EP0295980A1 - Process for colouring metal surfaces of zinc or zinc alloys or of zinc plated surfaces - Google Patents

Process for colouring metal surfaces of zinc or zinc alloys or of zinc plated surfaces Download PDF

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Publication number
EP0295980A1
EP0295980A1 EP88401251A EP88401251A EP0295980A1 EP 0295980 A1 EP0295980 A1 EP 0295980A1 EP 88401251 A EP88401251 A EP 88401251A EP 88401251 A EP88401251 A EP 88401251A EP 0295980 A1 EP0295980 A1 EP 0295980A1
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Prior art keywords
zinc
dyes
parts
subjected
ion
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EP88401251A
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German (de)
French (fr)
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EP0295980B1 (en
Inventor
Yves Baziard
Robert Brun
Duprat Annette Puyoo
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Societe Civile de Recherche DBB
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Societe Civile de Recherche DBB
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Classifications

    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/84—Dyeing
    • 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
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/30—Change of the surface
    • B05D2350/33—Roughening
    • B05D2350/35—Roughening by chemical means

Definitions

  • the present invention relates to a process for coloring metallic surfaces of zinc, or of metals coated with zinc (galvanized, electro-galvanized parts, etc.).
  • the colors obtained belong to the whole visible spectrum.
  • Zinc coloring processes have been known for a long time, making it possible to obtain several colors, of which black and brown are the most common. Most of the known techniques are today abandoned because they are unsuitable for profitable industrialization.
  • C. BARNES - The Coloration of Metals, Rev. Prog. Coloring, Vol. 14, p. 127 (1984) - the techniques which make it possible to color zinc concern galvanized or electro-galvanized objects. These coloring techniques are generally used to increase the corrosion resistance of zinc; they then appear rather as anti-corrosion protection techniques, the contribution of color not being initially the aim sought.
  • the gray color is obtained by phosphating.
  • zinc can be colored greenish black by anodization in a solution containing hydrofluoric, chromic and phosphoric acids, but this process is not used because of the high voltages necessary to form a conversion layer on the surface of the metal.
  • the present invention achieves the above advantages.
  • the method for coloring zinc, zinc-plated and alloy metal parts is characterized in that the part is subjected to the action of an acidic aqueous bath to make the surface of the porous part over a thickness which is a fraction of the thickness of zinc which it comprises and in that the part is made to adsorb at least one sealing material.
  • the method relates to the coloring of zinc parts. It is specified that these are massive zinc parts, for example parts made from sheet metal or parts covered with zinc by any known process, for example by hot-dip galvanizing of parts of another metal, in particular of ferrous metal parts, the thickness of zinc resulting from hot galvanizing being of the order of 14 microns.
  • Electro-galvanized parts are included in the same way in the process of the invention, the zinc thickness of an electro-galvanized part being between 5 and 30 microns.
  • the piece of zinc previously formed or formed by a sheet intended to be shaped later is subjected to the action of a bath consisting of a mixture of acids in solution in the water also containing halide ions, in particular fluoride ions.
  • acids such as nitric acid and acetic acid.
  • a porous layer slightly grayer in color than the initial zinc color forms on the surface, highlighting the moiré or so-called "flower” appearance that zinc usually presents.
  • at least one of the salts of these acids eg KNO3, KOOCCH3, etc.
  • a satisfactory treatment is carried out by preparing, for the first step of the process, an aqueous solution containing 10% by volume of nitric acid, 5% by volume of acetic acid and 2% by weight of fluoride of sodium.
  • the zinc part when the zinc part has been subjected to the acid treatment described above and then rinsed with water, it is transferred, for the second stage of the process, to an aqueous coloring bath or else it is sprayed with a coloring solution.
  • the aqueous coloring solution preferably contains organic dyes such as azo or anthraquinone dyes or dyes based on phthalocyanine, these dyes being preferred because of their purity and also because they are very soluble in water. .
  • organic dyes are preferred, it is nevertheless possible to use certain inorganic dyes, in particular ferric sodium or ammonium oxalate.
  • the zinc part is subjected, for the third step of the process, to the action of sealing agents adsorbed in the porous layer created and covering it.
  • These agents are preferably constituted by driers or by synthetic resins, in particular polyurethanes and / or melamines. It is also possible to use sealants based on silicones, in particular when the part must subsequently undergo forming operations, in particular by folding and / or elongation.
  • the parts leaving the acid bath are rinsed with demineralized water, for example by spraying.
  • the bath was stirred and kept at a temperature of 20 ° C. During the immersion time, the agitation was interrupted. The treated sheet was then extracted and rinsed with demineralized water sprayed in the form of a mist.
  • the gray color obtained initially does not undergo any modification during subsequent aging tests, in particular in a humid atmosphere.
  • a hot-dip galvanized steel sheet was used, the galvanization having a thickness of 14 microns.
  • the simply dusted sheet was immersed in a bath containing: 14% by weight of 65% nitric acid, 5% by weight of 85% acetic acid, 20 g / l of sodium fluoride.
  • the sheet was rinsed with demineralized water and then, before it dried, was then immersed for 5 minutes in a coloring bath consisting of an aqueous solution containing an azo dye Green Aluminum LWN at a concentration 4g / l.
  • the temperature of the coloring bath was 50 ° C.
  • the sheet was rinsed with ordinary water and then dried in the open air.
  • the green color conferred on the sheet does not undergo variations after accelerated aging tests corresponding to a usage time of 2 years in a humid atmosphere.
  • Example 2 The same operations as those described in Example 2 were carried out but the melamine sealing treatment was replaced by the application of a colorless polyurethane resin, the polymerization of which was initiated by baking at 80 ° C. for 30 minutes.
  • An electrogalvanized mild steel sheet was treated, the sheet having a thickness of 8/10 mm and the thickness of deposited zinc being 10 microns.
  • the sheet was only dusted and then immersed in a bath containing: 150 g / l of potassium nitrate, 5% by weight of 85% acetic acid, 20 g / l sodium fluoride
  • the sheet was then rinsed by spraying demineralized water, which highlighted the "flower” of zinc appearing through a porous layer of slightly gray color.
  • the sheet was immersed in an aqueous bath containing a non-metallized anthraquinone dye supplied by the company Sandoz under the name Sanodal, the concentration of the dye in the bath brought to the temperature of 45 ° C. being 6 g. / l.
  • the colored sheet was covered with a colorless polyurethane varnish.
  • the polymerization of the synthetic resins constituting the sealing product can in a known manner be initiated and / or accelerated by the action of ultraviolet, infrared, high frequency or microwave radiation.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Coloring (AREA)
  • Coating With Molten Metal (AREA)
  • Gasket Seals (AREA)

Abstract

Process for colouring articles made of zinc, zinc-plated and made of an alloy of this metal, characterised in that the article is subjected to the action of an acidic aqueous bath to make the surface of the article porous over a thickness which is a fraction of the thickness of the zinc which it comprises and in that at least one sealing material is caused to be adsorbed by the article.

Description

La présente invention concerne un procédé de coloration de surfaces métalliques en zinc, ou de métaux recouverts de zinc (pièces galvanisées, électrozinguées, etc.). Les couleurs obtenues appartiennent à tout le spectre visi­ble.The present invention relates to a process for coloring metallic surfaces of zinc, or of metals coated with zinc (galvanized, electro-galvanized parts, etc.). The colors obtained belong to the whole visible spectrum.

On connaît depuis longtemps des procédés de coloration du zinc permettant d'obtenir plusieurs couleurs, parmi lesquelles le noir et le brun sont les plus courantes. La plupart des techniques connues sont aujourd'hui abandon­nées car elles sont inadaptées à une industrialisation rentable. En réalité, selon C. BARNES, - The Coloration of Metals, Rev. Prog. Coloration, Vol. 14, p. 127 (1984) - les techniques qui permettent de colorer le zinc concernent les objets galvanisés ou électrozingués. Ces techniques de coloration sont en général employées afin d'accroître la résistance à la corrosion du zinc ; elles apparaissent alors plutôt comme des techniques de protec­tion anticorrosion, l'apport de la couleur n'étant pas initialement le but recherché.Zinc coloring processes have been known for a long time, making it possible to obtain several colors, of which black and brown are the most common. Most of the known techniques are today abandoned because they are unsuitable for profitable industrialization. In reality, according to C. BARNES, - The Coloration of Metals, Rev. Prog. Coloring, Vol. 14, p. 127 (1984) - the techniques which make it possible to color zinc concern galvanized or electro-galvanized objects. These coloring techniques are generally used to increase the corrosion resistance of zinc; they then appear rather as anti-corrosion protection techniques, the contribution of color not being initially the aim sought.

On peut citer ainsi les variations réalisées à partir du procédé CRONACK - ANDERSON, Proc. Am. Electroplater's Soc. Bow, 6 (1943) et ROPERT, Metal Finishing Journal, 14, N° 165, p. 285 (1968) qui, par chromatation, permet­tent de former à la surface du zinc une couche pouvant prendre, selon le cas, les couleurs jaune, verte, bronze ou noire.We can cite the variations made from the CRONACK-ANDERSON process, Proc. Am. Electroplater's Soc. Bow, 6 (1943) and ROPERT, Metal Finishing Journal, 14, N ° 165, p. 285 (1968) which, by chromating, make it possible to form on the surface of the zinc a layer which can take, depending on the case, the colors yellow, green, bronze or black.

Il est aussi possible de former à la surface du zinc un film de couleur bleu clair, résultant d'interférences optiques, avec une technique de chromatation aux propriétés anticorrosives moindres que celles du procédé CRONACK. Ce procédé ne convient cependant que pour l'identification par la couleur d'objets ainsi traités, car ce film a une durée de vie relativement courte.It is also possible to form on the surface of the zinc a film of light blue color, resulting from optical interference, with a technique of chromation with less anticorrosive properties than those of the CRONACK process. This process is however only suitable for the identification by color of objects thus treated, since this film has a relatively short lifespan.

Un procédé bien connu et utilisé actuellement en dépit de son coût élevé et de sa toxicité est celui utilisant la chromatation noire aux sels d'argent. On commence à lui préférer des procédés dont le plus important est basé sur l'action des sels de chrome trivalent - BARNES, WARD and CARTER, Inst. Metal Finishing Annuel Technical Conference (May 1982) - et qui colorent le zinc d'irisations bleues ou jaunes.A well-known process which is currently used despite its high cost and its toxicity is that using black chromation with silver salts. We are starting to prefer processes, the most important of which is based on the action of trivalent chromium salts - BARNES, WARD and CARTER, Inst. Metal Finishing Annual Technical Conference (May 1982) - and which color the zinc with blue or yellow iridescence.

La couleur grise est obtenue par phosphatation.The gray color is obtained by phosphating.

Enfin, le zinc peut être coloré en noir verdâtre, par anodisation dans une solution contenant des acides fluorhydrique, chromique et phosphorique, mais ce procédé est peut utilisé en raison des tensions élevées nécessai­res pour former une couche de conversion à la surface du métal.Finally, zinc can be colored greenish black by anodization in a solution containing hydrofluoric, chromic and phosphoric acids, but this process is not used because of the high voltages necessary to form a conversion layer on the surface of the metal.

On s'aperçoit ainsi qu'aucun de ces traitements de surface ne présente simultanément les avantages sui­vants :
- protection contre la corrosion
- variété des couleurs
- facilité de mise en oeuvre
- pas de toxicité
- faible coût.We can see that none of these surface treatments simultaneously offers the following advantages:
- corrosion protection
- variety of colors
- ease of implementation
- no toxicity
- low cost.

La présente invention permet d'obtenir les avantages ci-dessus.The present invention achieves the above advantages.

Conformément à l'invention, le procédé pour la coloration de pièces en zinc, zinguées et en alliage de ce métal, est caractérisé en ce qu'on soumet la pièce à l'action d'un bain aqueux acide pour rendre la surface de la pièce poreuse sur une épaisseur qui est une fraction de l'épais­seur de zinc qu'elle comporte et en ce qu'on fait adsor­ber par la pièce au moins une matière d'étanchéification.In accordance with the invention, the method for coloring zinc, zinc-plated and alloy metal parts, is characterized in that the part is subjected to the action of an acidic aqueous bath to make the surface of the porous part over a thickness which is a fraction of the thickness of zinc which it comprises and in that the part is made to adsorb at least one sealing material.

Diverses autres caractéristiques de l'invention ressor­tent d'ailleurs de la description détaillée qui suit.Various other characteristics of the invention will also emerge from the detailed description which follows.

Dans ce qui suit, il est indiqué que le procédé concerne la coloration de pièces en zinc. Il est précisé qu'il s'agit de pièces en zinc massives, par exemple de pièces fabriquées à partir de tôles ou de pièces recouvertes de zinc par un procédé quelconque connu, par exemple par galvanisation à chaud de pièces en un autre métal, notamment de pièces en métaux ferreux, l'épaisseur de zinc résultant de la galvanisation à chaud étant de l'ordre de 14 microns.In what follows, it is indicated that the method relates to the coloring of zinc parts. It is specified that these are massive zinc parts, for example parts made from sheet metal or parts covered with zinc by any known process, for example by hot-dip galvanizing of parts of another metal, in particular of ferrous metal parts, the thickness of zinc resulting from hot galvanizing being of the order of 14 microns.

Des pièces électrozinguées sont incluses de la même façon dans le procédé de l'invention, l'épaisseur de zinc d'une pièce électrozinguée étant comprise entre 5 et 30 microns.Electro-galvanized parts are included in the same way in the process of the invention, the zinc thickness of an electro-galvanized part being between 5 and 30 microns.

Selon le procédé de l'invention la pièce en zinc préala­blement mise en forme ou constituée par une tôle destinée à être mise en forme ultérieurement est soumise à l'ac­tion d'un bain constitué d'un mélange d'acides en solu­tion dans l'eau contenant aussi des ions halogénures, en particulier des ions fluorures.According to the process of the invention, the piece of zinc previously formed or formed by a sheet intended to be shaped later is subjected to the action of a bath consisting of a mixture of acids in solution in the water also containing halide ions, in particular fluoride ions.

Il est alors avantageux d'utiliser des acides tels que l'acide nitrique et l'acide acétique. Une couche poreuse de couleur légèrement plus grise que la couleur initiale du zinc se forme à la surface, mettant en valeur l'aspect moiré ou dit "de fleur" que présente habituellement le zinc. Il est aussi avantageux d'utiliser au moins l'un des sels de ces acides (ex : KNO₃, KOOCCH₃, etc.).It is therefore advantageous to use acids such as nitric acid and acetic acid. A porous layer slightly grayer in color than the initial zinc color forms on the surface, highlighting the moiré or so-called "flower" appearance that zinc usually presents. It is also advantageous to use at least one of the salts of these acids (eg KNO₃, KOOCCH₃, etc.).

A titre d'exemple, un traitement satisfaisant est conduit en préparant, pour la première étape du procédé, une solution aqueuse contenant 10 % en volume d'acide nitri­que, 5 % en volume d'acide acétique et 2 % en poids de fluorure de sodium.For example, a satisfactory treatment is carried out by preparing, for the first step of the process, an aqueous solution containing 10% by volume of nitric acid, 5% by volume of acetic acid and 2% by weight of fluoride of sodium.

Suivant un développement de l'invention, lorsque la pièce de zinc a été soumise au traitement acide décrit ci-­dessus puis rincée à l'eau, elle est transférée, pour la deuxième étape du procédé, dans un bain aqueux de colora­tion ou bien elle est soumise à une pulvérisation d'une solution de coloration.According to a development of the invention, when the zinc part has been subjected to the acid treatment described above and then rinsed with water, it is transferred, for the second stage of the process, to an aqueous coloring bath or else it is sprayed with a coloring solution.

La solution aqueuse de coloration contient de préférence des colorants organiques tels que des colorants azoïques ou anthraquinoniques ou encore des colorants à base de phtalocyanine, ces colorants étant préférés du fait de leur pureté et également du fait qu'ils sont très solu­bles dans l'eau.The aqueous coloring solution preferably contains organic dyes such as azo or anthraquinone dyes or dyes based on phthalocyanine, these dyes being preferred because of their purity and also because they are very soluble in water. .

Bien que les colorants organiques soient préférés, il est possible néanmoins d'utiliser certains colorants miné­raux, notamment de l'oxalate ferrique de sodium ou d'ammonium.Although organic dyes are preferred, it is nevertheless possible to use certain inorganic dyes, in particular ferric sodium or ammonium oxalate.

Après application du colorant, la pièce en zinc est soumise, pour la troisième étape du procédé, à l'action d'agents d'étanchéification adsorbés dans la couche poreuse créée et recouvrant celle-ci.After application of the dye, the zinc part is subjected, for the third step of the process, to the action of sealing agents adsorbed in the porous layer created and covering it.

Ces agents sont de préférence constitués par des produits siccatifs ou encore par des résines de synthèse, notam­ment des polyuréthannes et/ou des mélamines. Il est possible également aussi bien d'utiliser des produits d'étanchéification à base de silicones en particulier lorsque la pièce doit subir ultérieurement des opérations de formage, notamment par pliage et/ou allongement.These agents are preferably constituted by driers or by synthetic resins, in particular polyurethanes and / or melamines. It is also possible to use sealants based on silicones, in particular when the part must subsequently undergo forming operations, in particular by folding and / or elongation.

Afin d'éviter une détérioration du ou des colorants lorsque ceux-ci sont mis en oeuvre, il est avantageux que les pièces sortant du bain acide soient rincées à l'eau déminéralisée, par exemple par pulvérisation.In order to avoid deterioration of the dye or dyes when they are used, it is advantageous for the parts leaving the acid bath to be rinsed with demineralized water, for example by spraying.

On décrit maintenant différents exemples de mise en oeuvre de l'invention :We now describe various examples of implementation of the invention:

EXEMPLE 1EXAMPLE 1

Dans cet exemple, on a traité une tôle de zinc pur de 6/10 de mm d'épaisseur qui fut seulement dépoussiérée sans être soumise ni à un dégraissaage ni à un décapage chimique.In this example, a sheet of pure zinc 6/10 mm thick was treated which was only dusted without being subjected either to degreasing or to chemical pickling.

Elle fut immergée pendant 3 minutes dans un bain aqueux contenant :
10 % en volume d'acide nitrique à 65 %
5 % en volume d'acide acétique à 85 %
20 g/l de fluorure de sodium.It was immersed for 3 minutes in an aqueous bath containing:
10% by volume of 65% nitric acid
5% by volume of 85% acetic acid
20 g / l of sodium fluoride.

Avant l'immersion de la pièce, le bain fut agité et maintenu à une température de 20°C. Pendant la durée d'immersion, l'agitation fut interrompue. La tôle traitée fut ensuite extraite et rincée à l'eau déminéralisée projetée sous forme de brouillard.Before immersion of the piece, the bath was stirred and kept at a temperature of 20 ° C. During the immersion time, the agitation was interrupted. The treated sheet was then extracted and rinsed with demineralized water sprayed in the form of a mist.

Cette première phase de traitement mit en évidence la "fleur" ou le moirage du zinc dont l'aspect présentait un gris légèrement plus soutenu qu'avant le traitement.This first phase of treatment highlighted the "flower" or moire of zinc, the appearance of which presented a slightly stronger gray than before the treatment.

Après séchage, de la mélamine en solution dans de l'éthy­lène glycol fut projetée au pistolet pneumatique sur la tôle et cette dernière fut finalement maintenue en étuve à 140°C pendant 25 minutes.After drying, melamine in solution in ethylene glycol was sprayed on the sheet with a pneumatic gun and the latter was finally kept in an oven at 140 ° C for 25 minutes.

La couleur grise obtenue initialement ne subit aucune modification au cours d'essais de vieillissement ulté­rieur, notamment en atmosphère humide.The gray color obtained initially does not undergo any modification during subsequent aging tests, in particular in a humid atmosphere.

EXEMPLE 2EXAMPLE 2

Dans cet exemple, une tôle d'acier galvanisée à chaud fut utilisée, la galvanisation présentant une épaisseur de 14 microns.In this example, a hot-dip galvanized steel sheet was used, the galvanization having a thickness of 14 microns.

La tôle simplement dépoussiérée fut plongée dans un bain contenant :
14 % en poids d'acide nitrique à 65 %,
5 % en poids d'acide acétique à 85 %,
20 g/l de fluorure de sodium.The simply dusted sheet was immersed in a bath containing:
14% by weight of 65% nitric acid,
5% by weight of 85% acetic acid,
20 g / l of sodium fluoride.

L'immersion dura 1 minute dans le bain porté à la tempé­rature de 20°C.Immersion lasted 1 minute in the bath brought to a temperature of 20 ° C.

A la sortie du bain, la tôle fut rincée à l'eau déminé­ralisée puis, avant qu'elle ne sèche, fut plongée ensuite pendant 5 minutes dans un bain de coloration constitué par une solution aqueuse contenant un colorant azoïque Vert Aluminium LWN à une concentration de 4g/l.La tempé­rature du bain de coloration était de 50°C.At the end of the bath, the sheet was rinsed with demineralized water and then, before it dried, was then immersed for 5 minutes in a coloring bath consisting of an aqueous solution containing an azo dye Green Aluminum LWN at a concentration 4g / l. The temperature of the coloring bath was 50 ° C.

Après traitement la tôle fut rincée à l'eau ordinaire puis séchée à l'air libre.After treatment, the sheet was rinsed with ordinary water and then dried in the open air.

De la mélamine en solution dans de l'éthylène glycol fut ensuite projetée sur la tôle au moyen d'un pistolet électrostatique et celle-ci fut placée pendant 25 minutes dans une étuve portée à la température de 140°C. Le polymère ainsi appliqué sur la tôle était incolore.Melamine in solution in ethylene glycol was then sprayed onto the sheet using an electrostatic gun and this was placed for 25 minutes in an oven brought to a temperature of 140 ° C. The polymer thus applied to the sheet was colorless.

La couleur verte conférée à la tôle ne subit pas de variations à l'issue de tests de vieillissement accéléré correspondant à un temps d'usage de 2 ans en atmosphère humide.The green color conferred on the sheet does not undergo variations after accelerated aging tests corresponding to a usage time of 2 years in a humid atmosphere.

EXEMPLE 3EXAMPLE 3

Les mêmes opérations que celles décrites à l'exemple 2 furent mises en oeuvre mais le traitement d'étanchéi­fication à la mélamine fut remplacé par l'application d'une résine polyuréthanne incolore dont la polymé­risation fut amorcée par un étuvage à 80°C pendant 30 minutes.The same operations as those described in Example 2 were carried out but the melamine sealing treatment was replaced by the application of a colorless polyurethane resin, the polymerization of which was initiated by baking at 80 ° C. for 30 minutes.

EXEMPLE 4EXAMPLE 4

On traita une tôle d'acier doux électrozinguée, la tôle présentant une épaisseur de 8/10 de mm et l'épaisseur de zinc déposée étant de 10 microns.An electrogalvanized mild steel sheet was treated, the sheet having a thickness of 8/10 mm and the thickness of deposited zinc being 10 microns.

Comme dans les exemples précédents la tôle fut seulement dépoussiérée puis immergée dans un bain contenant :
150 g/l de nitrate de potassium,
5 % en poids d'acide acétique à 85 %,
20 g/l de fluorure de sodiumAs in the previous examples, the sheet was only dusted and then immersed in a bath containing:
150 g / l of potassium nitrate,
5% by weight of 85% acetic acid,
20 g / l sodium fluoride

L'immersion dura 3 minutes dans le bain porté à la température de 20°C. La tôle fut ensuite rincée par projection d'eau déminéralisée, ce qui mit en évidence la "fleur" du zinc apparaissant à travers une couche poreuse de couleur légèrement grise.The immersion lasted 3 minutes in the bath brought to a temperature of 20 ° C. The sheet was then rinsed by spraying demineralized water, which highlighted the "flower" of zinc appearing through a porous layer of slightly gray color.

Après le traitement au bain acide, la tôle fut immergée dans un bain aqueux contenant un colorant anthraquino­nique non métallisé fourni par la société Sandoz sous la dénomination Sanodal, la concentration du colorant dans le bain porté à la température de 45°C étant de 6 g/l.After the acid bath treatment, the sheet was immersed in an aqueous bath containing a non-metallized anthraquinone dye supplied by the company Sandoz under the name Sanodal, the concentration of the dye in the bath brought to the temperature of 45 ° C. being 6 g. / l.

Après séchage, la tôle colorée fut recouverte par un vernis polyuréthanne incolore.After drying, the colored sheet was covered with a colorless polyurethane varnish.

L'invention n'est pas limitée aux exemples de réalisation décrits en détail car diverses modifications peuvent y être apportées sans sortir de son cadre. En particulier, la polymérisation des résines de synthèse constituant le produit d'étanchéification peut de façon connue être amorcée et/ou accélérée par l'action d'un rayonnement ultraviolet, infrarouge, haute fréquence ou micro-ondes.The invention is not limited to the embodiments described in detail since various modifications can be made thereto without departing from its scope. In particular, the polymerization of the synthetic resins constituting the sealing product can in a known manner be initiated and / or accelerated by the action of ultraviolet, infrared, high frequency or microwave radiation.

Claims (12)

1 - Procédé pour la coloration de pièces en zinc, zin­guées et en alliage de ce métal, caractérisé en ce qu'on soumet la pièce à l'action d'un bain aqueux acide pour rendre la surface de la pièce poreuse sur une épaisseur qui est une fraction de l'épaisseur de zinc qu'elle comporte et en ce qu'on fait adsorber par la pièce au moins une matière d'étanchéification.1 - Process for coloring zinc, zinc-plated and alloyed parts of this metal, characterized in that the part is subjected to the action of an acidic aqueous bath to make the surface of the part porous over a thickness which is a fraction of the thickness of zinc it contains and in that the part is adsorbed by at least one sealing material. 2 - Procédé suivant la revendication 1, caractérisé en ce qu'on fait adsorber un colorant par la couche poreuse avant celle de la matière d'étanchéification.2 - Process according to claim 1, characterized in that a dye is adsorbed by the porous layer before that of the sealing material. 3 - Procédé suivant l'une des revendications 1 et 2, caractérisé en ce que le bain acide contient des ions halogènes (F⁻, Cl⁻, I⁻,...).3 - Method according to one of claims 1 and 2, characterized in that the acid bath contains halogen ions (F⁻, Cl⁻, I⁻, ...). 4 - Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que la solution aqueuse acide, dont la température est voisine de l'ambiante, contient de l'acide nitrique et de l'acide acétique.4 - Method according to one of claims 1 to 3, characterized in that the acidic aqueous solution, the temperature of which is close to ambient, contains nitric acid and acetic acid. 5 - Procédé suivant l'une des revendications 1 à 4, caractérisé en ce que la solution aqueuse acide, dont la température est voisine de la température ambiante, contient l'ion nitrate ou un autre anion d'un oxyacide d'azote ou un peroxyde, l'ion fluorure ou un autre ion halogéné seul ou lié à l'oxygène, l'ion acétate ou un autre ion carboxylate.5 - Method according to one of claims 1 to 4, characterized in that the acidic aqueous solution, the temperature of which is close to room temperature, contains the nitrate ion or another anion of a nitrogen oxyacid or a peroxide, fluoride ion or another halogenated ion alone or linked to oxygen, acetate ion or another carboxylate ion. 6 - Procédé suivant l'une des revendications 1 à 5, caractérisé en ce que la solution aqueuse colorante contient au moins un colorant et se présente à une température comprise entre l'ambiante et 60°C.6 - Method according to one of claims 1 to 5, characterized in that the aqueous coloring solution contains at least one dye and is at a temperature between ambient and 60 ° C. 7 - Procédé suivant l'une des revendications 1 à 6, caractérisé en ce qu'après traitement au bain acide la pièce est soumise à un rinçage puis en ce qu'on fait adsorber un colorant dans la couche poreuse avant l'ap­plication de la matière d'étanchéification sur cette couche.7 - Method according to one of claims 1 to 6, characterized in that after treatment with an acid bath the part is subjected to a rinsing then in that a dye is made to adsorb in the porous layer before the application of the sealing material on this layer. 8 - Procédé suivant l'une des revendications 1 à 7, caractérisé en ce que les colorants utilisés sont des colorants solubles dans l'eau.8 - Method according to one of claims 1 to 7, characterized in that the dyes used are water-soluble dyes. 9 - Procédé suivant l'une des revendications 1 à 8, caractérisé en ce que les colorants sont des colorants organiques plus particulièrement des colorants métal­lifères en particulier des colorants azoïques, anthraqui­noniques ou à base de phtalocyanine.9 - Method according to one of claims 1 to 8, characterized in that the dyes are organic dyes more particularly metalliferous dyes in particular azo dyes, anthraquinone or phthalocyanine. 10 - Procédé suivant l'une des revendications 1 à 9, caractérisé en ce que les colorants sont des colorants minéraux en particulier l'oxalate ferrique de sodium ou d'ammonium.10 - Process according to one of claims 1 to 9, characterized in that the dyes are mineral dyes in particular ferric oxalate of sodium or ammonium. 11 - Procédé suivant l'une des revendications 1 à 10, caractérisé en ce que les pièces en zinc, alliages de zinc ou revêtues de zinc sont soumises à l'action de la solution aqueuse acide, pendant la première étape du procédé, puis à la solution aqueuse colorante, lors de la deuxième étape du procédé, soit par immersion des pièces dans les solutions soit par pulvérisation des solutions sur les pièces.11 - Method according to one of claims 1 to 10, characterized in that the zinc parts, zinc alloys or coated with zinc are subjected to the action of the acidic aqueous solution, during the first step of the process, then to the aqueous coloring solution, during the second step of the process, either by immersing the parts in the solutions or by spraying the solutions onto the parts. 12 - Procédé suivant l'une des revendications 1 à 11, caractérisé en ce que la concentration en acide de la solution à laquelle sont soumises les pièces lors de la première étape du procédé, ainsi que le temps de traitement sont choisis pour créer une couche poreuse dont l'épaisseur est de l'ordre du micron.12 - Method according to one of claims 1 to 11, characterized in that the acid concentration of the solution to which the parts are subjected during the first step of the process, as well as the time of treatment are chosen to create a porous layer whose thickness is of the order of a micron.
EP88401251A 1987-05-25 1988-05-24 Process for colouring metal surfaces of zinc or zinc alloys or of zinc plated surfaces Expired - Lifetime EP0295980B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8707346A FR2615870B1 (en) 1987-05-25 1987-05-25 PROCESS FOR THE COLORING OF ZINC-PLATED, ZINC-PLATED AND ALLOYED SURFACES THEREOF
FR8707346 1987-05-25

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EP0295980A1 true EP0295980A1 (en) 1988-12-21
EP0295980B1 EP0295980B1 (en) 1991-12-18

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EP88401251A Expired - Lifetime EP0295980B1 (en) 1987-05-25 1988-05-24 Process for colouring metal surfaces of zinc or zinc alloys or of zinc plated surfaces

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EP (1) EP0295980B1 (en)
CA (1) CA1323827C (en)
DE (1) DE3866963D1 (en)
ES (1) ES2030878T3 (en)
FR (1) FR2615870B1 (en)

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JP6115548B2 (en) * 2014-11-13 2017-04-19 Ｊｆｅスチール株式会社 Method for producing electrogalvanized steel sheet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2086712A (en) * 1932-01-21 1937-07-13 Parker Rust Proof Co Coating zinc and the coated article
FR2378828A1 (en) * 1977-01-28 1978-08-25 Parker Ste Continentale BLACK COLORING COMPOSITION AND ITS APPLICATION TO THE TREATMENT OF METAL PARTS
EP0083263A2 (en) * 1981-12-30 1983-07-06 Asturienne France Process for applying a block coating to objects having at least one zinc surface

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1994499A (en) * 1932-12-31 1935-03-19 Grasselli Chemical Co Engraver's etching acid of increased efficiency
JPS54145336A (en) * 1978-05-04 1979-11-13 Mitsui Mining & Smelting Co Dyeing zinc and zinc alloys
US4200475A (en) * 1978-09-26 1980-04-29 Mitsui Mining & Smelting Co., Ltd. Process for dyeing aluminum-containing zinc-based alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2086712A (en) * 1932-01-21 1937-07-13 Parker Rust Proof Co Coating zinc and the coated article
FR2378828A1 (en) * 1977-01-28 1978-08-25 Parker Ste Continentale BLACK COLORING COMPOSITION AND ITS APPLICATION TO THE TREATMENT OF METAL PARTS
EP0083263A2 (en) * 1981-12-30 1983-07-06 Asturienne France Process for applying a block coating to objects having at least one zinc surface

Non-Patent Citations (1)

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Title
PATENT ABSTRACTS OF JAPAN, vol. 11, no. 85 (C-410)[2532], 14 mars 1987; & JP-A-61 238 979 (KOBE STEEL LTD) 24-10-1986 *

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DE3866963D1 (en) 1992-01-30
EP0295980B1 (en) 1991-12-18
FR2615870B1 (en) 1992-12-31
ES2030878T3 (en) 1992-11-16
CA1323827C (en) 1993-11-02
FR2615870A1 (en) 1988-12-02
US4943453A (en) 1990-07-24

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