EP0258343A1 - New anticorrosive pigments, preparation and utilization thereof - Google Patents

New anticorrosive pigments, preparation and utilization thereof

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Publication number
EP0258343A1
EP0258343A1 EP87901433A EP87901433A EP0258343A1 EP 0258343 A1 EP0258343 A1 EP 0258343A1 EP 87901433 A EP87901433 A EP 87901433A EP 87901433 A EP87901433 A EP 87901433A EP 0258343 A1 EP0258343 A1 EP 0258343A1
Authority
EP
European Patent Office
Prior art keywords
pigments
weight
dichromate
pigment
chromate
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.)
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Application number
EP87901433A
Other languages
German (de)
French (fr)
Inventor
Manfred Gawol
Gerhard Adrian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dr Hans Heubach GmbH and Co KG
Original Assignee
Dr Hans Heubach GmbH and Co KG
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Publication of EP0258343A1 publication Critical patent/EP0258343A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • C09C1/40—Compounds of 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
    • 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
    • C09C1/0003—Compounds of molybdenum
    • 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
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • 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
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
    • 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
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • 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
    • C09C1/04—Compounds of zinc
    • 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
    • C09C1/22—Compounds of iron
    • 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
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the object of the present invention is to develop environmentally friendly, in particular occupationally less harmful corrosion protection pigments which are able to replace zinc and strontium chromate, especially in base coats for different metal substrates.
  • Chromic acid can be improved significantly.
  • the invention accordingly relates to metal oxide
  • -phosphate and / or molybdate-containing corrosion protection pigments preferably basic metal phosphate and molybdate pigments based on the metals zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combination, in addition to metal oxide,
  • Metal phosphate and / or metal molybdate has a soluble sodium dichromate content of 0.03-2% by weight, preferably 0.2-0.6% by weight, or equivalent amounts of potassium or ammonium dichromates or equivalent amounts of the corresponding Chromates or chromic acid, based on the total weight of the pigment.
  • the combination for example the basic metal phosphate pigments with the soluble alkali metal or ammonium dichromate or the corresponding chromate or chromic acid, has proven to be particularly effective according to the invention if it combines with the pigment sludge of the base pigment after the chemical reaction and wet confectioning are thoroughly mixed before drying, in particular using shear forces. In this way, the uniform distribution of the dissolved chromate component required for optimum effectiveness can be achieved.
  • the uniform and optimal distribution of the chromate component in the pigment or in a pigment combination . n is also possible by dry mixing the components, but subsequent intensive grinding, for example in a pin, turbo or jet mill, is necessary.
  • This preparation of the dried pigment can also be advantageous if the chromate components are added to the wet pigment before drying. In both cases, final screening to achieve fractions with certain particle sizes can be advantageous for certain applications.
  • a further advantageous variant of the combination of the corrosion protection pigment with the chromate components mentioned is to add pigments and / or fillers such as titanium dioxide, barium sulfate or talcum etc. to the pigment sludge before drying or the dried pigment after addition of the chromate components mentioned usually used in the formulation of primers.
  • the pigments and filler components can also be added before the soluble chromate components are added.
  • the amount of such additives is preferably 5 to 20% by weight, in particular 15 to 20% by weight, of the total pigment. -4- l According to a preferred embodiment, the
  • Example 1 basic zinc phosphate is prepared and this is then in the aqueous slurry at a temperature of 70 - 90 ° C with an almost boiling solution of 0.8 wt .-% (based on dry pigment) phthalic anhydride and 10 parts of water for a period of 30 min.
  • the product separated by filtration is mixed with 0.3% by weight (based on dry pigment) of sodium dichromate, this is mixed in uniformly in an intensive mixer and then the pigment sludge is dried at 105 ° C. and the dried product is then ground or marry and sighted.
  • Example 2 basic zinc phosphate is prepared, then phthalic acid or phthalic anhydride is added in the manner described, 10% by weight (based on dry pigment) barium sulfate and 10% by weight (based on dry pigment) talc are then added and after the addition from 0.4. % By weight (based on dry pigment) sodium dichromate is mixed intensively. The pigment sludge obtained is then dried at 105 ° C. and the dried product is then ground or ground and classified.
  • the basic zinc phosphate prepared according to Example 3 with barium and talc is dried (without the addition of dichromate) at 105 ° C. and, after dry preparation, 0.4 wt.% Ammonium dichromate is added in a mixer and the intensively premixed product is then added grind on a turbo mill.
  • Epoxy resin epoxy equivalent weight 450-525
  • Epoxy resin epoxy equivalent weight 450-525
  • Epoxy resin (epoxy equivalent weight 175-185) 8.4 Organically modified ontmorinonite 1.15
  • PV / KPVK (critical pigment volume concentration) 0.7

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Des pigments anti-corrosifs contenant des oxydes métalliques, des phosphates métalliques et/ou du molybdate à base de métaux zinc, aluminium, fer, baryum, strontium, calcium, magnésium et titane, isolés ou associés, contiennent en outre entre 0,03 et 2% en poids de bichromate de sodium soluble ou d'une quantité équivalente de bichromate de potassium ou d'ammonium ou des quantités équivalentes des chromates ou acides chromiques correspondants. Ces pigments sont préparés par homogénéisation totale des parties chromates et ils sont utilisés comme apprêt sur des fonds métalliques ferreux ou non ferreux.Anti-corrosive pigments containing metal oxides, metal phosphates and / or molybdate based on zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, isolated or combined, contain in addition between 0.03 and 2% by weight of soluble sodium dichromate or an equivalent quantity of potassium or ammonium dichromate or equivalent quantities of the corresponding chromates or chromic acids. These pigments are prepared by total homogenization of the chromate parts and they are used as a primer on ferrous or non-ferrous metallic bases.

Description

Neue Korrosionsschutzpigmente und ihre Herstellung und AnwendungNew anti-corrosion pigments and their manufacture and application
Bei der Pigmentierung von Lacksystemen für NE-Metall- Untergründe, besonders aber auch für Anlagen und Fahr¬ zeuge, die aus verschiedenen Metallen, wie z.B. Eisen, verzinktem Eisen und Aluminium bestehen, war man bisher auf Zinkchromat und Strontiumchromat als aktive Korro- sionsschutzpigmente angewiesen, da nur diese zu der besonders auf Aluminium geforderten Haltbarkeit der Beschichtungen führen.When pigmenting paint systems for non-ferrous metal substrates, but especially for systems and vehicles made of different metals, e.g. So far, iron, galvanized iron and aluminum have been reliant on zinc chromate and strontium chromate as active corrosion protection pigments, since only these lead to the durability of the coatings, which is particularly required on aluminum.
Versuche für diese Anwendungsbereiche, die als kanzero- gen eingestuften Zinkchromat- und Strontiumchromat- pigmente durch Zinkphosphat bzw. modifizierte Zink- phosphatpigmente zu ersetzen, führten nicht zum ge¬ wünschten Erfolg.Attempts in these areas of application to replace the zinc chromate and strontium chromate pigments classified as carcinogenic with zinc phosphate or modified zinc phosphate pigments did not lead to the desired success.
Vor allen Dingen die speziell von Zink- und Strontium¬ chromat auf verschiedenen Aluminiumlegierungen unter bewitterungsbedingten Einwirkungen erreichten sehr guten Haftungseigenschaften, konnten mit den Phosphatpigmenten bisher nicht nachvollzogen werden.Above all, the very good adhesion properties achieved especially by zinc and strontium chromate on various aluminum alloys under the effects of weathering have so far not been able to be reproduced with the phosphate pigments.
Aufgabe der vorliegenden Erfindung ist die Entwicklung umweltfreundlicher, insbesondere arbeitsmedizinisch weniger bedenklicher Korrosionsschutzpigmente, die in der Lage sind, Zink- und Strontiumchromat, insbesondere in Grundanstrichen für unterschiedliche Metallunter¬ gründe, zu ersetzen.The object of the present invention is to develop environmentally friendly, in particular occupationally less harmful corrosion protection pigments which are able to replace zinc and strontium chromate, especially in base coats for different metal substrates.
Es wurde gefunden, daß die für Eisenuntergründe optimal wirkenden modifizierten basischen Phosphatpigmente in ihrer Wirksamkeit auch für Leichtmetalluntergründe durch Kombination mit sehr geringen Mengen an löslichen Alkali- oder Ammoniumdichromaten bzw. -chromaten oderIt was found that the effectiveness of the modified basic phosphate pigments, which work optimally for iron substrates, is also effective for light metal substrates by combining them with very small amounts of soluble alkali or ammonium dichromates or chromates or
Chromsäure ganz wesentlich verbessert werden können.Chromic acid can be improved significantly.
Diese sehr geringen Anteile der löslichen Chromatver- bindungen oder von Chromsäure ergeben eine deutliche Verbesserung der Haftungs- und Korrosionsschutzeigen- schaften der damit pigmentierten Grundierungen.These very small proportions of soluble chromate compounds or chromic acid result in a significant improvement in the adhesion and corrosion protection properties of the primers pigmented with them.
Dabei ist es sogar möglich, den Anteil an löslichen Alkali- oder Ammoniumdichromaten oder Chromsäure so niedrig zu halten, daß der von der Arbeitsstoff¬ verordnung angegebene kennzeichnungspflichtige Konzen¬ trationsbereich nicht überschritten wird.It is even possible to keep the proportion of soluble alkali or ammonium dichromates or chromic acid so low that the concentration range specified by the working substances regulation is not exceeded.
Gegenstand der Erfindung sind demnach Metalloxid-,The invention accordingly relates to metal oxide,
-phosphat- und/oder molybdathaltige Korrosionsschutzpig¬ mente, vorzugsweise basische Metallphosphat- und -molyb- datpigmente auf der Basis der Metalle Zink, Aluminium, Eisen, Barium, Strontium, Calcium, Magnesium und Titan, einzeln oder in Kombination, die neben Metalloxid,-phosphate and / or molybdate-containing corrosion protection pigments, preferably basic metal phosphate and molybdate pigments based on the metals zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combination, in addition to metal oxide,
Metallphosphat und/oder Metallmolybdat einen Anteil an löslichem Natriumdichromat von 0,03 - 2 Gew.-%, vorzugs¬ weise 0,2 - 0,6 Gew.-%, bzw. äquivalente Mengen von Kalium- oder Ammoniumdichromaten oder äquivalente Mengen der entsprechenden Chromate oder Chro säure, bezogen auf das Gesamtgewicht des Pigmentes, enthalten.Metal phosphate and / or metal molybdate has a soluble sodium dichromate content of 0.03-2% by weight, preferably 0.2-0.6% by weight, or equivalent amounts of potassium or ammonium dichromates or equivalent amounts of the corresponding Chromates or chromic acid, based on the total weight of the pigment.
Obwohl versucht wurde, Pigmente mit löslichen Chromat- anteilen durch Kombination der Phosphatpigmente mit Zinkchromat bzw. Strontiumchromat zu erhalten, erwiesen sich diese aber nur bei sehr hohen Strontium- und Zink- chromatanteilen so effektiv wie die erfindungsgemäßen Korrosionsschutzpigmente, also mit Chromatmengen, die um Größenordnungen höher liegen, als bei den erfindungs- gemäßen Korrosionsschutzpigmenten. -2a- Man hat schon vor längerer Zeit versucht, Phosphate bzw. Oxide mit Chromat zu kombinieren. Gemäß DE-PS 667 135 wird ein Pigment durch Absättigung adsorbierend wirkender pulverförmiger Feststoffe mit wässrigen Lösungen von Chromsäure oder Chromaten und anschließendes Trocknen undAlthough attempts have been made to obtain pigments with soluble chromate components by combining the phosphate pigments with zinc chromate or strontium chromate, these have only proven to be as effective as the corrosion protection pigments according to the invention, that is to say with chromate quantities, in the case of very high strontium and zinc chromate components lie higher than with the corrosion protection pigments according to the invention. -2a- Attempts to combine phosphates or oxides with chromate have been attempted for a long time. According to DE-PS 667 135 a pigment is absorbed by saturating powdery solids with aqueous solutions of chromic acid or chromates and then drying and
Vermählen erhalten. Dies erfordert jedoch ca. 25 % bis 53 % Chromsäure oder Chromat, bezogen auf adsorbierenden Feststoff bzw. 20 bis 35 %, bezogen auf Endpigment. Dies- ist eine Menge, die arbeitsmedizinisch untragbar ist.Get married. However, this requires approx. 25% to 53% chromic acid or chromate, based on the adsorbing solid or 20 to 35%, based on the final pigment. This is a lot that is occupationally intolerable.
In der DD-PS 1082 wird Bleichromat auf ein Trägermaterial aufgefällt. Es entsteht dabei unlösliches Bleichromat und kein löslicher Chromatrestanteil in Mengen von 5 bis 11 Gew.-%. Es ist also bekannt, Chromat in festadsorbierter oder unlöslicher Form zu verwenden. Es ist jedoch neu und überraschend, daß durch die Verwendung sehr geringer Mengen löslicher Chromverbindungen bessere Korrosionsschutzer¬ gebnisse erzielt werden als nach dem Stand der Technik, da festgestellt wurde, daß bei höheren Mengen (über 2, insbesondere über 5 %) nicht nur die Auslaugung der löslichen Verbindung, sondern auch erhöhte Blasenbildung bei der Bewitterung der Anstrichfilme einsetzt. Es war daher nicht naheliegend, die bekannten, arbeitsmedizinisch bedenklichen Mengen von 5 % oder mehr auf Mengen zu er- niedrigen, die arbeitsmedinzinisch unbedenklich oder kaum bedenklich sind und trotzdem bessere Ergebnisse zu erzielen. In DD-PS 1082 lead chromate is struck on a carrier material. This produces insoluble lead chromate and no soluble chromate residue in amounts of 5 to 11% by weight. It is therefore known to use chromate in a firmly adsorbed or insoluble form. However, it is new and surprising that the use of very small amounts of soluble chromium compounds achieves better corrosion protection results than according to the prior art, since it has been found that higher amounts (more than 2%, in particular more than 5%) not only leach out of the soluble compound, but also increased blistering when weathering the paint films. It was therefore not obvious to reduce the known, occupationally mediocre quantities from 5% or more to quantities that are harmless or hardly objectionable in terms of occupational medicine and still achieve better results.
-3- Als erfindungsgem ß besonders wirksam erweist sich die Kombination,bei- spielsweise der basischen Metallphosphatpigmente mit dem löslichen Alkali- oder Ammoniumdichromat bzw. dem ent¬ sprechenden Chromat oder Chromsäure, wenn diese dem Pig- mentschlamm des Basispigmentes nach der chemischen Umset¬ zung und Naßkonfektionierung vor der Trocknung gründlich zugemischt werden, insbesondere unter Anwendung von Scher¬ kräften. Auf diese Weise kann die für eine optimale Wirk¬ samkeit erforderliche gleichmäßige Verteilung der gelösten Chromatkomponente erreicht werden.The combination, for example the basic metal phosphate pigments with the soluble alkali metal or ammonium dichromate or the corresponding chromate or chromic acid, has proven to be particularly effective according to the invention if it combines with the pigment sludge of the base pigment after the chemical reaction and wet confectioning are thoroughly mixed before drying, in particular using shear forces. In this way, the uniform distribution of the dissolved chromate component required for optimum effectiveness can be achieved.
Die gleichmäßige und optimale Verteilung der Chromatkompo¬ nente im Pigment oder in einer Pigmentkombinatio.n ist auch durch Trockenvermischung der Komponenten möglich, wobei aber eine nachfolgende intensive Vermahlung, beispielswei¬ se in einer Stift-, Turbo- oder Strahlmühle, notwendig wird. Diese Aufbereitung des getrockneten Pigments kann auch bei Zugabe der Chromatanteile zum nassen Pigment vor der Trocknung von Vorteil sein. In beiden Fällen kann ab- schließendes Sichten zur Erzielung von Fraktionen mit be¬ stimmten Teilchengrößen für gewisse Anwendungszwecke von Vorteil sein.The uniform and optimal distribution of the chromate component in the pigment or in a pigment combination . n is also possible by dry mixing the components, but subsequent intensive grinding, for example in a pin, turbo or jet mill, is necessary. This preparation of the dried pigment can also be advantageous if the chromate components are added to the wet pigment before drying. In both cases, final screening to achieve fractions with certain particle sizes can be advantageous for certain applications.
Eine weitere vorteilhafte Variante der Kombination des Korrosionsschutzpigmentes mit den genannten Chromatantei- len besteht darin, dem Pigmentschlamm vor der Trocknung oder dem getrockneten Pigment nach Zugabe der genannten Chromatanteile noch Pigmente und/oder Füllstoffe, wie Ti¬ tandioxid, Bariumsulfat oder Talkum etc., die üblicherwei- se bei der Formulierung von Grundierungen mit verwendet werden, zuzusetzen. Die Zugabe der Pigmente und Füllstoff¬ komponenten kann auch vor der Zugabe der löslichen Chromat¬ anteile erfolgen. Die Menge solcher Additive beträgt vor¬ zugsweise 5 bis 20 Gew.-%, insbesondere 15 bis 20 Gew.-% des Gesamtpigments. -4- l Gemäß einer bevorzugten Ausführungsform wird auf dasA further advantageous variant of the combination of the corrosion protection pigment with the chromate components mentioned is to add pigments and / or fillers such as titanium dioxide, barium sulfate or talcum etc. to the pigment sludge before drying or the dried pigment after addition of the chromate components mentioned usually used in the formulation of primers. The pigments and filler components can also be added before the soluble chromate components are added. The amount of such additives is preferably 5 to 20% by weight, in particular 15 to 20% by weight, of the total pigment. -4- l According to a preferred embodiment, the
Pigment nach der chemischen Umsetzung in der Naßphase oder auf das trockene Pigment Phthalsäure oder Phthal- säureanhydrid in einer Menge bis zu 10 Gew.-%, insbeson- dere 0,3 bis 3 Gew.-%, ggfs. unter Erhitzen, aufgefällt und danach werden die Chromatanteile zugegeben, wie dies in der DE-AS 30 46 697 für solche Pigmente ohne lösliche Chromanteile gezeigt ist.Pigment after the chemical reaction in the wet phase or on the dry pigment phthalic acid or phthalic anhydride in an amount of up to 10% by weight, in particular 0.3 to 3% by weight, if appropriate with heating, and then afterwards the chromate components are added, as shown in DE-AS 30 46 697 for such pigments without soluble chromium components.
Schließlich kann man den Chromatanteil auch einem fertigenFinally, the chromate content can also be made to you
Pigment oder Grundierungsrrittel zugeben. 3ei Anwendung der für die Herstellung von Lackansätzen üblichen Schnell- rührer kann häufig eine hinreichende Homogenisierung erzielt werden. Sollte dies nicht der Fall sein, so kann man eine Vermahlung des Grundiermittels mit den gemischten Chromatanteilen vornehmen.Add pigment or primer third. Adequate homogenization can often be achieved when using the high-speed stirrers customary for the production of paint batches. If this is not the case, the primer can be ground with the mixed chromate components.
Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
Beispiel 1example 1
100 kg Zinkoxid werden in einem Rührbehälter mit 800 1 Wasser aufgeschlämmt und in ca. 2 Std. mit 71 kg einer 75 %igen Phosphorsäure zu einem basischen Zinkphosphat umgesetzt.100 kg of zinc oxide are slurried in a stirred tank with 800 l of water and converted into a basic zinc phosphate with 71 kg of a 75% phosphoric acid in about 2 hours.
Nach der Naßkonfektionierung wird der Pigmentschlamm vor dem Trocknen mit 0,4 Gew.-% (bezogen auf Trockenpigment) Natriumchromat versetzt und dieses in einem Intensiv¬ mischer gleichmäßig im Pigmentschlamm verteilt. Danach wird bei 105°C getrocknet und in üblicher Weise, z.B. durch Mahlen oder Mahlen und Sichten aufbereitet. -5-After the wet assembly, 0.4% by weight (based on dry pigment) of sodium chromate is added to the pigment sludge before drying, and this is evenly distributed in the pigment sludge in an intensive mixer. It is then dried at 105 ° C. and processed in the usual way, for example by milling or milling and sifting. -5-
Beispiel 2Example 2
Gemäß Beispiel 1 wird basisches Zinkphosphat hergestellt und dieses danach in der wässrigen Aufschlämmung bei einer Temperatur von 70 - 90°C mit einer fast kochenden Lösung von 0,8 Gew.-% (bezogen auf Trockenpigment) Phthalsäureanhydrid und 10 Teilen Wasser während einer Zeitspanne von 30 min versetzt. Nach der Naßkonfektio- nierung wird das durch Filtrieren abgetrennte Produkt mit 0,3 Gew.-% (bezogen auf Trockenpigment) Natrium- dichromat versetzt, dieses in einem Intensivmischer gleichmäßig untergemischt und danach der Pigmentschlamm bei 105°C getrocknet und das getrocknete Produkt danach vermählen bzw. vermählen und gesichtet.According to Example 1, basic zinc phosphate is prepared and this is then in the aqueous slurry at a temperature of 70 - 90 ° C with an almost boiling solution of 0.8 wt .-% (based on dry pigment) phthalic anhydride and 10 parts of water for a period of 30 min. After wet confectioning, the product separated by filtration is mixed with 0.3% by weight (based on dry pigment) of sodium dichromate, this is mixed in uniformly in an intensive mixer and then the pigment sludge is dried at 105 ° C. and the dried product is then ground or marry and sighted.
Beispiel 3Example 3
Gemäß Beispiel 2 wird basisches Zinkphosphat hergestellt, danach Phthalsäure oder Phthalsäureanhydrid in der be¬ schriebenen Weise zugegeben, dem Pigmentschlamm danach 10 Gew.-% (bezogen auf Trockenpigment) Bariumsulfat und 10 Gew.-% (bezogen auf Trockenpigment) Talkum zugesetzt und nach Zugabe von 0,4. Gew.-% (bezogen auf Trockenpigment) Natriumdichromat eine intensive Vermischung vorgenommen. Der erhaltene Pigmentschlamm wird anschließend bei 105 °C getrocknet und das getrocknete Produkt danach vermählen bzw. vermählen und gesichtet. According to Example 2, basic zinc phosphate is prepared, then phthalic acid or phthalic anhydride is added in the manner described, 10% by weight (based on dry pigment) barium sulfate and 10% by weight (based on dry pigment) talc are then added and after the addition from 0.4. % By weight (based on dry pigment) sodium dichromate is mixed intensively. The pigment sludge obtained is then dried at 105 ° C. and the dried product is then ground or ground and classified.
-6--6-
Beispiel 4Example 4
Das nach Beispiel 3 hergestellte basische Zink¬ phosphat mit Barium und Talkum wird (ohne Zugabe von Dichromat) bei 105°C getrocknet und nach der Trockenaufbereitung in einem Mischer mit 0,4 Gew.-% Ammoniumdichromat versetzt und das intensiv vorge¬ mischte Produkt anschließend auf einer Turbomühle vermählen.The basic zinc phosphate prepared according to Example 3 with barium and talc is dried (without the addition of dichromate) at 105 ° C. and, after dry preparation, 0.4 wt.% Ammonium dichromate is added in a mixer and the intensively premixed product is then added grind on a turbo mill.
Die auf diese Weise erhaltenen Produkte mit löslischen Alkali- oder Ammoniumdichromat- bzw. -chromat-Anteilen wurden in nachfolgend beschriebener Rezeptur für eine Grundierung für Nutzfahrzeuge in Mischbauweise auf Metalluntergründen, Eisen, verzinktem Eisen und Aluminium und bei Trockenschichtdicken von 90 - 100μm nach 1200 Std. im Salzsprühtest geprüft.The products obtained in this way with soluble alkali or ammonium dichromate or chromate components were used in the formulation described below for a primer for commercial vehicles in mixed construction on metal substrates, iron, galvanized iron and aluminum and with dry layer thicknesses of 90 - 100μm after 1200 hours tested in the salt spray test.
Rezeptur für 2-Komponenten-Beschichtung für Nutzfahrzeuge in Mischbauweise mit einem erfindungsgemäßen PigmentRecipe for 2-component coating for commercial vehicles in mixed construction with a pigment according to the invention
Gew. _ Gew. _
_. Λ Teile_ . Λ parts
Komponente AComponent A
Epoxidharz (Epoxidäquivalentgewicht 450-525) ' 11,2Epoxy resin (epoxy equivalent weight 450-525) '11 .2
Epoxidharz (Epoxidäquivalentgewicht 175-185) 8,4 Organisch modifizierter ontmorinonit 1,15Epoxy resin (epoxy equivalent weight 175-185) 8.4 Organically modified ontmorinonite 1.15
Netzmittel 0,17Wetting agent 0.17
Entschäumer 0,08Defoamer 0.08
Chromatrnodifiziertes Zinkphosphat (Beispiel 2) 19,6Chromate-modified zinc phosphate (Example 2) 19.6
Bariumsulfat (nat.) max. 10 μm 17,0 Magnesiumsili at max. 15 μm 5,4Barium sulfate (nat.) Max. 10 μm 17.0 magnesium silicate at max. 15 μm 5.4
Titandioxid 8,0Titanium dioxide 8.0
Methyläthylketon 12,5Methyl ethyl ketone 12.5
Xylol 10,0Xylene 10.0
Komponente BComponent B
Modifizieres al i phatisches Polyamin 6 ,5 H-Aktiv-Äquival entgewi cht 80Modified aliphatic polyamine 6, 5 H active equivalent equals 80
100 ,0 -7-100, 0 -7-
Pigmentvolumen-Konzentration (PVK) in % = 39Pigment volume concentration (PVC) in% = 39
PV /KPVK (kritische Pigmentvolumen- Konzentration) = 0,7PV / KPVK (critical pigment volume concentration) = 0.7
Festkörpergehalt in % = 74 Solids content in% = 74
Zum Vergleich wurden entsprechende Grundierungen mit Zinkchromat und Strontiumchromat hergestellt und in gleicher Weise geprüft.For comparison, appropriate primers were made with zinc chromate and strontium chromate and tested in the same way.
Die Grundierungen mit den erfindungsgemäßen Pigmenten ergaben in einer Gesamtbewertung, wobei Haftung, Rost¬ bildung und Blasenbildung bewertet wurden, praktisch die gleichen Ergebnisse wie die mit Zink-und Strontium¬ chromat pigmentierten Grundierungen. An overall evaluation of the primers with the pigments according to the invention, adhesion, rust formation and blister formation being evaluated, gave practically the same results as the primers pigmented with zinc and strontium chromate.

Claims

-8--8th-
P a t e n t a n s p r ü c h eP a t e n t a n s r u c h e
1. Metalloxid-, -phosphat- und/oder -molybdathaltige Korrosions¬ schutzpigmente auf der Basis der Metalle Zink, Aluminium, Eisen, Barium, Strontium, Calcium, Magnesium und Titan, einzeln oder in Kombination, dadurch gekennzeichnet, daß die Pigmente zusätzlich 0,03 - 2 Gew.-% lösliches Natrium- dichromat oder äquivalente Mengen von Kaliumdichromat, Ammoniumdichromat bzw. äquivalente Mengen der entsprechen¬ den Chromate oder von Chromsäure, einzeln oder im Gemisch, enthalten.1. Metal oxide, phosphate and / or molybdate-containing corrosion protection pigments based on the metals zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combination, characterized in that the pigments additionally 0 , 03-2% by weight soluble sodium dichromate or equivalent amounts of potassium dichromate, ammonium dichromate or equivalent amounts of the corresponding chromates or chromic acid, individually or in a mixture.
2. Pigmente nach Anspruch 1, dadurch gekennzeichnet, daß basi¬ sche Pigmente eine auf sie aufgefällte Menge an bis zu -. -2. Pigments according to claim 1, characterized in that basic pigments have a striking amount of up to -. -
10' Gew.-%, insbesondere 0,3 - 3 Gew.-%, Phthalsäure oder Phthalsäureanhydrid enthalten und darauf Dichromat, Chromat und/oder Chromsäure aufgebracht ist.Contain 10% by weight, in particular 0.3-3% by weight, of phthalic acid or phthalic anhydride and dichromate, chromate and / or chromic acid is applied thereon.
3. Pigmente nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie zusätzlich übliche Additive, andere Pigmente und/oder Füllstoffe, wie Titandioxid und/oder Barium¬ sulfat und/oder Talkum in Mengen von 1 bis 40 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, bezogen auf Gesamtpigment aufweisen, die vor oder nach der Zugabe der Chromatan¬ teile zugefügt sind.3. Pigments according to claim 1 or 2, characterized in that they additionally conventional additives, other pigments and / or fillers such as titanium dioxide and / or barium sulfate and / or talc in amounts of 1 to 40 wt .-%, preferably 5 have up to 20% by weight, based on the total pigment, which are added before or after the addition of the chromatic components.
4. Pigmente nach einem der Ansprüche 1 bis 3, dadurch ge¬ kennzeichnet, daß sie 0,2 bis 0,6 Gew.-% lösliches Na- triumdichromat oder äquivalente Mengen Kaliumdichromat, Ammoniumdichromat oder der entsprechenden Chromate oder von Chromsäure, einzeln oder im Gemisch, enthalten.4. Pigments according to one of claims 1 to 3, characterized ge indicates that they contain 0.2 to 0.6 wt .-% soluble sodium dichromate or equivalent amounts of potassium dichromate, ammonium dichromate or the corresponding chromates or chromic acid, individually or in Mixture.
5. Verfahren zur Herstellung der Pigmente nach Anspruch 1 bis 4 durch übliche chemische Umsetzung der Metalloxide, dadurch gekennzeichnet, daß nach der Naßkonfektionie¬ rung dem Pigmentschlamm vor dem Trocknen 0,03 bis 2 Gew.-% lösliches Natriumdichromat oder äquivalente Men¬ gen an Kaliumdichromat, Ammoniumdichromat oder äquiva¬ lente Mengen der entsprechenden Chromate oder von Chrom¬ säure, einzeln oder im Gemisch, zugesetzt werden und das Gemisch homogenisiert und danach in üblicher Weise getrocknet und aufbereitet wird.5. A process for the preparation of the pigments as claimed in claims 1 to 4 by customary chemical conversion of the metal oxides, characterized in that, after wet confectioning, the pigment sludge, before drying, contains 0.03 to 2% by weight of soluble sodium dichromate or equivalent amounts Potassium dichromate, ammonium dichromate or equivalent amounts of the corresponding chromates or of chromic acid, individually or in a mixture, are added and the mixture is homogenized and then dried and processed in the customary manner.
6. Abänderung des Verfahrens nach Anspruch 5, dadurch gekennzeichnet, daß der Pigmentschlamm nach der Na߬ konfektionierung zunächst getrocknet wird und, nach der Aufbereitung des getrockneten Pigmentes diesem, bzw. einem von vornherein trockenen Pigment, 0,03 -6. Modification of the method according to claim 5, characterized in that the pigment sludge is first dried after the wet processing and, after the processing of the dried pigment, or a pigment which is dry from the outset, 0.03 -
2 Gew.-% der Dichromat-, Chromat- oder Chromsäureanteile zugemischt werden und danach zur gleichmäßigen Verteilung der Chromkomponenten eine Trockenvermahlung erfolgt. -iO-2% by weight of the dichromate, chromate or chromic acid components are added and then dry grinding is carried out in order to distribute the chromium components evenly. -iO-
1 7. Verfahren nach Anspruch 5 oder 6 , dadurch gekennzeich¬ net, daß nach der chemischen Umsetzung in der Naßphase oder beim trockenen Pigment Phthalsäure oder Phthalsäu¬ reanhydrid in einer Menge bis zu 10 Gew . -% , insbesonde-1 7. The method according to claim 5 or 6, characterized gekennzeich¬ net that after the chemical reaction in the wet phase or with the dry pigment phthalic acid or phthalic anhydride in an amount up to 10 wt. -%, in particular
5 re 0 , 3 bis 3 Gew. -% auf das Pigment, gegebenenfal ls un¬ ter Erhitzen, aufgebracht wird und danach die Chromatan¬ teile zugegeben werden.5, 0, 3 to 3% by weight is applied to the pigment, if necessary with heating, and the chromatic portions are then added.
8. Verfahren nach einem oder mehreren der Ansprüche 5 , 6 0 oder 7 , dadurch gekennzeichnet, daß nach der Herstel¬ lung der Pigmente, diesen, gegsbenaifalls unter Zugabe von Addi¬ tiven, in der Naßphase oder in getrocknetem Zustand andere Pig¬ mente und/oder Füllstoffe, insbesondere Titandioxid und/oder Ba- riumsulfat und/oder Talkum in Mengen von 1 bis 40 Gew.-%, vorzugs- 5 weise 5 bis 20 Gew.-%, vor oder nach dar 2_gabe der Chromatanteile zu¬ gefügt werden und nach der intensiven Vermischung der Komponenten die Aufbereitung des Gemisches, gegebenenfalls unter Trocknen und/oder gründlichem Verm hlen, vorgen πmen wird.8. The method according to one or more of claims 5, 6 0 or 7, characterized in that after the manufacture of the pigments, these, gegsbenaifalls with the addition of additives, in the wet phase or in the dried state, other pigments and / or fillers, in particular titanium dioxide and / or barium sulfate and / or talc in amounts of 1 to 40% by weight, preferably 5 to 20% by weight, are added before or after the addition of the chromate components and after the intensive mixing of the components, the preparation of the mixture, if appropriate with drying and / or thorough grinding, is carried out.
0 9. Verwendung der Korrosionsschutzpigmente nach Anspruch 1 bis 4 zur Pigmentierung in Grundierungen für Eisen und Nichteisen-Metalluntergründe oder für Beschichtun¬ gen für Nutzfahrzeuge in Metal l-Mischbauweise .9. Use of the anti-corrosion pigments according to claim 1 to 4 for pigmentation in primers for iron and non-ferrous metal substrates or for coatings for commercial vehicles in mixed metal construction.
2510. Verwendung nach Anspruch 9 in Grundierungen " für unter¬ schiedliche Metalluntergründe , insbesondere Eisen, ver¬ zinktes Eisen und Aluminium, die entsprechend den für die Pigmentierung verwendeten Pigmentanteilen, lös liche Dichromate bzw. Chromate oder Chromsäure , einzeln oder2510. Use according to claim 9 in primers " for different metal substrates, in particular iron, galvanized iron and aluminum, which, according to the pigment proportions used for the pigmentation, soluble dichromates or chromates or chromic acid, individually or
30 im Gemisch, entsprechend Anspruch 1 bis 4 enthal ten, ins¬ besondere einen Anteil an lös lichem Natriumdichromat zwischen 0 , 0075 und 0, 5 Gew. -% bei einer 25 %igen Piqmentie- rung oder äquivalente Mengen der anderen Chromatanteile gemäß Anspruch 1 einzeln oder im Gemisch.30 in the mixture, according to claims 1 to 4, in particular a proportion of soluble sodium dichromate between 0.0075 and 0.5% by weight in the case of 25% concentration or equivalent amounts of the other chromate components according to claim 1 individually or in a mixture.
35 -w- 11. Verwendung von löslichem Natriumdichromat in einer35 -w- 11. Use of soluble sodium dichromate in a
Menge von 0,03 - 2 Gew.-% oder von äquivalenten Mengen von Kaliumdichromat, Ammoniumdichromat bzw. äquivalen¬ ten Mengen der entsprechenden Chromate oder von Chrom- säure zur Erhöhung der Haftfestigkeit und Korrosions¬ schutzwirkung von Grundierungen auf der Basis von metalloxid-, -phosphat- und/oder molybdathaltigen Korrosionsschutzpigmenten auf der Basis der Metalle: Zink, Aluminium, Eisen, Barium, Strontium, Calcium, Magnesium und Titan, einzeln oder in Kombinationen. Quantity of 0.03-2% by weight or equivalent quantities of potassium dichromate, ammonium dichromate or equivalent quantities of the corresponding chromates or chromic acid to increase the adhesive strength and corrosion protection effect of primers based on metal oxide, -phosphate and / or molybdate-containing corrosion protection pigments based on the metals: zinc, aluminum, iron, barium, strontium, calcium, magnesium and titanium, individually or in combinations.
EP87901433A 1986-02-20 1987-02-13 New anticorrosive pigments, preparation and utilization thereof Withdrawn EP0258343A1 (en)

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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3731737A1 (en) * 1987-09-21 1989-03-30 Heubach Hans Dr Gmbh Co Kg CORROSION PROTECTION PIGMENTS BASED ON ERDALKALIHYDROGEN PHOSPHATES
DE3813335A1 (en) * 1988-04-21 1989-11-02 Basf Ag METAL OXIDE COATED ALUMINUM PIGMENTS
US5244956A (en) * 1988-08-09 1993-09-14 Lockheed Corporation Corrosion inhibiting coating composition
AT404182B (en) * 1993-06-03 1998-09-25 Ica Innoconsult Ag CORROSION PROTECTION METHOD FOR COMBUSTION PLANTS
US5993523A (en) * 1998-06-05 1999-11-30 Silberline Manufacturing Co., Inc. Inhibited metal pigment pastes containing molybdate pigments and suitable for aqueous coating compositions
CA2453005A1 (en) * 2003-12-17 2005-06-17 Fermag Inc. Hydrometallurgical process for separating steel mill dust using an arc furnace and pigments obtained by the process
JP4313750B2 (en) * 2004-11-04 2009-08-12 新日本製鐵株式会社 Steel columns with corrosion protection at the buried underground
BRPI0611831A2 (en) * 2005-06-17 2010-09-28 Ferrinov Inc anti-corrosion pigments derived from the dust of an arc flash furnace and containing sacrificial calcium
US8322754B2 (en) * 2006-12-01 2012-12-04 Tenaris Connections Limited Nanocomposite coatings for threaded connections
AR100953A1 (en) 2014-02-19 2016-11-16 Tenaris Connections Bv THREADED PIPE FOR AN OIL WELL PIPING
DE102014119472A1 (en) 2014-12-22 2016-06-23 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Process for the preparation of anisotropic zinc phosphate particles and zinc metal mixed phosphate particles and their use

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1082C (en) * 1877-08-27 E. LANGEN in Köln Method of producing hard white sugar using the centrifuge
DE667135C (en) * 1934-07-01 1938-11-04 Axel Viggo Blom Dr Anti-rust paint containing chromium compounds
US2172505A (en) * 1935-12-16 1939-09-12 Henry A Gardner Pigment and process for preparing the same
DE747780C (en) * 1939-01-21 1944-10-13 Manufacture of anti-corrosive pigments
US3248251A (en) * 1963-06-28 1966-04-26 Teleflex Inc Inorganic coating and bonding composition
US3443977A (en) * 1967-11-13 1969-05-13 Pfizer & Co C Anticorrosion pigments
US3963472A (en) * 1969-06-27 1976-06-15 Union Oil Company Of California Process for preventing corrosion by incorporative soluble metal chromates in fertilizer solutions
US3656975A (en) * 1970-02-16 1972-04-18 Teleflex Inc Coating composition
US3969127A (en) * 1972-07-07 1976-07-13 The Sherwin-Williams Company Molybdate corrosion inhibiting pigment and method for preparing same
US3874883A (en) * 1972-07-07 1975-04-01 American Metal Climax Inc Corrosion inhibiting pigment and method of making same
US4017315A (en) * 1975-06-27 1977-04-12 Amax Inc. Molybdate-phosphate corrosion inhibiting pigment
DE3046697A1 (en) * 1980-12-11 1982-07-15 Goslarer Farbenwerke Dr. Hans Heubach GmbH & Co KG, 3394 Langelsheim CORROSION PROTECTION PIGMENTS AND THEIR USE IN PAINTING AGENTS
CA1162727A (en) * 1981-12-11 1984-02-28 Wigo Haacke Anti-corrosion pigments and their use in paints

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8705040A1 *

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