EP0407015A1 - Produit métallique à revêtement de phosphate, procédé de sa production, concentré à utiliser dans ce procédé et concentré pour le remontage de la solution de revêtement - Google Patents

Produit métallique à revêtement de phosphate, procédé de sa production, concentré à utiliser dans ce procédé et concentré pour le remontage de la solution de revêtement Download PDF

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Publication number
EP0407015A1
EP0407015A1 EP90305186A EP90305186A EP0407015A1 EP 0407015 A1 EP0407015 A1 EP 0407015A1 EP 90305186 A EP90305186 A EP 90305186A EP 90305186 A EP90305186 A EP 90305186A EP 0407015 A1 EP0407015 A1 EP 0407015A1
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Prior art keywords
zinc
ion
phosphate
film
treating
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EP90305186A
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German (de)
English (en)
Inventor
Akio Tokuyama
Koetsu Endo
Tamotsu Sobata
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Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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Publication of EP0407015A1 publication Critical patent/EP0407015A1/fr
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    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/367—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing alkaline earth metal cations
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the present invention relates to a coating product in which, as pre-treatment ( under treatment ) for coating, in particular, pre-treatment for cationic electrocoating, a phosphate film is formed on a metal surface, and to a process for producing the product, a concentrated agent for treating with phosphate, and a concentrated treating agent for supplementary use.
  • an aqueous acidic phosphate-treating solution which, as essential components, contains a zinc ion, a phosphoric ion as well as a nitrite ion and/or a m-nitrobenzenesufonate ion in the concentrations; 0.5 ⁇ 1.5 g/l for the zinc ion, 5 ⁇ 30 g/l for the phosphate ion, and 0.01 ⁇ 0.2 g/l for the nitrite ion and/or 0.05 ⁇ 2 g/l for the m-nitrobenzenesulfo­nate ion.
  • the method is carried out by first subjecting the metal surface to dipping treatment with said aqueous acidic phosphate-treating solution for 15 seconds or more at temperature of 40 ⁇ 70 °C, and followed by spraying for 2 seconds or more.
  • a conversion film which is suitable for electrocoating became possible to be provided by treating with zinc phosphate by means of an immersing method and thus, the immersing method has established a firm ground for conversion treatment with zinc phosphate, of which main object is an improvement of corrosion-resistance not only for building materials and small articles, but also for wide variety of articles such as an automobile body and automobile parts which have an iron and zinc surfaces and these alloy surfaces.
  • a treating process which is a process for treating with zinc phosphate for a metal surface that has an iron-based surface or both the iron-based surface and a zinc-based surface, and with which not only a conversion film of corrosion-resistance which is suitable for coating, in particular, for electrocoating is given, but also the resistance against scab corrosion ( hereinafter refered to as "scab-resistance” ) on the iron-­based surface and the resistance against warm brine of the iron-based surface and zinc-based surface are greatly improved as well as the secondary adhesion when the intermediate and top coating on the electrocoated plate being carried out is further improved.
  • scab-resistance resistance against scab corrosion
  • the first object of the present invention is to provide a coating product in which a conversion film having corrosion-resistance is formed in the pre-treatment suitable for the cationic electrocoating, scab-resistance of an iron-based surface as well as resistance of an iron-­based surface and a zinc-based surface against warm brine are greatly improved, and also the secondary adhesion is improved when the electrocoating, intermediate coating, and top coating are carried out.
  • the second object of the present invention is to provide a process for producing which is able to obtain a coating product such as the forementioned product by treatment at low temperature.
  • the third object of the present invention is to provide concentrated agents which are used for said process.
  • the coating product relating to the invention as claimed in the claim 1, having a zinc phosphate film for coating on a metal surface and thereon a coating film is specialized by that the zinc phosphate film contains 20 ⁇ 42 weight % of zinc, 0.5 ⁇ 8 weight % of calcium, and 1.0 ⁇ 8 % weight of nickel.
  • the process for producing the coating product relating to the invention as claimed in the claim 2 is specialized by that, as a pre­treatment for coating, a dipping treatment of the metal surface is carried out in an aqueous solution for treating with acidic phosphate, which contains, as essential components, at least, a zinc ion in concentration of 0.1 ⁇ 2 g/l, a phosphate ion in concentration of 5 ⁇ 40 g/l, a calcium ion in concentration of 0.5 ⁇ 4 g/l, a nickel ion in concentration of 0.5 ⁇ 4 g/l, a fluorine compound in concentration of 0.05 ⁇ 4 g/l ( on a basis being converted into a fluoride ion ), and an accelerator for converting into a film, in such proportion that their weight ratios are 0.5 ⁇ 4.0 between the calcium ion and the zinc ion ( hereinafter, taking the former ion as a numerator and the latter ion as a
  • the concentrated phosphate treating agent relating to the invention as claimed in the claim 3 is led by being diluted with water to said aqueous solution for treating with an acidic phosphate.
  • the concentrated treating agent for supplementary use relating to the invention as claimed in the claim 4 is used to supplement a lacking component when the component in said aqueous solution for treating with acidic phosphate is consumed during said process.
  • said aqueous solution for treating with acidic phosphate in case of necessity, contains a water-soluble tungsten compound in concentration of 0.005 ⁇ 20 g/l as the tungsten element.
  • weight of the film can be increased, so that the effect of this invention can be displayed in a multiplication way.
  • the present invention is most effective for a case of that a metal surface having both the iron-based suface and the zinc-based surface at the same time is an object for treating, but not only this case, but also with a similar object an iron-based surface only or a zinc-based surface only as well as a zinc alloy-based surface can be treated.
  • a metal surface having both the iron-based suface and the zinc-based surface at the same time is an object for treating, but not only this case, but also with a similar object an iron-based surface only or a zinc-based surface only as well as a zinc alloy-based surface can be treated.
  • iron-based surface are cited a cold rolled steel plate, a hot rolled steel plate, and an acid-washed hot rolled steel plate.
  • As said zinc-based and zinc alloy-­based surfaces are pratically cited, for example, a hot dipped galvanized steel plate, a hot dipped zinc alloy plated steel plate, an electro galvanized steel plate, and an electro zinc-all
  • a phosphate film modified by that 20 % or more of zinc, 0.5 % or more of calcium, and 1.0 % or more of nickel is contained for improvement of the rust-resistance and secondary adhesion. If the calcium contents of said zinc phosphate coating film modified are less than 0.5 weight %, the warm brine-resistance on the iron-based surface does not sufficiently elevate and the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces does not sufficiently elevate. Said calcium contents are preferable if those are 8 weight or less.
  • the warm brine-resistance on the iron-based surface may lower and, if the contents exceed 42 weight %, the scab-­resistance on the iron-based surface as well as the water-­resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces may lower.
  • the weight of said zinc phosphate film modified with calcium and nickel prefers to be 0.5 ⁇ 5 g/m2 in a case of formation on the iron-based surface and more prefers to be 1.5 ⁇ 3 g/m2. If the weight of the film is less than 0.5 g/m2, the warm brine-resistance and scab-resistance on the iron-based surface may not elevate sufficiently and, if it exceeds 5 g/m2, elevation of the effects reachs to the top and an economical disadvantage may happen.
  • the weight of said zinc phosphate film modified with calcium and nickel, when it is formed on the zinc-based and zinc alloy-based surfaces prefers to be 0.5 ⁇ 10 g/m2 and more prefers to be 3 ⁇ 5 g/m2.
  • the warm brine-resistance on the zinc-based and zinc alloy-based surfaces may not elevate sufficiently and, if it exceeds 10 g/m2, the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces may lower.
  • a metal surface is degreased by being sprayed with an alkaline degreasing agent at the temperature of 30 ⁇ 60 °C for 2 minutes and/or by being subjected to dipping treatment with the agent, rinsed with water, and then treated with spraying of a surface conditioner at room temperature for 10 ⁇ 30 seconds and/or with dipping.
  • a metal surface treated with the surface conditioner is treated with dipping at the temperature of 30 ⁇ 70 °C for 15 seconds or more by using an aqueous solution for treating with acidic phosphate which contains a zinc ion, a phosphate ion, a calcium ion, a nickel ion, and a fluoro compound as well as an accelerator for converting into a film as the main components. Then, it is rinsed with tap water and further with deionized water, wherby a metal surface treated with coating pre-treatment is obtained. On the pre-treatment of the metal surface, for example, usual cationic electrocoating and furthermore, in case of necessity, intermediate coating and top coating are carried out to get a electrocoated product.
  • the treating temperature for said aqueous solution for treating with acidic phosphate prefers to be 30 ⁇ 70 °C and more prefers to be 35 ⁇ 60 °C . If temperature is lower than the range, the converting into a film is bad and the treating may require a long period and also, if it is higher than the range, decomposition of the accelerator for converting into a film and precipitation of the treating solution may take place, so that balancing of the treating solution may easily collapse and a superior film is hard to get.
  • the treating time for dipping prefers to be 15 seconds or more and more prefers to be 30 ⁇ 120 seconds. If it is less than that, a film having desired crystals may not sufficiently be formed.
  • the treating practically requires dipping for 15 seconds or more or, more preferably, for 30 ⁇ 90 seconds and then, spraying for 2 seconds or more or, more preferably, for 5 ⁇ 45 seconds.
  • the spray treatment is preferably carried out for as long a period as possible.
  • the dipping treatment according to the present invention includes combination of the dipping in said aqueous solution for treating with phosphate followed by spraying.
  • the zinc ion which is a main component of said aqueous solution for treating with acidic phosphate prefers concentration of 0.1 ⁇ 2 g/l and more prefers that of 0.7 ⁇ 1.2 g/l. If the concentration is less than 0.1 g/l, the phosphate film is not uniformly formed on the iron-based surface and a film of blue color partly is formed.
  • the phosphate film being formed on the iron-based surface easily converts into crystals of a leaf shape and also, since the calcium contents in the film become less than 0.5 weight %, the warm brine-resistance can not sufficiently be elevated and the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces can not sufficiently be elevated.
  • the phosphate ion prefers concentration of 5 ⁇ 40 g/l and more prefers that of 10 ⁇ 20 g/l. If it is less than 5 g/l, an ununiform film is apt to be formed and also, if it exceeds 40 g/l, the elevation of effects reachs to the top resulting in waste of chemicals with an economical disadvantage.
  • the calcium ion prefers concentration of 0.5 ⁇ 4 g/l and more prefers that of 0.5 ⁇ 2 g/l . If it is less than 0.5 g/l, the calcium contents in a film become less than 0.5 weight %, so that the warm brine-resistance on the iron-based surface is not sufficiently elevated and the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces is not sufficiently elevated. If it exceeds 4 g/l, not only the elevation of effects reachs to the top, but also the warm brine-resiastance on the iron-based surface trends to decrease with lowering of the film quantity.
  • the weight ratio between the calcium ion and zinc ion is set in a range of 0.5 ⁇ 4. If the weight ratio is less than 0.5, calcium contents of a film become less than 0.5 weight % and, the warm brine-­resistance on the iron-based surface is not sufficiently elevated and the water-resisting, secondary adhesion is not sufficiently elevated. Also, if the ratio exceeds 4, the elevation of effects reachs to the top as well as a decreasing trend in the film quantity and in the warm brine-resistance is seen.
  • the nickel ion prefers concentration of 0.5 ⁇ 4 g/l and more prefers that of 0.5 ⁇ 2 g/l. If the concentration is less than 0.5 g/l, the nickel contents in a film become less than 1 weight %, so that the scab-­resistance on the iron-based surface is not sufficiently elevated and the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces is not sufficiently elevated. If the concentration exceeds 4 g/l, not only the elevation of effects reachs to the top, but also there is seen a decreasing trend of the warm brine-­resistance on the iron-based surface with decresing quantity of the film.
  • the weight ratio between the nickel ion and the zinc ion is set in a range of 1.0 ⁇ 4.0. If the weight ratio is less than 1.0, the nickel contents in the film become less than 1.0 weight % and, the scab-­resistance on the iron-based surface and the water-­resisting, secondary adhesion on the zinc-based surface are not elevated and also, if the weight ratio exceeds 4.0, the elevation of effects reachs to the top as well as a decreasing trend of the film quantity and of the warm brine-­resistance on the iron-based surface is seen.
  • the fluorine compound prefers, on a basis being converted into a fluoride ion, concentration of 0.05 ⁇ 4 g/l and more prefers that of 0.1 ⁇ 2 g/l . If the concentration is less than 0.05 g/l, the phosphate-treating at low temperature is not attained, so that the calcium contents in the film become less than 0.5 weight % and then, the warm brine-resistance on the iron-based surface is not sufficiently elevated and the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces is not sufficiently elevated.
  • the concentration exceeds 4 g/l, not only the elevation of effects reachs to the top resulting in an economical disadvantage, but also there is seen a decreasing trend of the warm brine-resistance on the iron-based surface with decresing quantity of the film.
  • the weight ratio between the fluorine compound and the phosphate ion is set in a range of 0.05 ⁇ 2 which is calculated on a basis being converted into the orthophosphate ion ( PO4 ).
  • the weight ratio is less than 0.05, the calcium contents in the film become less than 0.5 weight % and thus, the warm brine-resistance on the iron-based surface is not sufficiently elevated as well as the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces is not elevated. Also, if the weight ratio exceeds 2, the elevation of effects reachs to the top resulting in an economical disadvantage.
  • Said aqueous solution for treating with acidic phosphate prefers to contain, in case of necessity, a water-soluble tungsten compound in concentration of 0.005 ⁇ 20.0 g/l calculated on a basis being converted into the tungsten element and more prefers to contain the compound in concentration of 0.05 ⁇ 10 g/l. If the amount of the water-soluble tungsten compound is less than the above range, the effect on increase of the film weight quantity without deterioration of the film quality can not be obtained and, if the amount exceeds the above range, an sufficiently good effects are not obtained and instead, the amount of chemicals for use increases resulting in an economical disadvantage.
  • aqueous solution for treating with acidic zinc phosphate for example, at least one kind of agent selected from a nitrite ion, m-nitrobenzenesulfonate ion, and hydrogen peroxide is used.
  • the nitrite ion prefers concentration of 0.01 ⁇ 0.2 g/l and more prefers that of 0.04 ⁇ 0.15 g/l.
  • the m-nitrobenzenesulfonate ion prefers concentration of 0.05 ⁇ 2 g/l and more prefers that of 0.1 ⁇ 1.5 g/l.
  • the hydrogen peroxide prefers concentration of 0.5 ⁇ 5 g/l, calculated on a basis being converted into 100 % H2O2, and more prefers that of 1 ⁇ 4 g/l. If these accelerators for converting into a film does not reach to the above concentration range, sufficient conversion into a film on the iron-based surface is not attained and instead, conversion into a yellow rust occurs and, if the agent exceeds the above concentration range, an ununiform film of blue color is apt to be formed on the iron-based surface.
  • the zinc ion for example, zinc oxide, zinc carbonate, and zinc nitrate etc. are used.
  • the phosphate ion is supplied from, for example, phosphoric acid, zinc phosphate, and calcium phosphate etc.
  • the calcium ion is supplied from, for example, calcium carbonate, calcium nitrate, calcium chloride, and calcium phosphate etc.
  • the nickel ion is supplied from, for example, nickel carbonate, nickel nitrate, nickel chloride, and nickel phosphate etc.
  • the fluoro compound is supplied from, for example, hydrogen fluoride ( hydrofluoric acid ), fluoboric acid, fluosilic acid, and these metal salts (for example, a zinc salt and a nickel salt, but a sodium salt is excluded because an expected effect is not attained ) and so on.
  • the water-soluble tungsten compounds of suitable use are, for example, a tungstate such as sodium tungstate and ammonium tungstate, borotungstic acid, phosphotungstic acid, phosphotungstate, and in addition, particularly silicotungstic acid and silicotungstate.
  • said aqueous solution for treating with acidic phosphate may contain only the forementioned essential components, or besides the essential components, may contain, for example, a nitrate ion and a chlorate ion etc., respectively by alone or in combination of the two or more kinds.
  • the nitrate ion prefers concentration of 1 ⁇ 10 g/l and more prefers that of 2 ⁇ 8 g/l.
  • the chlorate ion prefers concentration of 0.05 ⁇ 2 g/l and more prefers that of 0.2 ⁇ 1.5 g/l.
  • nitrate ion sodium nitrate, ammonium nitrate, zinc nitrate, and nickel nitrate etc.
  • chlorate ion sodium chlorate and ammonium chlorate etc.
  • the aqueous solution for treating with acidic phosphate of said composition is obtained by diluting with water the concenrated phosphate-treating agent relating to the present invention.
  • the aqueous solution for treating with acidic phosphate used in the pre-treatment for electrocoating etc. is not generally marketed in a concentration adjusted for acutual use and, instead, has been arranged as a concentrated solution for preparing in use.
  • the concentrated phosphate-treating solution should contain, for getting the treating solution of said composition by diluting 1 ⁇ 4 g of the concentrated phosphate-treating solution with 100 ml of water ( 1 ⁇ 4 w/v % ), sufficient amounts of the zinc ion resources, phosphate ion resource, calcium ion resource, nickel ion resource, and fluorine compound resource and, in case of necessity, the water-soluble tungsten compound resource, but should not contain a sodium derivative and a manganese derivative. If the fluoride ion and sodium ion coexists, a problem of precipitate formation may take place when said treating solution is prepared. Also, no use of a manganese derivative is an important point.
  • a sodium derivative for example, sodium nitrite, sodium nitrate, sodium chlorate, and sodium tungstate etc. .
  • a sodium derivative for example, sodium nitrite, sodium nitrate, sodium chlorate, and sodium tungstate etc.
  • the concentrated treating agent for supplementary use relating to the present invention is used to supplement a lacking component when the component in the aqueous solution for treating with acidic phosphate is consumed during the pre-treatment for coating such as cationic electrocoating. That is, when said aqueous solution for treating with acidic phosphate is used on the pre-treatment for cationic electrocoating, all the components are not consumed in the same proportion, but a component is consumed in an one-sided manner. Because of this, a suplementation of the consumed component is carried out by adding the concentrated treating agent for suplementary use into said aqueous solution for treating with acidic phosphate.
  • the concentrated treating agent for suplementary use is excemplified as the undermentioned A, A′, and B.
  • ⁇ part ⁇ To 28 weight parts ( hereinafter simply referred to as ⁇ part ⁇ ) of water were added 45 parts of 75 % phosphoric acid, and 5 parts of 70 % nitric acid, and then 10 parts of zinc white ( zinc oxide ) were added and dissolved. Furthermore, 5 parts of calcium carbonate and 5 parts of nickel carbonate were added and dissolved, and after cooling, 2 parts of 40 % fluosilicic acid were added with good mixing, whereby 100 parts in total of the concentrated treating agent were obtained.
  • the method for preparing the concentrated treating agent for supplementary use A was repeated except that 27.9 parts of water and 0.1 part of silicotungstic acid were dissolved, whereby 100 parts in total of the concentrated treating agent A′ were obtained.
  • the warm brine-resistance and scab-­resistance on the iron-based surface are enhanced without use of manganese and also, the water-resisting, secondary adhesion on the zinc-based and zinc alloy-based surfaces are enhanced.
  • the scab-resistance is elevated more than the case of manganese modification.
  • a zinc phosphate film modified with calcium and nickel is formed on a metal surface by that, as pre-­treatment, dipping treatment of the metal surface is carried out in an aqueous solution for treating with acidic phosphate, which contains, as essential components, at least a zinc ion, a phosphate ion, a calcium ion, a nickel ion, and a fluorine compound as well as an accelerator for converting into a film and also, contains a zinc ion in concentration of 0.1 ⁇ 2 g/l, a phosphate ion in concentration of 5 ⁇ 40 g/l, a calcium ion in concentration of 0.5 ⁇ 4 g/l, a nickel ion in concentration of 0.5 ⁇ 4 g/l , and a fluorine compound in concentration of 0.05 ⁇ 4 g/l ( on a basis being converted into a fluoride ion ) in such proportion that their weight ratios are 0.5 ⁇ 4.0 between the calcium ion and the zinc i
  • the film thickness can be increased without deterioration in quality of the zinc phosphate film and with enhancing properties of the film.
  • a surface-conditioning agent Surf Fine 5N-5, made by Nippoon Paint Co., Ltd., 0.1 weight % concentration
  • dipping treatment was carried out at room temperature for 15 seconds.
  • Drying was carried out with hot air at 100 °C for 10 minutes.
  • the film was dissolved by using a chromic acid solution, the weight of the dissolved film determined, and the amounts of zinc, calcium, nickel, and manganese in the film-dissolved solution were determined with an atomic absorption analysis method, and thus the contents of each metal in the film ( weight % ) were determined.
  • a cationic electrocoating composition ( Power Top U-­1000 Grey, made by Nippon Paint Co., Ltd. ) was coated so as to make a dry film of thickness 35 ⁇ m after baking ( voltage 240 V, current-carrying capacity 0.16 coulombs/cm2, electricity-applying time 3 minutes ), and the surface was baked at 170 °C for 20 minutes.
  • a part of the electrocoated plates thus-obtained were used for the hot brine dipping test.
  • the other remaining electrocoated plates were coated with an intermediate coating compositon ( Orga TO 4811 Grey, made by Nippon Paint Co., Ltd., melamine-alkyd resin base ) by spraying so as to make a dry film of thickness 30 ⁇ m after baking, and the surfaces were baked at 140 °C for 20 minutes.
  • an intermediate coating compositon Orga TO 4811 Grey, made by Nippon Paint Co., Ltd., melamine-alkyd resin base
  • a top coating composition ( Orga TO 630 Dover White, made by Nippon Paint Co., Ltd., melamine-alkyd resin base ) by spraying so as to make a dry film of thickness 30 ⁇ m after baking, and the surfaces were baked at 140 °C for 20 minutes, to obtain coated plates having in total the 3-coatings and 3-bakings, which were then subjected to the adhesion test and scab-­corrosion test.
  • the coated plate was dipped in deionized water at 40 °C for 20 days and provided with grids ( 100 squares each ) which were made at 1 mm intervals and 2 mm intervals using a sharp cutter.
  • grids 100 squares each
  • an adhesive tape was applied, after which it was peeled off and the number of remaining coated squares on the coated plate was counted as the adhesive test result.
  • the example for comparison 2 does not contain nickel, the water-resisting secondary adhesion and scab-resistance are especially inferior and, since the example for comparison 3 does not contain calcium, the warm brine-­resistance is especially inferior. Since the example for comparison 4 does not use calcium and nickel, but manganese, the scab-resistance is inferior.
  • the example for comparison 6 shows in the treating solution a weight ratio between the nickel ion and zinc ion as lower than 1.0, the nickel contents in the film is less than 1.0 weight %, and, as a result, the water-­ resisting secondary adhesion on the zinc-based surface and the scab-resistance on the cold rolled steel plate are both bad.
  • the example for comparison 8 shows a weight ratio between the nickel ion and zinc ion as lower than 1.0 and a weight ratio between the fluorine compound converted in to the fluorine element and the phosphate ion converted into the orthophosphoric acid as lower than 0.05, the nickel contents in the film is less than 1 weight %, and, as a result, the scab-resistance on the cold rolled steel plate is bad.
  • the alkali-resisting solubilities of zinc phosphate films on the conversion-treated plates in said example 1, and examples for comparison 3 and 4 are shown in Fig. 1.
  • the curve 1 is for the example for comparison 3, the curve 2 for the example for comparison 4, and the curve 3 for the example 1.
  • the conversion-treated plates were subjected to cationic electrocoating under a condition of three kinds of electric currents ( boosted from 0 volt to a set voltage during 30 seconds and treated with currents of a set voltage of 220 V and a constant voltage of 260 and 290 V for 2.5 minutes ) and the alkali-resisting solubilities were determined with variation of a corroding current value ( Ic ) for a conversion-treated plates in which a wet coating film that is before putting together by baking and hardening was dissolved in tetrahydrofuran. As the Ic value is smaller and smaller, the corroding is harder.
  • the corroding current value ( Ic ) was determined under a condition of that an area in contact with the solution was 1 cm2 and the electrolyte was a 3 weight % solution of sodium chloride of 20 °C.
  • the cross axis indicates current-­carrying capacity during cationic electrocoating. As seen in Fig. 1, the product from the example 1 hardly suffers coating film damage.
  • the coating product relating to the invention as claimed in claim 1 has a zinc phosphate film being formed as pre-treatment for coating which contains zinc in an amount of 20 ⁇ 42 weight %, calcium in an amount of 0.5 ⁇ 8 weight %, and nickel in an amount of 1.0 ⁇ 8 weight % and, thus, the scab-resistance on the iron-based surface and the warm brine-resistance on the iron-based and zinc-based surfaces are greatly improved, and further improvement of the secondary adhesion is shown when the electrocoating, intermediate coating, and top coating are performed on said film.
  • the concentrated phosphate treating agent relating to the invention as claimed in claim 3 is used, with proper dilution by water, for preparing the aqueous solution for treating with acidic phosphate, which is used for forming a zinc phosphate film modified with calcium and nickel with low temperature treatment.
  • the concentrated treating agent for supplementary use relating to the invention as claimed in claim 4 is used for adjusting the component in the aqueous solution for treating with acidic phosphate, which is used to form a zinc phosphate film modified with calcium and nickel.
  • the zinc phosphate film modified with calcium and nickel is able to increases the film weight without deterioration in quality of the film.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
EP90305186A 1989-05-15 1990-05-15 Produit métallique à revêtement de phosphate, procédé de sa production, concentré à utiliser dans ce procédé et concentré pour le remontage de la solution de revêtement Withdrawn EP0407015A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12077589 1989-05-15
JP120775/89 1989-05-15

Publications (1)

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EP0407015A1 true EP0407015A1 (fr) 1991-01-09

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EP90305186A Withdrawn EP0407015A1 (fr) 1989-05-15 1990-05-15 Produit métallique à revêtement de phosphate, procédé de sa production, concentré à utiliser dans ce procédé et concentré pour le remontage de la solution de revêtement

Country Status (3)

Country Link
EP (1) EP0407015A1 (fr)
JP (1) JPH0375379A (fr)
CA (1) CA2016798A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0759096A4 (fr) * 1994-05-11 1997-06-04 Henkel Corp Procede de pre-traitement de materiaux en aluminum avant leur peinture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015165600A1 (fr) 2014-04-30 2015-11-05 Rio Verwaltungs Ag Dispositif et procédé de traitement pour décaper et phosphater des pièces métalliques
JP7729641B2 (ja) * 2024-02-02 2025-08-26 株式会社ケミコート カチオン電着塗装の前処理用のリン酸亜鉛皮膜化成剤

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1391804A (fr) * 1962-12-26 1965-03-12 Lubrizol Corp Solutions de phosphatation et leur procédé d'application
FR2111665A1 (fr) * 1970-10-16 1972-06-09 Lubrizol Corp
EP0015020A1 (fr) * 1979-02-14 1980-09-03 Metallgesellschaft Ag Procédé de traitement de surfaces de métaux et son utilisation pour le traitement de surfaces en aluminium
EP0018841A1 (fr) * 1979-05-02 1980-11-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition et procédé pour revêtir de phosphate de zinc la surface d'un métal, surface revêtue d'un métal et procédé pour le vernissage de la surface enduite
EP0045110A1 (fr) * 1980-07-25 1982-02-03 Metallgesellschaft Ag Procédé pour la production de revêtements de phosphate sur les surfaces de fer et d'acier et son usage
EP0155547A1 (fr) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1391804A (fr) * 1962-12-26 1965-03-12 Lubrizol Corp Solutions de phosphatation et leur procédé d'application
FR2111665A1 (fr) * 1970-10-16 1972-06-09 Lubrizol Corp
EP0015020A1 (fr) * 1979-02-14 1980-09-03 Metallgesellschaft Ag Procédé de traitement de surfaces de métaux et son utilisation pour le traitement de surfaces en aluminium
EP0018841A1 (fr) * 1979-05-02 1980-11-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition et procédé pour revêtir de phosphate de zinc la surface d'un métal, surface revêtue d'un métal et procédé pour le vernissage de la surface enduite
EP0045110A1 (fr) * 1980-07-25 1982-02-03 Metallgesellschaft Ag Procédé pour la production de revêtements de phosphate sur les surfaces de fer et d'acier et son usage
EP0155547A1 (fr) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0759096A4 (fr) * 1994-05-11 1997-06-04 Henkel Corp Procede de pre-traitement de materiaux en aluminum avant leur peinture
US5795407A (en) * 1994-05-11 1998-08-18 Henkel Corporation Method for pre-treating aluminum materials prior to painting

Also Published As

Publication number Publication date
JPH0375379A (ja) 1991-03-29
CA2016798A1 (fr) 1990-11-15

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