et pigments métalliques anticorrosion et leur procédé de production
EP2296829B1 (fr) Substrats revêtus et leur procédé de fabrication
WO2008015169A2 (fr) Matière pour moulage thermoplastique pour la fabrication d'éléments métallisables galvaniquement
DE3545636A1 (de) Hartstoffbeschichtung auf grundkoerpern
WO2007039323A1 (fr) Objets en plastique pour la metallisation a proprietes de façonnage ameliorees
DE2246653B2 (de) Beschichteter organischer Polymerisatformkörper und Verfahren zur Herstellung desselben
EP1532286A1 (fr) Composant protege de la corrosion, procede pour le realiser, et dispositif pour mettre en oeuvre le procede
WO2007140850A1 (fr) Utilisation d'acides phosphiniques et/ou d'acides phosphoniques dans des procédés redox
EP3149091B1 (fr) Utilisation de pigments métalliques dans une formulation polymère liquide
DE10114306A1 (de) Kompositschicht und Verfahren zur Herstellung einer Kompositschicht
DE10103460A1 (de) Mehrschichtige Plasmapolymerbeschichtung Verfahren zu ihrer Herstellung und ihre Verwendung

Legal Events

Date Code Title Description
122 Ep: pct application non-entry in european phase

Ref document number: 08833912

Country of ref document: EP

Kind code of ref document: A2