CA2381774A1 - Process for forming a phosphate conversion coating on metal - Google Patents
Process for forming a phosphate conversion coating on metal Download PDFInfo
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- CA2381774A1 CA2381774A1 CA002381774A CA2381774A CA2381774A1 CA 2381774 A1 CA2381774 A1 CA 2381774A1 CA 002381774 A CA002381774 A CA 002381774A CA 2381774 A CA2381774 A CA 2381774A CA 2381774 A1 CA2381774 A1 CA 2381774A1
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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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
- C23C22/368—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 magnesium cations
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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
- C23C22/40—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
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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
- C23C22/73—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 characterised by the process
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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
- C23C22/78—Pretreatment of the material to be coated
Abstract
A metal surface on which a phosphate conversion coating is to be formed and which has been surface conditioned by contact with a liquid surface conditioner composition that contains dispersed fine particles of solid phosphate of at least one divalent or trivalent cations type and an adhesion promoting agent. After such conditioning, a very high quality conversion coating can be formed on the surface by contact with a nickel-free liquid phosphating composition that contains at least acid, zinc cations, and phosphate anions and optionally and preferably also contains other materials.
Description
Description PROCESS FOR FORMING A PHOSPHATE CONVERSION COATING ON METAL
FIELD AND BACKGROUND OF THE INVENTION
This invention relates to processes for the phosphate conversion treatment of metals wherein said processes employ a nickel ion-free phosphate conversion treatment bath and produce a uniform, strongly paint-adherent, and highly post-painting corrosion-resistant coating on such metals as steel sheet, zinc-plated steel sheet, aluminum alloys, and magnesium alloys.
Phosphate conversion treatments are currently executed as a pre-paint treatment on automotive body components in order to enhance corrosion resistance and improve the steel sheet-to-paint adherence. In these phosphate conversion treatments, the metal ,o is first brought into contact with a colloidal titanium surface conditioning bath and is then brought into contact with an acidic solution containing phosphate ions, zinc ions, nickel ions, and manganese ions in order to precipitate a phosphate coating on the metal.
However, in association with today's heightened concern with environmental pro-tection, the regulatory situation with regard to nickel in wastewater has become increas-,5 ingly stringent, particularly in Europe. It is certainly prudent to anticipate that regulations on nickel in wastewater might also become much more demanding in other countries in the future. These considerations make it desirable to eliminate the nickel from the con-version treatment baths used in zinc phosphate treatments.
Unfortunately, a number of negative effects are caused by removal of the nickel 2o from many phosphate treatment baths used in the aforementioned phosphate treatment processes: The crystals in the phosphate coating undergo coarsening; the phosphate coating suffers from a loss of uniformity, the post-painting corrosion resistance declines, and the secondary (water-resistant) adherence of paint to zinc-plated material also de-clines.
25 Japanese Laid Open Patent Application (PCT) Number Hei 7-505445 (505,445/1995) teaches a nickel-free phosphate treatment process in order to solve the problems referenced above. This treatment process involves formation of a nickel-free phosphate coating by treatment with a phosphate conversion bath containing 0.2 to 2 grams of zinc ions per liter of bath (this unit of concentration being freely used hereinafter so for any constituent of any liquid and being usually abbreviated as "g/1"), 0.5 to 25 milli-grams of copper ions per liter, and 5 to 30 g/1 phosphate ions. This process uses copper as a substitute metal for nickel, but still suffers from several problems.
Since the allow-able copper level in this conversion treatment bath is so very low, management of the copper concentration in real-world lines is exceedingly difficult. Another concern is with electrolytic corrosion of the equipment accompanied by displacement copper plating on parts of the equipment.
Given this background, there is a desire for development of a phosphate conver-sion treatment process that does not use nickel but nevertheless affords a post-painting adherence and post-painting corrosion resistance that are the equal of those afforded by existing phosphate conversion treatments that use nickel. One major object of this invention is to provide a phosphate conversion treatment process that treats metal surfaces with a nickel-free conversion treatment bath and produces a phosphate ,o conversion coating that evidences an excellent post-painting corrosion resistance and excellent paint adherence.
BRIEF SUMMARY OF THE INVENTION
It has been found that most or all of the problems caused by the removal of nickel from previous phosphating treatments can be eliminated by using a surface conditioning ,s composition that contains very fine, dispersed solid phosphate particles.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
More specifically, a process according to the invention for forming a phosphate conversion on a metal substrate surface comprises, preferably consists essentially of, or more preferably consists of the following operations:
zo (I) contacting the metal substrate surface with an aqueous liquid surface condition-ing composition (hereinafter for brevity often called a "bath" without intending any implication that it must be contacted with the metal substrate by immersion of the metal substrate in a volume of the aqueous liquid surface conditioning composi-tion) that comprises, preferably consists essentially of, or more preferably con-z5 sists of, water and the following components:
(1.A) dispersed solid phosphate particles that:
(i) have a diameter no greater than 5 micrometres, this unit of length being hereinafter usually abbreviated as "Nm"; and (ii) comprise, preferably consist essentially of, or more preferably consist of, so at least one substance selected from the group consisting of phosphates that contain at least one divalent or trivalent metal cation; and (1.B) as adhesion-promoting component, at least one selection from the group consisting of the following subgroups:
(1 ) monosaccharides, polysaccharides, and derivatives thereof;
ss (2) phosphorus containing solutes selected from the group consisting of orthophosphoric acid, condensed phosphoric acids, and organophos-phonic acid compounds;
FIELD AND BACKGROUND OF THE INVENTION
This invention relates to processes for the phosphate conversion treatment of metals wherein said processes employ a nickel ion-free phosphate conversion treatment bath and produce a uniform, strongly paint-adherent, and highly post-painting corrosion-resistant coating on such metals as steel sheet, zinc-plated steel sheet, aluminum alloys, and magnesium alloys.
Phosphate conversion treatments are currently executed as a pre-paint treatment on automotive body components in order to enhance corrosion resistance and improve the steel sheet-to-paint adherence. In these phosphate conversion treatments, the metal ,o is first brought into contact with a colloidal titanium surface conditioning bath and is then brought into contact with an acidic solution containing phosphate ions, zinc ions, nickel ions, and manganese ions in order to precipitate a phosphate coating on the metal.
However, in association with today's heightened concern with environmental pro-tection, the regulatory situation with regard to nickel in wastewater has become increas-,5 ingly stringent, particularly in Europe. It is certainly prudent to anticipate that regulations on nickel in wastewater might also become much more demanding in other countries in the future. These considerations make it desirable to eliminate the nickel from the con-version treatment baths used in zinc phosphate treatments.
Unfortunately, a number of negative effects are caused by removal of the nickel 2o from many phosphate treatment baths used in the aforementioned phosphate treatment processes: The crystals in the phosphate coating undergo coarsening; the phosphate coating suffers from a loss of uniformity, the post-painting corrosion resistance declines, and the secondary (water-resistant) adherence of paint to zinc-plated material also de-clines.
25 Japanese Laid Open Patent Application (PCT) Number Hei 7-505445 (505,445/1995) teaches a nickel-free phosphate treatment process in order to solve the problems referenced above. This treatment process involves formation of a nickel-free phosphate coating by treatment with a phosphate conversion bath containing 0.2 to 2 grams of zinc ions per liter of bath (this unit of concentration being freely used hereinafter so for any constituent of any liquid and being usually abbreviated as "g/1"), 0.5 to 25 milli-grams of copper ions per liter, and 5 to 30 g/1 phosphate ions. This process uses copper as a substitute metal for nickel, but still suffers from several problems.
Since the allow-able copper level in this conversion treatment bath is so very low, management of the copper concentration in real-world lines is exceedingly difficult. Another concern is with electrolytic corrosion of the equipment accompanied by displacement copper plating on parts of the equipment.
Given this background, there is a desire for development of a phosphate conver-sion treatment process that does not use nickel but nevertheless affords a post-painting adherence and post-painting corrosion resistance that are the equal of those afforded by existing phosphate conversion treatments that use nickel. One major object of this invention is to provide a phosphate conversion treatment process that treats metal surfaces with a nickel-free conversion treatment bath and produces a phosphate ,o conversion coating that evidences an excellent post-painting corrosion resistance and excellent paint adherence.
BRIEF SUMMARY OF THE INVENTION
It has been found that most or all of the problems caused by the removal of nickel from previous phosphating treatments can be eliminated by using a surface conditioning ,s composition that contains very fine, dispersed solid phosphate particles.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
More specifically, a process according to the invention for forming a phosphate conversion on a metal substrate surface comprises, preferably consists essentially of, or more preferably consists of the following operations:
zo (I) contacting the metal substrate surface with an aqueous liquid surface condition-ing composition (hereinafter for brevity often called a "bath" without intending any implication that it must be contacted with the metal substrate by immersion of the metal substrate in a volume of the aqueous liquid surface conditioning composi-tion) that comprises, preferably consists essentially of, or more preferably con-z5 sists of, water and the following components:
(1.A) dispersed solid phosphate particles that:
(i) have a diameter no greater than 5 micrometres, this unit of length being hereinafter usually abbreviated as "Nm"; and (ii) comprise, preferably consist essentially of, or more preferably consist of, so at least one substance selected from the group consisting of phosphates that contain at least one divalent or trivalent metal cation; and (1.B) as adhesion-promoting component, at least one selection from the group consisting of the following subgroups:
(1 ) monosaccharides, polysaccharides, and derivatives thereof;
ss (2) phosphorus containing solutes selected from the group consisting of orthophosphoric acid, condensed phosphoric acids, and organophos-phonic acid compounds;
(3) water-soluble polymers that are homopolymers or copolymers of vinyl acetate and derivatives of these homopolymers and copolymers; and (4) copolymers and polymers as afforded by the polymerization of:
(a) at least one selection from:
-- monomers, exclusive of vinyl acetate, that conform to general chemical formula (I):
R' H2C=C-COORz (I), where R' = H or CH3 and Rz = H, C, to CS alkyl, or C, to C5 hydroxyalkyl; and -- other a,~3-unsaturated carboxylic acid monomers; and, optionally, ,s (b) not more than 50 % by weight of monomers that are not vinyl acetate and are not within the description of part (a) immediately above but are copolymerizable with said monomers that are within the description of said part (a);
and 20 (II) contacting the metal substrate surface as conditioned in operation (I) as described above with a nickel-free phosphate conversion treatment bath that comprises, preferably consists essentially of, or more preferably consists of water and the following amounts of the following components:
(11.A) from 0.5 to 5 g/1 of zinc cations;
25 (11.B) from 5 to 30 g/1 of phosphate ions; and (11.C) a component of conversion accelerator.
In a preferred embodiment, the above-specified conversion treatment baths also contain from 0.1 to 3.0 g/1 of at least one type of metal containing ions selected from the group consisting of magnesium ions, cobalt ions, manganese ions, calcium ions, tungs so tate ions, and strontium ions.
The features of this invention are explained in greater detail hereinbelow.
When ever a group of materials from which a constituent can be selected is specified, whether by a specific list, use of generic chemical terms, and/or conformance to a general chem ical formula, any two or more of the group may be selected instead of a single member ss with equal preference, unless explicitly stated otherwise.
While no particular limitations apply to the metal on which the inventive phosphate treatment process may be executed, this metal is preferably steel sheet, zinc-plated steel sheet, zinc alloy-plated steel sheet, magnesium alloy, or aluminum alloy.
It is preferred in the practice of the invention that the metal substrate surface be clean prior to the phosphate conversion treatment. Metal whose surface is already clean can be brought without further treatment into contact with the surface conditioning bath.
However, in the case of treatment of metal whose surface is contaminated with adherent materials such as iron particles, dust, and oil, the contaminants adhering on the surface should be removed by cleaning, for example, by cleaning with a water-based alkaline de-greaser or an emulsion degreaser or by solvent degreasing. When a water-based cleaner is used, the cleaning bath remaining on the metal surface is preferably removed ,o by the provision of, for example, a water rinse step after the cleaning step.
At least some of the particles of divalent and/or trivalent metal phosphate present in a surface conditioning bath in a process according to the invention must have a particle size or diameter no greater than 5 Nm. (Insolubles of larger size are undesirable because - depending on the particular circumstances - they often cannot be stably ,5 maintained in the aqueous bath.) These phosphate particles are believed to function as nuclei during phosphate crystal deposition and also to promote the deposition reaction itself, by undergoing partial dissolution in the phosphate conversion treatment bath and inducing a substantial acceleration of the initial phosphate crystal deposition reactions by supplying one or more main components of the phosphate crystals to the region 2o immediately adjacent to the metal surface.
The divalent and trivalent metals used here are not critical, but preferably com-prise at least one selection from Zn, Fe, Mn, Co, Ca, Mg, and AI. The divalent and/or tri-valent metal phosphate particles are preferably present at a concentration from 0.001 to 30 g/1. Acceleration of the initial phosphate crystal deposition reactions does not 2s normally occur at a divalent and/or trivalent metal phosphate particle concentration below 0.001 g/1 due to the small amount of divalent and/or trivalent metal phosphate particles that become adsorbed on the metal surface at such low concentrations.
Concentrations below 0.001 g/1 also prevent acceleration of the crystal deposition reactions due to the small number of divalent and/or trivalent metal phosphate particles available to act as so crystal nuclei. Divalent and/or trivalent metal phosphate particle concentrations in excess of 30 g/1 cannot be expected to provide additional promotion of the phosphate conversion reactions and hence will be uneconomical.
The adhesion-promoting component that must be present in the inventive surface conditioning bath functions to improve the dispersion stability of the divalent and/or trival-35 ent metal phosphate particles and to accelerate adsorption of the divalent and/or trivalent metal phosphate particles onto the metal surface. More specifically, the adhesion pro-moting component is believed to adsorb on the surface of the divalent and/or trivalent metal phosphate particles and, through a steric hindrance activity and repulsive forces arising from its electrical charge, to prevent collisions among the divalent and/or trivalent metal phosphate particles in the surface conditioning bath and thereby inhibit their aggre-gation and sedimentation. In addition, due to its structure, the adhesion-promoting com-ponent itself is believed to have an ability to adsorb to metal surfaces and thereby to ac-celerate adsorption to metal surfaces by the divalent and/or trivalent metal phosphate particles, so that the surface conditioning activity manifests upon contact between the metal workpiece and surface conditioning bath.
,o The adhesion-promoting component concentration is preferably from 1 to 2,000 parts by weight of the adhesion promoting component per 1000 parts by weight of the total conditioning composition, this unit of concentration being hereinafter usually abbre-viated as "ppm". At concentrations below 1 ppm a surface conditioning activity can not usually be produced just by contact between the metal workpiece and the surface condi-,s tinning bath. Not only can no additional benefit be expected at concentrations in excess of 2,000 ppm, but such concentrations can impair the phosphate conversion coating formed, perhaps as a result of excessive adsorption of the adhesion promoting compon-ent on the metal substrate surface.
A saccharide type of adhesion-promoting component for the surface conditioning 20 operation in a process according to the invention may be exemplified by fructose, taga-tose, psicose, sorbose, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, al-trose, glucose, mannose, gulose, idose, galactose, talose, and the sodium and ammon-ium salts of all of these saccharides.
A phosphorus containing acid type of adhesion-promoting component in the sur-25 face conditioning process is exemplified by orthophosphoric acid, polyphosphoric acids, and organophosphonic acid compounds, or more individually by pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine-so pentamethylenephosphonic acid, and the sodium and ammonium salts of all of the preceding acids. Sodium salts are preferred for the organophosphonic acids if they are to be used in salt form.
Polymeric adhesion promoting components derived from polyvinylacetate in a surface conditioning operation in a process according to the invention are exemplified ss by polyvinyl alcohols afforded by the hydrolysis of vinyl acetate polymers, cyanoethylated polyvinyl alcohols afforded by the cyanoethylation of polyvinyl alcohol with acrylonitrile, formalated polyvinyl alcohols afforded by the acetalation of polyvinyl alcohol with formaldehyde, urethanized polyvinyl alcohols afforded by the urethanation of polyvinyl alcohol with urea, and water-soluble polymers afforded by the introduction of carboxyl moieties, sulfonic moieties, or amide moieties into polyvinyl alcohol.
Suitable vinyl s acetate-copolymerizable monomers are exemplified by acrylic acid, crotonic acid, and malefic anhydride. The effects associated with the present invention will be fully mani-fested as long as the vinyl acetate polymer or derivative thereof or the copolymer of vinyl acetate and vinyl acetate-copolymerizable monomer is soluble in water. Within this limi-tation, these effects are independent of the degree of polymerization and the degree of ,o functional group introduction of the subject polymers.
Suitable monomers for other polymeric adhesion promoting components for the surface conditioning operation are exemplified by: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethyl ,s methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl meth-acrylate, and hydroxypentyl methacrylate as examples of polymers according to formula (I); acrylic acid, methacrylic acid, and malefic acid as unsaturated acids;
and styrene, vinyl chloride, and vinylsulfonic acid as optional comonomers.
A surface conditioning bath used by the inventive phosphate treatment processes 2o can also optionally contain an alkali metal salt or ammonium salt or a mixture thereof, selected from the group consisting of orthophosphate salts, metaphosphate salts, ortho-silicate salts, metasilicate salts, carbonate salts, bicarbonate salts, nitrate salts, nitrite salts, sulfate salts, borate salts, organic acid salts, and combinations of two or more se-lections from the aforesaid alkali metal and ammonium salts. The concentration of this 2s component is not critical, but when used is preferably from 0.5 to 20 g/1.
The surface conditioning bath may also contain a surfactant to promote uniform wetting of the surface being treated.
The phosphate conversion treatment process of this invention will now be consid-ered in greater detail. A zinc ions concentration below 0.5 g/1, because it can prevent the so formation of a coating of acceptable weight and can result in a diminished coverage ratio by the deposited phosphate crystals, can produce an inadequate post-painting corrosion resistance. A zinc ions concentration in excess of 5.0 g/1 can cause a coarsening of the coating crystals, resulting in particular in a decline in the post-painting adherence. The use of a phosphate ions concentration below 5.0 g/1 strongly impairs the production of ss a normal conversion coating. Concentrations in excess of 30.0 g/1 are uneconomical since they provide no additional effect. Phosphate ions can be supplied by the addition of phosphoric acid or its aqueous solution to the phosphate conversion treatment bath or by the dissolution of, for example, sodium, magnesium, or zinc phosphate in the phos-phate conversion treatment bath.
The conversion treatment bath also contains a component known as a "conver s sion accelerator" or simply "accelerator". The accelerator acts to restrain gaseous hydro gen production during etching, an action sometimes called "depolarizing" the metal sub strate surface. Otherwise, however, no particular limitations apply to the accelerator, and any material or combination of materials recognized as a conversion accelerator in prior art may be used.
The phosphate conversion treatment bath of this invention can also contain from 0.1 to 3.0 g/1 of at least one type of metal containing ions selected from the group con-sisting of magnesium cations, cobalt cations, manganese cations, calcium cations, tung-state anions, and strontium cations. The presence of this component in the phosphate conversion treatment bath, through its incorporation into the phosphate coating and ,s through its precipitation in a form separate from the phosphate, provides additional performance enhancements in the post-painting corrosion resistance and post-painting adherence, respectively. The use of a concentration below 0.1 g/1 usually does not effect any improvement in painting performance. A concentration above 3.0 g/1 is economically wasteful, since no additional improvements in painting performance usually results; a 2o high concentration can actually hinder deposition of the zinc phosphate that is the main component of an effectively protective conversion coating produced according to this invention. The source of one of the types of metal cations can be, for example, an oxide, hydroxide, carbonate, sulfate, nitrate, or phosphate of the particular metal.
The source of tungstate can be, for example, the sodium or potassium salt.
25 An etchant may be added to the phosphate conversion treatment bath in order to induce a uniform etch of the surface of the metal workpiece. Usable as this etchant are, for example, fluoride ions and complex fluoride ions such as fluorosilicate ions. The fluorine compound used here can be, for example, hydrofluoric acid, fluorosilicic acid, or a water soluble metal salt (e.g., sodium salt, potassium salt) of the preceding.
so The phosphate conversion treatment can be carried out by immersion or spraying or some combination thereof. Treatment for about 1 to 5 minutes can form a conversion coating satisfactorily robust for practical applications. The temperature of the phosphate conversion treatment bath is preferably from 30 to 60 °C.
The phosphate conversion treatment is preferably followed by at least one water ss rinse, and deionized water is preferably used in the final water rinse.
Working and comparative examples of actual treatments are provided below in order to demonstrate the advantageous effects of this invention in specific terms. The working examples that follow are simply examples of the application of the invention and in no way limit the applications of the invention or materials usable in the application of the invention.
Materials tested The following metal substrates were treated in the working and comparative examples: electrogalvanized steel sheet ("EG"), sheet thickness = 0.8 millimeters (here-inafter usually abbreviated as "mm"), plating add-on = 20 grams of plated zinc per square meter of sheet surface, this unit of coating weight being hereinafter freely used for any ,o coating on any surface and being hereinafter usually abbreviated as "g/m2;
galvannealed hot-dip galvanized steel sheet ("GA"), sheet thickness = 0.8 mm, coating add-on = 45 g/m2; and cold-rolled steel sheet ("CRS"), sheet thickness = 0.8 mm, type SPCC-SD.
Treatment operations sequence (common to the working and comparative examples;
as noted in the description of the testing below, not all of the specimens tested were ,s subjected to the operations numbered 8 or higher) (1 ) Degreasing with diluted FINECLEANER~ L4460 alkaline degreaser concentrate, a product of Nihon Parkerizing Co., Ltd., the working degreaser containing 20 g/1 of agent A and 12 g/1 of agent B, 43 °C, 120 seconds, dipping.
(2) Water rinse with tapwater: ambient temperature, 30 seconds, spray.
20 (3) Surface conditioning The conditions are described below in the tables for the working and comparative examples. The colloidal titanium surface conditioning treatments were run using PREPALENE~ ZN, a product of Nihon Parkerizing Co., Ltd.
(4) Phosphate conversion treatment 2s The conditions are described below in the tables for the working and comparative examples. The treatment time was 120 seconds in all cases.
(a) at least one selection from:
-- monomers, exclusive of vinyl acetate, that conform to general chemical formula (I):
R' H2C=C-COORz (I), where R' = H or CH3 and Rz = H, C, to CS alkyl, or C, to C5 hydroxyalkyl; and -- other a,~3-unsaturated carboxylic acid monomers; and, optionally, ,s (b) not more than 50 % by weight of monomers that are not vinyl acetate and are not within the description of part (a) immediately above but are copolymerizable with said monomers that are within the description of said part (a);
and 20 (II) contacting the metal substrate surface as conditioned in operation (I) as described above with a nickel-free phosphate conversion treatment bath that comprises, preferably consists essentially of, or more preferably consists of water and the following amounts of the following components:
(11.A) from 0.5 to 5 g/1 of zinc cations;
25 (11.B) from 5 to 30 g/1 of phosphate ions; and (11.C) a component of conversion accelerator.
In a preferred embodiment, the above-specified conversion treatment baths also contain from 0.1 to 3.0 g/1 of at least one type of metal containing ions selected from the group consisting of magnesium ions, cobalt ions, manganese ions, calcium ions, tungs so tate ions, and strontium ions.
The features of this invention are explained in greater detail hereinbelow.
When ever a group of materials from which a constituent can be selected is specified, whether by a specific list, use of generic chemical terms, and/or conformance to a general chem ical formula, any two or more of the group may be selected instead of a single member ss with equal preference, unless explicitly stated otherwise.
While no particular limitations apply to the metal on which the inventive phosphate treatment process may be executed, this metal is preferably steel sheet, zinc-plated steel sheet, zinc alloy-plated steel sheet, magnesium alloy, or aluminum alloy.
It is preferred in the practice of the invention that the metal substrate surface be clean prior to the phosphate conversion treatment. Metal whose surface is already clean can be brought without further treatment into contact with the surface conditioning bath.
However, in the case of treatment of metal whose surface is contaminated with adherent materials such as iron particles, dust, and oil, the contaminants adhering on the surface should be removed by cleaning, for example, by cleaning with a water-based alkaline de-greaser or an emulsion degreaser or by solvent degreasing. When a water-based cleaner is used, the cleaning bath remaining on the metal surface is preferably removed ,o by the provision of, for example, a water rinse step after the cleaning step.
At least some of the particles of divalent and/or trivalent metal phosphate present in a surface conditioning bath in a process according to the invention must have a particle size or diameter no greater than 5 Nm. (Insolubles of larger size are undesirable because - depending on the particular circumstances - they often cannot be stably ,5 maintained in the aqueous bath.) These phosphate particles are believed to function as nuclei during phosphate crystal deposition and also to promote the deposition reaction itself, by undergoing partial dissolution in the phosphate conversion treatment bath and inducing a substantial acceleration of the initial phosphate crystal deposition reactions by supplying one or more main components of the phosphate crystals to the region 2o immediately adjacent to the metal surface.
The divalent and trivalent metals used here are not critical, but preferably com-prise at least one selection from Zn, Fe, Mn, Co, Ca, Mg, and AI. The divalent and/or tri-valent metal phosphate particles are preferably present at a concentration from 0.001 to 30 g/1. Acceleration of the initial phosphate crystal deposition reactions does not 2s normally occur at a divalent and/or trivalent metal phosphate particle concentration below 0.001 g/1 due to the small amount of divalent and/or trivalent metal phosphate particles that become adsorbed on the metal surface at such low concentrations.
Concentrations below 0.001 g/1 also prevent acceleration of the crystal deposition reactions due to the small number of divalent and/or trivalent metal phosphate particles available to act as so crystal nuclei. Divalent and/or trivalent metal phosphate particle concentrations in excess of 30 g/1 cannot be expected to provide additional promotion of the phosphate conversion reactions and hence will be uneconomical.
The adhesion-promoting component that must be present in the inventive surface conditioning bath functions to improve the dispersion stability of the divalent and/or trival-35 ent metal phosphate particles and to accelerate adsorption of the divalent and/or trivalent metal phosphate particles onto the metal surface. More specifically, the adhesion pro-moting component is believed to adsorb on the surface of the divalent and/or trivalent metal phosphate particles and, through a steric hindrance activity and repulsive forces arising from its electrical charge, to prevent collisions among the divalent and/or trivalent metal phosphate particles in the surface conditioning bath and thereby inhibit their aggre-gation and sedimentation. In addition, due to its structure, the adhesion-promoting com-ponent itself is believed to have an ability to adsorb to metal surfaces and thereby to ac-celerate adsorption to metal surfaces by the divalent and/or trivalent metal phosphate particles, so that the surface conditioning activity manifests upon contact between the metal workpiece and surface conditioning bath.
,o The adhesion-promoting component concentration is preferably from 1 to 2,000 parts by weight of the adhesion promoting component per 1000 parts by weight of the total conditioning composition, this unit of concentration being hereinafter usually abbre-viated as "ppm". At concentrations below 1 ppm a surface conditioning activity can not usually be produced just by contact between the metal workpiece and the surface condi-,s tinning bath. Not only can no additional benefit be expected at concentrations in excess of 2,000 ppm, but such concentrations can impair the phosphate conversion coating formed, perhaps as a result of excessive adsorption of the adhesion promoting compon-ent on the metal substrate surface.
A saccharide type of adhesion-promoting component for the surface conditioning 20 operation in a process according to the invention may be exemplified by fructose, taga-tose, psicose, sorbose, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, al-trose, glucose, mannose, gulose, idose, galactose, talose, and the sodium and ammon-ium salts of all of these saccharides.
A phosphorus containing acid type of adhesion-promoting component in the sur-25 face conditioning process is exemplified by orthophosphoric acid, polyphosphoric acids, and organophosphonic acid compounds, or more individually by pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine-so pentamethylenephosphonic acid, and the sodium and ammonium salts of all of the preceding acids. Sodium salts are preferred for the organophosphonic acids if they are to be used in salt form.
Polymeric adhesion promoting components derived from polyvinylacetate in a surface conditioning operation in a process according to the invention are exemplified ss by polyvinyl alcohols afforded by the hydrolysis of vinyl acetate polymers, cyanoethylated polyvinyl alcohols afforded by the cyanoethylation of polyvinyl alcohol with acrylonitrile, formalated polyvinyl alcohols afforded by the acetalation of polyvinyl alcohol with formaldehyde, urethanized polyvinyl alcohols afforded by the urethanation of polyvinyl alcohol with urea, and water-soluble polymers afforded by the introduction of carboxyl moieties, sulfonic moieties, or amide moieties into polyvinyl alcohol.
Suitable vinyl s acetate-copolymerizable monomers are exemplified by acrylic acid, crotonic acid, and malefic anhydride. The effects associated with the present invention will be fully mani-fested as long as the vinyl acetate polymer or derivative thereof or the copolymer of vinyl acetate and vinyl acetate-copolymerizable monomer is soluble in water. Within this limi-tation, these effects are independent of the degree of polymerization and the degree of ,o functional group introduction of the subject polymers.
Suitable monomers for other polymeric adhesion promoting components for the surface conditioning operation are exemplified by: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethyl ,s methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl meth-acrylate, and hydroxypentyl methacrylate as examples of polymers according to formula (I); acrylic acid, methacrylic acid, and malefic acid as unsaturated acids;
and styrene, vinyl chloride, and vinylsulfonic acid as optional comonomers.
A surface conditioning bath used by the inventive phosphate treatment processes 2o can also optionally contain an alkali metal salt or ammonium salt or a mixture thereof, selected from the group consisting of orthophosphate salts, metaphosphate salts, ortho-silicate salts, metasilicate salts, carbonate salts, bicarbonate salts, nitrate salts, nitrite salts, sulfate salts, borate salts, organic acid salts, and combinations of two or more se-lections from the aforesaid alkali metal and ammonium salts. The concentration of this 2s component is not critical, but when used is preferably from 0.5 to 20 g/1.
The surface conditioning bath may also contain a surfactant to promote uniform wetting of the surface being treated.
The phosphate conversion treatment process of this invention will now be consid-ered in greater detail. A zinc ions concentration below 0.5 g/1, because it can prevent the so formation of a coating of acceptable weight and can result in a diminished coverage ratio by the deposited phosphate crystals, can produce an inadequate post-painting corrosion resistance. A zinc ions concentration in excess of 5.0 g/1 can cause a coarsening of the coating crystals, resulting in particular in a decline in the post-painting adherence. The use of a phosphate ions concentration below 5.0 g/1 strongly impairs the production of ss a normal conversion coating. Concentrations in excess of 30.0 g/1 are uneconomical since they provide no additional effect. Phosphate ions can be supplied by the addition of phosphoric acid or its aqueous solution to the phosphate conversion treatment bath or by the dissolution of, for example, sodium, magnesium, or zinc phosphate in the phos-phate conversion treatment bath.
The conversion treatment bath also contains a component known as a "conver s sion accelerator" or simply "accelerator". The accelerator acts to restrain gaseous hydro gen production during etching, an action sometimes called "depolarizing" the metal sub strate surface. Otherwise, however, no particular limitations apply to the accelerator, and any material or combination of materials recognized as a conversion accelerator in prior art may be used.
The phosphate conversion treatment bath of this invention can also contain from 0.1 to 3.0 g/1 of at least one type of metal containing ions selected from the group con-sisting of magnesium cations, cobalt cations, manganese cations, calcium cations, tung-state anions, and strontium cations. The presence of this component in the phosphate conversion treatment bath, through its incorporation into the phosphate coating and ,s through its precipitation in a form separate from the phosphate, provides additional performance enhancements in the post-painting corrosion resistance and post-painting adherence, respectively. The use of a concentration below 0.1 g/1 usually does not effect any improvement in painting performance. A concentration above 3.0 g/1 is economically wasteful, since no additional improvements in painting performance usually results; a 2o high concentration can actually hinder deposition of the zinc phosphate that is the main component of an effectively protective conversion coating produced according to this invention. The source of one of the types of metal cations can be, for example, an oxide, hydroxide, carbonate, sulfate, nitrate, or phosphate of the particular metal.
The source of tungstate can be, for example, the sodium or potassium salt.
25 An etchant may be added to the phosphate conversion treatment bath in order to induce a uniform etch of the surface of the metal workpiece. Usable as this etchant are, for example, fluoride ions and complex fluoride ions such as fluorosilicate ions. The fluorine compound used here can be, for example, hydrofluoric acid, fluorosilicic acid, or a water soluble metal salt (e.g., sodium salt, potassium salt) of the preceding.
so The phosphate conversion treatment can be carried out by immersion or spraying or some combination thereof. Treatment for about 1 to 5 minutes can form a conversion coating satisfactorily robust for practical applications. The temperature of the phosphate conversion treatment bath is preferably from 30 to 60 °C.
The phosphate conversion treatment is preferably followed by at least one water ss rinse, and deionized water is preferably used in the final water rinse.
Working and comparative examples of actual treatments are provided below in order to demonstrate the advantageous effects of this invention in specific terms. The working examples that follow are simply examples of the application of the invention and in no way limit the applications of the invention or materials usable in the application of the invention.
Materials tested The following metal substrates were treated in the working and comparative examples: electrogalvanized steel sheet ("EG"), sheet thickness = 0.8 millimeters (here-inafter usually abbreviated as "mm"), plating add-on = 20 grams of plated zinc per square meter of sheet surface, this unit of coating weight being hereinafter freely used for any ,o coating on any surface and being hereinafter usually abbreviated as "g/m2;
galvannealed hot-dip galvanized steel sheet ("GA"), sheet thickness = 0.8 mm, coating add-on = 45 g/m2; and cold-rolled steel sheet ("CRS"), sheet thickness = 0.8 mm, type SPCC-SD.
Treatment operations sequence (common to the working and comparative examples;
as noted in the description of the testing below, not all of the specimens tested were ,s subjected to the operations numbered 8 or higher) (1 ) Degreasing with diluted FINECLEANER~ L4460 alkaline degreaser concentrate, a product of Nihon Parkerizing Co., Ltd., the working degreaser containing 20 g/1 of agent A and 12 g/1 of agent B, 43 °C, 120 seconds, dipping.
(2) Water rinse with tapwater: ambient temperature, 30 seconds, spray.
20 (3) Surface conditioning The conditions are described below in the tables for the working and comparative examples. The colloidal titanium surface conditioning treatments were run using PREPALENE~ ZN, a product of Nihon Parkerizing Co., Ltd.
(4) Phosphate conversion treatment 2s The conditions are described below in the tables for the working and comparative examples. The treatment time was 120 seconds in all cases.
(5) Water rinse (tapwater): ambient temperature, 30 seconds, spray (6) Deionized water rinse (deionized water with an electrical conductivity <_ 0.2 microSiemens per centimeter): ambient temperature, 20 seconds, spray so (7) Drain/dry: 120 seconds, forced hot air at 90 °C
(8) Cationic electrocoating to a film thickness of about 20 Nm, then bake for minutes at 180 °C
(9) Surface coating with a film thickness of about 40 Nm baked for 20 minutes at 140 °C
35 (10) Top coating with a film thickness of about 40 Nm baked for 20 minutes at 140 °C.
Test and other evaluation methods The coating appearance was evaluated on the following two-level scale (after operation (7) as described above:
+ : the coating was uniform;
x : the coating exhibited a significant lack of uniformity with visible voids.
The test conditions and evaluation scale for the secondary (water-resistant) ad-herence were as follows: The sheet after operation (10) as described above was im-mersed for 240 hours in a hot water bath (maintained at 40 °C) that was being bubbled with air. The sheet was allowed to stand for 2 hours after removal from the hot water bath, after which time the peeling behavior was evaluated by cutting a grid (2 mm on each edge) in the sheet and subjecting this to tape peeling. The peeling behavior was evaluated using the following three-level scale:
+ + : complete absence of peeling;
+ : some peeling observed at the edges of the grid cut;
x : substantial peeling.
15 The test conditions and evaluation scale for the hot saltwater immersion test were as follows. A cross cut was scribed with an acrylic cutter in the sheet after operation (8) as described above, and the specimen thus prepared was immersed for 240 hours in a % by weight solution of sodium chloride in water that was maintained at 55 °C and was bubbled with air. The specimen was allowed to stand for 1 hour after withdrawal from 2o the saltwater bath, after which time the cross cut was peeled with tape and the width of peeling from the cut was evaluated. The peeling behavior was evaluated using the following three-level scale:
For the CRS:
+ + : maximum peel width (both sides) less than 4 mm;
2s + : maximum peel width (both sides) at least 4 mm but less than 6 mm;
x : maximum peel width (both sides) at least 6 mm.
For the EG and GA:
+ + : maximum peel width (one side) less than 3 mm;
+ : maximum peel width (one side) at least 3 mm but less than 5 mm;
so x : maximum peel width (one side) at least 5 mm.
The test conditions and evaluation scale for salt spray testing were as follows:
A cross cut was scribed with an acrylic cutter in the sheet after operation (8) as described above, and the specimen thus prepared was tested using a salt spray tester (5 % by weight solution of sodium chloride in water) maintained at 35 °C. After the ss stipulated time (based on Japanese Industrial Standard Z-2371 ), the specimen was rinsed with water and the status of corrosion at the cross cut was evaluated using the following three-level scale:
For the CRS (salt spray test time = 960 hours):
+ + : maximum rust width (both sides) less than 4 mm;
+ : maximum rust width (both sides) at least 4 mm but less than 5 mm;
s x : maximum rust width (both sides) at least 5 mm.
For the EG and GA (salt spray test time = 480 hours):
+ + : maximum rust width (one side) less than 4 mm;
+ : maximum rust width (one side) at least 4 mm but less than 5 mm;
x : maximum rust width (one side) at least 5 mm.
,o Details of the surface conditioning processes and phosphate treatment processes for the Examples and Comparative Examples and the corresponding test results are reported in the following tables, in which the following abbreviations are used:
for the phosphate salt component:
Zn2FeP2 - ZnzFe(P04)z 4H20 ,s Zn3P2 - Zn3(P04)2~4H20 Zn2CaP2 - Zn2Ca(P04)2~4H20 for the surfactant component:
E011 NPE - polyoxyethylene (E0 : 11 ) nonylphenol ether for the phosphorus compounds:
2o ATMPA - aminotrimethylenephosphonic acid 1-HEDPA - 1-hydroxyethylidene-1,1-diphosphonic acid 2-HEDPA - 2-hydroxyethylidene-1,1-diphosphonic acid EDATMPA - ethylenediaminetetramethylenephosphonic acid.
other:
2s Deg. - Degree Polym. - Polymerization Ex. - Example Comp. Ex. - Comparative Example VA - vinyl acetate so PVAIc - polyvinylalcohol Wt% - Percent by weight.
Table 1 : EXAMPLES 1 TO 5 Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2 Zn2FeP2Zn2FeP2 Zn2FeP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 0.5 0.5 0.5 hum Concentration,1 1 1 1 1 g/1 Surface Monosaccharideglucose glucoseglucose glucosefructose Unit Condi-Sacchar-Substituent(s)CH COOH CH,COOHCHZCOOH none none boningide-Based ~Oz NOz T
reat- Constitu-ment ents: Deg. of Substitution_< 1.8 _< 1.8 0.7 none 0 Com- Deg <_ 3,000< 3,000< 100 1 <_ 100 of Polym. .
posi- Concentration,5 1,000 10 2,000 2,000 tion ppm Con- Salt Chemical Formulanone none NaNOz MgS none stitu-con- O
stituent(s TFI
) ents . Concentration,none none 0.5 0.5 none d g/1 an Sur- Abbreviation none none none none none Processfactant Condi-Constit-Concentration,none none none none none tions:uents: g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds P043~ 10 15 20 18 16 Zn2+ 0.8 1.3 2.2 1.5 1.4 Mgz+ 2.0 none none none 2.5 Phos-phate Co2+ none 1.0 none none none Con- Mnz+ 0.5 none 1.0 none none versionGrams Treat-per Caz+ none none none 1.5 none t Liter of:
men Srz+ none none none none 0.9 Com-posi- _z tion WOa none none 0.3 none none Con- N03 8.3 7.6 9.0 8.0 7.3 stitu-ents F- 0.1 none 0.1 none 0.1 and Process NOi 0.01 none 0.01 none 0.01 Condi- NHQOH none 1.5 none 3.0 none tions:
Treatment 40 45 50 35 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 2: EXAMPLES 6 To 10 Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2CaP2 Phosphateparticle size,0.5 0.6 1.2 0.4 0.4 Particles:pm Concentration,1 1 1 10 5 g/1 Monosaccharideglucoseglucose glucoseglucose fructose Surface Unit xylose Condi-acchar- galactose boningide-BasedSubstituent(s)none CHZCOOH CHZCOOHCH_,COOHnone Treat-Constitu- CH
ents:
ment Deg. of Substitution0 >_ 2 1.9 1.0 0 Com-position of Polym. <_ _< 200 _< 1,000< 2,000 _< 500 Deg. 500 _ Constit- Concentration,100 100 1 10 5 ts ppm uen Salt Chemical Formulanone none Na20Si02Na~C03 Na3P04 and con- 5H~ 0 12H20 Process stituent(s):
Condi- Concentration,none none 5 1 10 g/1 tions:
SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds Zn2+ 0.9 1.3 2.0 1.5 1.4 Phos- Mga+ 2.0 none none none 2.5 phate Co2+ none none none none none Conver-sion Mn2+ 0.6 none 1.0 none none Treat-Grams Ca2+ none none none 1.0 none ment per Literz+
Compo-of: Sr none none none none 0.9 sition W04 Z none none 0.3 none none Constit- N03- 8.9 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process Npz 0.01 none 0.01 none none i -Cond NHqOH none 1.5 none 3.0 3.5 tions:
Treatment 38 43 49 55 59 Temperature, C
Treatment 120 120 I 120 120 ~ 120 Time, I I
Seconds I
Tabl2 3: COMPARATIVE EXAMPLES 1 TO 5 Comparative Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn3P2 Zn3P2 Phosphateparticle size, 0.5 0.6 1.2 0.5 0.5 Particles:pm Concentration, 1 1 1 1 1 g/1 Monosaccharide glucoseglucose glucoseglucosefructose Surface Unit xy lose Condi-acchar- galactose tinningide-BasedSubstituent(s) none CHzCOOH CH=COOHnone none Treat-Constitu- CH3 nts:
ment e Deg. of Substitution0 >_ 2 1.9 none none Com-position Deg. of Polym. _< 500 _< 200 _< 1,0001 s 100 Constit-uents Concentration, 100 100 1 2000 2000 ppm and Chemical Formulanone none NazOSiOzMgS04 none ProcessSalt con- SHZO 7 Hz0 tit t Condi-(s):
dons: uen Concentration, none none 5 0.5 none s g/1 SurfactantAbbreviation none none none none none Constit-uents: Concentration, none none none none none g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds P043- 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate z+
Conver- Co none none none none none sion Mnz+ 0.6 none 1.0 1.0 none Treat-ment Caz+ none none none none none Compo- Srz+ none none none 3.0 0.9 sitionGrams Constit-per WOa z none none 0.3 none none Liter uents of: NO; 8.9 7.6 9.0 8.0 7.3 d an F- 0.1 none 0.1 none 0.1 Process Condi- NOz 0.01 none 0.01 none none tions:
NH40H none 1.5 none 3.0 3.5 Treatment 38 43 49 55 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 4: COMPARATIVE EXAMPLES 6 TO 10 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphateparticle size, none 0.6 6.5 0.4 0.5 Particles:pm Concentration, none 1 1 10 0.00001 g/1 Monosaccharide none none glucoseglucose glucose Unit Surface Substituent(s) none none CHZCOOHCH~COOH CHZCOOH
Condi-Sacchar- CH
ide-Based tinningConstitu-Deg. of Substitutionnone none 1.9 1.0 0.7 Treat-ents:
men t Deg. of Polym.none none < 1,000<_ 2,000_< 100 Com- Concentration, none none 1 5,000 10 osition ppm p Salt Chemical Formulanone none Na,OSiOZNa~C03 NaN02 Constit-con- SHz O
uents stituent(s):
and Concentration, none none 5 1 0.5 P g/1 rocess Condi-SurfactantAbbreviation none none none none none tions:Constit-uents: Concentration, none none none none none g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds PO4~- 11 15 22 18 16 Znz+ 0.9 1.3 2.0 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none none none none none Conver-sion Mnz+ 0.6 none 1.0 none none Treat- Caz+ none none none 1.0 none ment Srz+ none none none none 0.9 Compo-sitionGrams W04 z none none 0.3 none none Constit-per NO~ 8.9 7.6 9.0 8.0 7.3 uents Liter of:
and F' 0.1 none 0.1 none 0.1 Process NOZ 0.01 none 0.01 none none Condi-tions: NHaOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, I
Seconds Table 5: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- EXAMPLE
NUMBER
STRATE
Coating Appearance CRS + + + + + + + + + +
EG + + + + + + + + + +
GA + + + + + + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + + +
+ + + + + + + + + +
Adherence EG + + + + + + + + + +
+ + + + + + + +
GA ++ ++ + ++ ++ ++ ++ + ++ ++
CRS ++ ++ ++ ++ + ++ + ++ ++ +
Resistance to Hot SaltEG + + + + + + + + + +
Water + + + + + + + + +
GA ++ ++ ++ ++ ++ ++ + ++ ++ ++
CRS + ++ ++ + + + + + ++ +
Resistance to Salt Spray EG ++ + ++ + ++ ++ + + ++ ++
GA ++ + ++ + ++ ++ + + ++ ++
Table 6: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x Table 7: EXAMPLES 11 TO 15 Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 1.7 0.6 0.5 hum Concentration,5 1 1 5 10 g/1 SurfacePhosphor-Substance tripoly-hexameta-ATMPA 1-HBDPADATMPA
Condi-us Con- phos- phosphoric boningtaming phoricacid Treat-Solute: acid ment Concentration,1 100 500 50 1,000 ppm Com-position Chemical FormulaMgS047Na,OSiOZnone Na~C0 Na ConstitSalt 3 3 con-H,O 5H H,O
uent stituent(s): s z and Concentration,0.5 1 none 5 10 g/1 Process Condi-SurfactantAbbreviation none none none none EO11NPE
tions:Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P043~ 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mga+ 2.0 none none none 2.5 phate Co2+ none 1.0 none none none Conver-sion Mn2+ 0.5 none 1.0 none none Treat- Caa+ none none none 1.5 none ment Compo- Srz+ none none none none 0.9 sitionGrams W04 2 none none 0.3 none none Constit-per NO; 8.3 7.6 9.0 8.0 7.3 Liter uents of:
and F- 0.1 none 0.1 none 0.1 Process Npz 0.01 none 0.01 none 0.01 di -Con tions: NHqOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 I 120 120 120 Time, I
Seconds I
TablB 8: COMPARATIVE EXAMPLES 1 1 TO 15 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 1.7 0.6 0.5 pm Concentration,5 1 1 5 10 g/1 SurfacePhosphor-Substance tripoly-hexameta-ATMPA 2- DATMP
Condi-us Con- phos- phosphoric HEDPA
tinningtwining phoric acid Treat-Solute: acid ment Concentration,1 100 500 50 1,000 Com-Ppm osition p Constit- Chemical FormulaMg NaOH none Na~C03Na3P0412 Salt P1 s con 0 H O
=
stituent(s):
and Concentration,0.5 1 none 5 10 g/1 Process Condi-SurfactantAbbreviation none none none none EO11NPE
tions:
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds PO43- 11 15 1.0 18 16 Zn2+ 0.1 7.0 2.0 1.5 1.4 Phos- Mg2+ 2.0 none none none 2.5 phate a+
Conver- Co none none none none none sion Mn2+ 0.6 none 1.0 1.0 none Treat-ment Cwz+ none none none none none Compo- Sr2+ none none none 3.0 0.9 i G
i on rams s t Constit-per WO4 2 none none 0.3 none none Liter uents of: N03 8.9 7.6 9.0 8.0 7.3 and Process F' 0.1 none 0.1 none 0.1 Condi- NOZ 0.01 none 0.01 none none dons:
NH40H none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 9: COMPARATIVE EXAMPLES 16 TO 20 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn3P2 Zn3P2Zn2CaP2 Zn2FeP2 Phosphate ParticlesParticle size,none 0.5 6.5 0.6 0.00001 pm Concentration,none 1 1 5 10 g/1 SurfacePhosphor-Substance none none ATMPAhexametaphos-EDATMPA
Condi-us Con- phoric acid boningtwiningConcentration,none none 500 3,000 1,000 ppm Treat-Solute ment Chemical FormulaMgSO; none none NaZC03 Na~OSi02 Com Salt =
con-ositionstituent(s) 7Hz0 SHzO
p Constit- Concentration,0.5 none none 5 1 g/1 uents and SurfactantAbbreviation none none none none EO11NPE
ProcessConstit-uents Concentration,none none none none 2.0 g/1 Condi-tions:Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P043~ 11 15 22 18 16 ZnZ+ 0.9 1.3 2.0 1.5 1.4 Phos-phate Mga+ 2.0 none none none 2.5 Conver- Co2+ none none none none none sion Treat- Mn2+ 0.6 none 1.0 none none ment Grams Ca2+ none none none 1.0 none Compo-per z+
Liter sitionof: Sr none none none none 0.9 Constit- W04 Z none none 0.3 none none uents N03 8.9 7.6 9.0 8.0 7.3 and Process F- 0.1 none 0.1 none 0.1 Condi- NOi 0.01 none 0.01 none none i ons:
t NHQOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Tabl2 1 O: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
NUMBER
TESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
CRS ++ ++ ++ ++ ++
Secondary (Water-Resistant)EG + + + + + + + +
Adherence +
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot SaltEG + + + + + + + + +
Water +
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt EG + + + + + + + +
Spray GA ++ + ++ + ++
Table 1 1 : APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x Table 12: EXAMPLES 16 To 20 Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphateparticle size,0.5 1.5 0.5 1.6 0.3 Particlespm Concentration,5 8 1 5 10 g/1 Water Substance Namepolyvinylcarboxyl-sulfonicCopolymerCopolyme SurfaceSoluble alcoholmodifiedacid- with with Condi-VA PVAIc modifiedVA VA
boningPolymer PVAIc Treat-or Comonomer withnone none none malefic crotonic ment DerivativeVA acid acid Com-position Comonomer ~o none none none 80 70 Constit- by Weight uents Concentration,1 500 2,000 1,000 10 ppm and ProcessSalt Chemical FormulaMgS04 NazOSi02none Na2C03 Na3P04 Condi-con- 7HzO 5H20 12H20 stituent(s) tions: Concentration,0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P04;- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none 1.0 none none none Conver-sion Mnz+ 0.5 none 1.0 none none Treat-Grams Caz+ none none none 1.5 none ment per z+
Compo-Liter Sr none none none none 0.9 of:
sition WO,; z none none 0.3 none none Constit- NO; 8.3 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process NOZ 0.01 none 0.01 none 0.01 Condi-tions: NHqOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds T3b12 13: COMPARATIVE EXAMPLES 21 TO 25 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn3P2 Phosphate Particles:Particle size,0.5 0.5 0.5 1.6 0.5 ~tm Concentration,5 1 1 5 1 g/1 SurfaceWater Substance polyvinyl-carboxyl-sulfonicCopoly-Copolyme Condi-SolubleName alcoholmodified acid-moth-mer mth boningVA PVAIc fied mth VA
PVAIc VA
Treat-Polymer ment or Comonomer none none none maleficcrotonic C Derivative:with acid acid VA
om- Comonomer none none none 80 70 position % by Constit- Weight uents Concentration,1 500 2,000 1,000 10 and ppm Process Condi-Salt Chemical FormulaMgSOq NazOSiOz none NaZC03 Na~POq dons: con-stituent(s): 7H20 SHZO 12H20 Concentration,0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds POq3 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 phate Mgz+ 2.0 none none none 2.5 Conver- Coz+ none none none none none sion Grams Treat- Mnz+ 0.6 none 1.0 1.0 none er Liter ment p Caz+ none none none none none of:
Compo-sition Srz+ none none none 3.0 0.9 Constit- WOQ z none none 0.3 none none uents and NO; 8.9 7.6 9.0 8.0 7.3 Process F- 0.1 none 0.1 none 0.1 di-C
on NOZ 0.01 none 0.01 none none tions:
NHqOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 14: COMPARATIVE EXAMPLES 26 TO 30 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn2FeP2Zn3P2 Zn2CaP2Zn2FeP2 Phosphateparticle size,none 1.7 6.5 1.6 0.3 Particles:hum Concentration,none 7 1 5 0.00001 g/1 Water Substance Namepolyvinyl sulfonicCopoly-Copoly-SurfaceSoluble alcohol none acid- mer mer Condi-VA modifiedwith with tinningPolymer PVAIc VA VA
Treat-or Comonomer withnone none none maleficcrotonic ment Derivative:VA
acid acid Com-position Comonomer % none none none 80 70 Constit- by Weight uents Concentration,1 none 2,000 3,000 10 ppm and ProcessSalt Chemical Formulanone NazOSiO,none NazC03Na3P0~
con- 5Hz0 12H
Condi- Y O
stituent(s): z tions: Concentration,none 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P04'- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none 1.0 none none none Conver-sion Mnz+ 0.5 none 1.0 none none Treat-Grams Caz+ none none none 1.5 none ment per Literz+
Compo-of: Sr none none none none 0.9 sition W04 z none none 0.3 none none Constit- NO; 8.3 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process NOz 0.01 none 0.01 none 0.01 Condi-tions: NHQOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 I 120 120 120 120 Time, ~
Seconds I
Table 15: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
NUMBER
TESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + +
+
Adherence EG + + + + + + + +
+
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot SaltEG + + + + + + + + +
Water +
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt Spray EG ++ + ++ + ++
GA ++ + ++ + ++
Tabl2 16: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt EG x + x x x + x x x x Spray GA x x x x x x x x x x Table 17: EXAMPLES 21 To 25 with Type (4) Polymer Adhesion Promoting Agents Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate ParticlesParticle size,0.5 0.5 1.7 0.6 0.5 hum Concentration,5 1 1 5 10 g/1 SurfaceMonomerR' H none none CH3 none Condi-N'lth Rz CzH40Hnone none C3H,OH none Formula tinning(1) wt% in Polymer100 none none 20 none Treat-ment Other Monomer Name none maleficacrylicmaleficmethacrylic Com- Un- acid acid acid acid saturated positionMonomer~'t,o in Polymernone 80 100 80 50 Constit-uents Other Monomer Name none vinyl none none styrenesulfonic and Co- acetate acid monomer Process Wt% in Polymernone 20 none none 50 Condi-tions:Polymer 1 500 2,000 1,500 5 Concentration, ppm Chemical FormulaMgS04 az0SiOznone KOH Na3P0~
stituent(s) 7HzO ~ 5H20 12H20 Concentration,0.5 1 none 5 10 g11 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P0,,3- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate z+
Conver- Co none 1.0 none none none sion Grams Mnz+ 0.5 none 1.0 none none Treat-per Caz+ none none none 1.5 none went Liter of:
Compo- Srz+ none none none none 0.9 Constit- ~'O4 z none none 0.3 none none uents N03 8.3 7.6 9.0 8.0 7.3 and F- 0.1 none 0.1 none 0.1 Process Condi- NOi 0.01 none 0.01 none 0.01 tions: NH40H none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, ~
Seconds Tabl2 18: COMPARATIVE EXAMPLES 31 TO 35 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 AbbreviationZn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphate ParFlclesParticle 0.5 0.5 1.7 0.6 0.5 size, hum oncentration,5 1 1 5 10 g/1 Surface Condi-Monomer R' H none none CH; none ith Form-tioning-~ ula RZ CzH40Hnone none C3H,OH none (I) Treat- Wt% in Polymer100 none none 20 none ment Com- Other Monomer Namenone maleficacrylic malefic methacrylic positionUn- acid acid acid acid saturated ConstitAcid y - Monomer Wt% in Pol none 80 100 80 50 uents mer and Other Monomer Namenone vinyl none none styrenesul-ProcessCo- acetate fonic monomer 'acid Condi- Wt% in Polymernone 20 none none 50 dons:polymer 1 500 2,000 1,500 5 Concentration, ppm Salt Chemical M~ a~0 none NazC03 l~POd con- ) Formula 004 O z stituent(s 7Hz z oncentration,0.5 1 none 5 10 g/1 SurfactantAbbreviationnone none none none EO11NPE
Constit-uents oncentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds PO4'' 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 Phos-phate Mgz+ 2.0 none none none 2.5 Convey- Coz+ none none none none none sion Mnz+ 0.6 none 1.0 1.0 none Treat-ment Grams Caz+ none none none none none Compo-Per Literz+
ition of: Sr one one one .0 .9 s WOq'z none none 0.3 none none Constit-uents NO; 8.9 7.6 9.0 8.0 7.3 and Process F- 0.1 none 0.1 none 0.1 Condi- NOz 0.01 none 0.01 none none tions:
NHQOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 ~ 120 120 Time, ~
Seconds Table 19: COMPARATIVE EXAMPLES 36 TO 40 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Surface Abbreviation none Zn2CaP2 Zn3P2 Zn2CaP2Zn2FeP2 Condi-Phosphate tinninParticlesParticle size, none 0.8 6.8 0.6 0.5 hum g Treat- Concentration, none 10 1 5 0.0001 g/1 ment MonomerRl H none none CH3 none Com- ith positionForm- Rz CZH40H none none C3H,OH none ~ ~
ula (I) Constit- Wt% in Polymer 100 none none 20 none uents Other Monomer Name none none acrylicmaleficmetha-and Un- acid acid crylic saturated acid ProcessAcid Condi-MonomerWt7o in Polymernone none 100 80 50 tions:ether Monomer Name none none none none styrenesul-Co- fonic monomer 'acid Wtlo in Polymernone none none none 50 Polymer 1 none 2,000 3,000 5 Concentration, ppm Salt Chemical FormulaM~S004 N;~H none NazC03 Ni~O~
con- 7Hz O z z stituent(s) z Concentration, 0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration, none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds Phos- Znz+ 0.8 1.3 2.2 1.5 1.4 Convey- Mgz+ 2.0 none none none 2.5 sion Grams Coz+ none 1.0 none none none i per Treat-L Mnz+ 0.5 none 1.0 none none ter of:
went Compo- Caz+ none none none 1.5 none sition Srz+ none none none none 0.9 Constit-uents WOa z none none 0.3 none none and NO~ 8.3 7.6 9.0 8.0 7.3 Process F- 0.1 none 0.1 none 0.1 Condi-tions: NOz 0.01 none 0.01 none 0.01 NH40H none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 I 120 120 120 Time, I
Seconds I
Table 20: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
T NUMBER
ESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + +
+
Adherence EG ++ ++ + ++ ++
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot Salt Water EG ++ ++ ++ ++ ++
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt Spray EG ++ + ++ + ++
GA ++ + ++ + ++
Table 21: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant) Adherence EG x x x x x x x x x x GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot Salt Water EG x + x x x + x x x +
GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x
(8) Cationic electrocoating to a film thickness of about 20 Nm, then bake for minutes at 180 °C
(9) Surface coating with a film thickness of about 40 Nm baked for 20 minutes at 140 °C
35 (10) Top coating with a film thickness of about 40 Nm baked for 20 minutes at 140 °C.
Test and other evaluation methods The coating appearance was evaluated on the following two-level scale (after operation (7) as described above:
+ : the coating was uniform;
x : the coating exhibited a significant lack of uniformity with visible voids.
The test conditions and evaluation scale for the secondary (water-resistant) ad-herence were as follows: The sheet after operation (10) as described above was im-mersed for 240 hours in a hot water bath (maintained at 40 °C) that was being bubbled with air. The sheet was allowed to stand for 2 hours after removal from the hot water bath, after which time the peeling behavior was evaluated by cutting a grid (2 mm on each edge) in the sheet and subjecting this to tape peeling. The peeling behavior was evaluated using the following three-level scale:
+ + : complete absence of peeling;
+ : some peeling observed at the edges of the grid cut;
x : substantial peeling.
15 The test conditions and evaluation scale for the hot saltwater immersion test were as follows. A cross cut was scribed with an acrylic cutter in the sheet after operation (8) as described above, and the specimen thus prepared was immersed for 240 hours in a % by weight solution of sodium chloride in water that was maintained at 55 °C and was bubbled with air. The specimen was allowed to stand for 1 hour after withdrawal from 2o the saltwater bath, after which time the cross cut was peeled with tape and the width of peeling from the cut was evaluated. The peeling behavior was evaluated using the following three-level scale:
For the CRS:
+ + : maximum peel width (both sides) less than 4 mm;
2s + : maximum peel width (both sides) at least 4 mm but less than 6 mm;
x : maximum peel width (both sides) at least 6 mm.
For the EG and GA:
+ + : maximum peel width (one side) less than 3 mm;
+ : maximum peel width (one side) at least 3 mm but less than 5 mm;
so x : maximum peel width (one side) at least 5 mm.
The test conditions and evaluation scale for salt spray testing were as follows:
A cross cut was scribed with an acrylic cutter in the sheet after operation (8) as described above, and the specimen thus prepared was tested using a salt spray tester (5 % by weight solution of sodium chloride in water) maintained at 35 °C. After the ss stipulated time (based on Japanese Industrial Standard Z-2371 ), the specimen was rinsed with water and the status of corrosion at the cross cut was evaluated using the following three-level scale:
For the CRS (salt spray test time = 960 hours):
+ + : maximum rust width (both sides) less than 4 mm;
+ : maximum rust width (both sides) at least 4 mm but less than 5 mm;
s x : maximum rust width (both sides) at least 5 mm.
For the EG and GA (salt spray test time = 480 hours):
+ + : maximum rust width (one side) less than 4 mm;
+ : maximum rust width (one side) at least 4 mm but less than 5 mm;
x : maximum rust width (one side) at least 5 mm.
,o Details of the surface conditioning processes and phosphate treatment processes for the Examples and Comparative Examples and the corresponding test results are reported in the following tables, in which the following abbreviations are used:
for the phosphate salt component:
Zn2FeP2 - ZnzFe(P04)z 4H20 ,s Zn3P2 - Zn3(P04)2~4H20 Zn2CaP2 - Zn2Ca(P04)2~4H20 for the surfactant component:
E011 NPE - polyoxyethylene (E0 : 11 ) nonylphenol ether for the phosphorus compounds:
2o ATMPA - aminotrimethylenephosphonic acid 1-HEDPA - 1-hydroxyethylidene-1,1-diphosphonic acid 2-HEDPA - 2-hydroxyethylidene-1,1-diphosphonic acid EDATMPA - ethylenediaminetetramethylenephosphonic acid.
other:
2s Deg. - Degree Polym. - Polymerization Ex. - Example Comp. Ex. - Comparative Example VA - vinyl acetate so PVAIc - polyvinylalcohol Wt% - Percent by weight.
Table 1 : EXAMPLES 1 TO 5 Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2 Zn2FeP2Zn2FeP2 Zn2FeP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 0.5 0.5 0.5 hum Concentration,1 1 1 1 1 g/1 Surface Monosaccharideglucose glucoseglucose glucosefructose Unit Condi-Sacchar-Substituent(s)CH COOH CH,COOHCHZCOOH none none boningide-Based ~Oz NOz T
reat- Constitu-ment ents: Deg. of Substitution_< 1.8 _< 1.8 0.7 none 0 Com- Deg <_ 3,000< 3,000< 100 1 <_ 100 of Polym. .
posi- Concentration,5 1,000 10 2,000 2,000 tion ppm Con- Salt Chemical Formulanone none NaNOz MgS none stitu-con- O
stituent(s TFI
) ents . Concentration,none none 0.5 0.5 none d g/1 an Sur- Abbreviation none none none none none Processfactant Condi-Constit-Concentration,none none none none none tions:uents: g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds P043~ 10 15 20 18 16 Zn2+ 0.8 1.3 2.2 1.5 1.4 Mgz+ 2.0 none none none 2.5 Phos-phate Co2+ none 1.0 none none none Con- Mnz+ 0.5 none 1.0 none none versionGrams Treat-per Caz+ none none none 1.5 none t Liter of:
men Srz+ none none none none 0.9 Com-posi- _z tion WOa none none 0.3 none none Con- N03 8.3 7.6 9.0 8.0 7.3 stitu-ents F- 0.1 none 0.1 none 0.1 and Process NOi 0.01 none 0.01 none 0.01 Condi- NHQOH none 1.5 none 3.0 none tions:
Treatment 40 45 50 35 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 2: EXAMPLES 6 To 10 Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2CaP2 Phosphateparticle size,0.5 0.6 1.2 0.4 0.4 Particles:pm Concentration,1 1 1 10 5 g/1 Monosaccharideglucoseglucose glucoseglucose fructose Surface Unit xylose Condi-acchar- galactose boningide-BasedSubstituent(s)none CHZCOOH CHZCOOHCH_,COOHnone Treat-Constitu- CH
ents:
ment Deg. of Substitution0 >_ 2 1.9 1.0 0 Com-position of Polym. <_ _< 200 _< 1,000< 2,000 _< 500 Deg. 500 _ Constit- Concentration,100 100 1 10 5 ts ppm uen Salt Chemical Formulanone none Na20Si02Na~C03 Na3P04 and con- 5H~ 0 12H20 Process stituent(s):
Condi- Concentration,none none 5 1 10 g/1 tions:
SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds Zn2+ 0.9 1.3 2.0 1.5 1.4 Phos- Mga+ 2.0 none none none 2.5 phate Co2+ none none none none none Conver-sion Mn2+ 0.6 none 1.0 none none Treat-Grams Ca2+ none none none 1.0 none ment per Literz+
Compo-of: Sr none none none none 0.9 sition W04 Z none none 0.3 none none Constit- N03- 8.9 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process Npz 0.01 none 0.01 none none i -Cond NHqOH none 1.5 none 3.0 3.5 tions:
Treatment 38 43 49 55 59 Temperature, C
Treatment 120 120 I 120 120 ~ 120 Time, I I
Seconds I
Tabl2 3: COMPARATIVE EXAMPLES 1 TO 5 Comparative Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn3P2 Zn3P2 Phosphateparticle size, 0.5 0.6 1.2 0.5 0.5 Particles:pm Concentration, 1 1 1 1 1 g/1 Monosaccharide glucoseglucose glucoseglucosefructose Surface Unit xy lose Condi-acchar- galactose tinningide-BasedSubstituent(s) none CHzCOOH CH=COOHnone none Treat-Constitu- CH3 nts:
ment e Deg. of Substitution0 >_ 2 1.9 none none Com-position Deg. of Polym. _< 500 _< 200 _< 1,0001 s 100 Constit-uents Concentration, 100 100 1 2000 2000 ppm and Chemical Formulanone none NazOSiOzMgS04 none ProcessSalt con- SHZO 7 Hz0 tit t Condi-(s):
dons: uen Concentration, none none 5 0.5 none s g/1 SurfactantAbbreviation none none none none none Constit-uents: Concentration, none none none none none g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds P043- 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate z+
Conver- Co none none none none none sion Mnz+ 0.6 none 1.0 1.0 none Treat-ment Caz+ none none none none none Compo- Srz+ none none none 3.0 0.9 sitionGrams Constit-per WOa z none none 0.3 none none Liter uents of: NO; 8.9 7.6 9.0 8.0 7.3 d an F- 0.1 none 0.1 none 0.1 Process Condi- NOz 0.01 none 0.01 none none tions:
NH40H none 1.5 none 3.0 3.5 Treatment 38 43 49 55 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 4: COMPARATIVE EXAMPLES 6 TO 10 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphateparticle size, none 0.6 6.5 0.4 0.5 Particles:pm Concentration, none 1 1 10 0.00001 g/1 Monosaccharide none none glucoseglucose glucose Unit Surface Substituent(s) none none CHZCOOHCH~COOH CHZCOOH
Condi-Sacchar- CH
ide-Based tinningConstitu-Deg. of Substitutionnone none 1.9 1.0 0.7 Treat-ents:
men t Deg. of Polym.none none < 1,000<_ 2,000_< 100 Com- Concentration, none none 1 5,000 10 osition ppm p Salt Chemical Formulanone none Na,OSiOZNa~C03 NaN02 Constit-con- SHz O
uents stituent(s):
and Concentration, none none 5 1 0.5 P g/1 rocess Condi-SurfactantAbbreviation none none none none none tions:Constit-uents: Concentration, none none none none none g/1 Treatment 20 20 20 20 20 Temperature, C
Treatment 30 30 30 30 30 Time, Seconds PO4~- 11 15 22 18 16 Znz+ 0.9 1.3 2.0 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none none none none none Conver-sion Mnz+ 0.6 none 1.0 none none Treat- Caz+ none none none 1.0 none ment Srz+ none none none none 0.9 Compo-sitionGrams W04 z none none 0.3 none none Constit-per NO~ 8.9 7.6 9.0 8.0 7.3 uents Liter of:
and F' 0.1 none 0.1 none 0.1 Process NOZ 0.01 none 0.01 none none Condi-tions: NHaOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, I
Seconds Table 5: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- EXAMPLE
NUMBER
STRATE
Coating Appearance CRS + + + + + + + + + +
EG + + + + + + + + + +
GA + + + + + + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + + +
+ + + + + + + + + +
Adherence EG + + + + + + + + + +
+ + + + + + + +
GA ++ ++ + ++ ++ ++ ++ + ++ ++
CRS ++ ++ ++ ++ + ++ + ++ ++ +
Resistance to Hot SaltEG + + + + + + + + + +
Water + + + + + + + + +
GA ++ ++ ++ ++ ++ ++ + ++ ++ ++
CRS + ++ ++ + + + + + ++ +
Resistance to Salt Spray EG ++ + ++ + ++ ++ + + ++ ++
GA ++ + ++ + ++ ++ + + ++ ++
Table 6: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x Table 7: EXAMPLES 11 TO 15 Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 1.7 0.6 0.5 hum Concentration,5 1 1 5 10 g/1 SurfacePhosphor-Substance tripoly-hexameta-ATMPA 1-HBDPADATMPA
Condi-us Con- phos- phosphoric boningtaming phoricacid Treat-Solute: acid ment Concentration,1 100 500 50 1,000 ppm Com-position Chemical FormulaMgS047Na,OSiOZnone Na~C0 Na ConstitSalt 3 3 con-H,O 5H H,O
uent stituent(s): s z and Concentration,0.5 1 none 5 10 g/1 Process Condi-SurfactantAbbreviation none none none none EO11NPE
tions:Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P043~ 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mga+ 2.0 none none none 2.5 phate Co2+ none 1.0 none none none Conver-sion Mn2+ 0.5 none 1.0 none none Treat- Caa+ none none none 1.5 none ment Compo- Srz+ none none none none 0.9 sitionGrams W04 2 none none 0.3 none none Constit-per NO; 8.3 7.6 9.0 8.0 7.3 Liter uents of:
and F- 0.1 none 0.1 none 0.1 Process Npz 0.01 none 0.01 none 0.01 di -Con tions: NHqOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 I 120 120 120 Time, I
Seconds I
TablB 8: COMPARATIVE EXAMPLES 1 1 TO 15 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate Particles:Particle size,0.5 0.5 1.7 0.6 0.5 pm Concentration,5 1 1 5 10 g/1 SurfacePhosphor-Substance tripoly-hexameta-ATMPA 2- DATMP
Condi-us Con- phos- phosphoric HEDPA
tinningtwining phoric acid Treat-Solute: acid ment Concentration,1 100 500 50 1,000 Com-Ppm osition p Constit- Chemical FormulaMg NaOH none Na~C03Na3P0412 Salt P1 s con 0 H O
=
stituent(s):
and Concentration,0.5 1 none 5 10 g/1 Process Condi-SurfactantAbbreviation none none none none EO11NPE
tions:
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds PO43- 11 15 1.0 18 16 Zn2+ 0.1 7.0 2.0 1.5 1.4 Phos- Mg2+ 2.0 none none none 2.5 phate a+
Conver- Co none none none none none sion Mn2+ 0.6 none 1.0 1.0 none Treat-ment Cwz+ none none none none none Compo- Sr2+ none none none 3.0 0.9 i G
i on rams s t Constit-per WO4 2 none none 0.3 none none Liter uents of: N03 8.9 7.6 9.0 8.0 7.3 and Process F' 0.1 none 0.1 none 0.1 Condi- NOZ 0.01 none 0.01 none none dons:
NH40H none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 9: COMPARATIVE EXAMPLES 16 TO 20 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn3P2 Zn3P2Zn2CaP2 Zn2FeP2 Phosphate ParticlesParticle size,none 0.5 6.5 0.6 0.00001 pm Concentration,none 1 1 5 10 g/1 SurfacePhosphor-Substance none none ATMPAhexametaphos-EDATMPA
Condi-us Con- phoric acid boningtwiningConcentration,none none 500 3,000 1,000 ppm Treat-Solute ment Chemical FormulaMgSO; none none NaZC03 Na~OSi02 Com Salt =
con-ositionstituent(s) 7Hz0 SHzO
p Constit- Concentration,0.5 none none 5 1 g/1 uents and SurfactantAbbreviation none none none none EO11NPE
ProcessConstit-uents Concentration,none none none none 2.0 g/1 Condi-tions:Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P043~ 11 15 22 18 16 ZnZ+ 0.9 1.3 2.0 1.5 1.4 Phos-phate Mga+ 2.0 none none none 2.5 Conver- Co2+ none none none none none sion Treat- Mn2+ 0.6 none 1.0 none none ment Grams Ca2+ none none none 1.0 none Compo-per z+
Liter sitionof: Sr none none none none 0.9 Constit- W04 Z none none 0.3 none none uents N03 8.9 7.6 9.0 8.0 7.3 and Process F- 0.1 none 0.1 none 0.1 Condi- NOi 0.01 none 0.01 none none i ons:
t NHQOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Tabl2 1 O: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
NUMBER
TESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
CRS ++ ++ ++ ++ ++
Secondary (Water-Resistant)EG + + + + + + + +
Adherence +
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot SaltEG + + + + + + + + +
Water +
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt EG + + + + + + + +
Spray GA ++ + ++ + ++
Table 1 1 : APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x Table 12: EXAMPLES 16 To 20 Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphateparticle size,0.5 1.5 0.5 1.6 0.3 Particlespm Concentration,5 8 1 5 10 g/1 Water Substance Namepolyvinylcarboxyl-sulfonicCopolymerCopolyme SurfaceSoluble alcoholmodifiedacid- with with Condi-VA PVAIc modifiedVA VA
boningPolymer PVAIc Treat-or Comonomer withnone none none malefic crotonic ment DerivativeVA acid acid Com-position Comonomer ~o none none none 80 70 Constit- by Weight uents Concentration,1 500 2,000 1,000 10 ppm and ProcessSalt Chemical FormulaMgS04 NazOSi02none Na2C03 Na3P04 Condi-con- 7HzO 5H20 12H20 stituent(s) tions: Concentration,0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P04;- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none 1.0 none none none Conver-sion Mnz+ 0.5 none 1.0 none none Treat-Grams Caz+ none none none 1.5 none ment per z+
Compo-Liter Sr none none none none 0.9 of:
sition WO,; z none none 0.3 none none Constit- NO; 8.3 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process NOZ 0.01 none 0.01 none 0.01 Condi-tions: NHqOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds T3b12 13: COMPARATIVE EXAMPLES 21 TO 25 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn3P2 Phosphate Particles:Particle size,0.5 0.5 0.5 1.6 0.5 ~tm Concentration,5 1 1 5 1 g/1 SurfaceWater Substance polyvinyl-carboxyl-sulfonicCopoly-Copolyme Condi-SolubleName alcoholmodified acid-moth-mer mth boningVA PVAIc fied mth VA
PVAIc VA
Treat-Polymer ment or Comonomer none none none maleficcrotonic C Derivative:with acid acid VA
om- Comonomer none none none 80 70 position % by Constit- Weight uents Concentration,1 500 2,000 1,000 10 and ppm Process Condi-Salt Chemical FormulaMgSOq NazOSiOz none NaZC03 Na~POq dons: con-stituent(s): 7H20 SHZO 12H20 Concentration,0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds POq3 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 phate Mgz+ 2.0 none none none 2.5 Conver- Coz+ none none none none none sion Grams Treat- Mnz+ 0.6 none 1.0 1.0 none er Liter ment p Caz+ none none none none none of:
Compo-sition Srz+ none none none 3.0 0.9 Constit- WOQ z none none 0.3 none none uents and NO; 8.9 7.6 9.0 8.0 7.3 Process F- 0.1 none 0.1 none 0.1 di-C
on NOZ 0.01 none 0.01 none none tions:
NHqOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 120 120 Time, Seconds Table 14: COMPARATIVE EXAMPLES 26 TO 30 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Abbreviation none Zn2FeP2Zn3P2 Zn2CaP2Zn2FeP2 Phosphateparticle size,none 1.7 6.5 1.6 0.3 Particles:hum Concentration,none 7 1 5 0.00001 g/1 Water Substance Namepolyvinyl sulfonicCopoly-Copoly-SurfaceSoluble alcohol none acid- mer mer Condi-VA modifiedwith with tinningPolymer PVAIc VA VA
Treat-or Comonomer withnone none none maleficcrotonic ment Derivative:VA
acid acid Com-position Comonomer % none none none 80 70 Constit- by Weight uents Concentration,1 none 2,000 3,000 10 ppm and ProcessSalt Chemical Formulanone NazOSiO,none NazC03Na3P0~
con- 5Hz0 12H
Condi- Y O
stituent(s): z tions: Concentration,none 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents: Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P04'- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate Coz+ none 1.0 none none none Conver-sion Mnz+ 0.5 none 1.0 none none Treat-Grams Caz+ none none none 1.5 none ment per Literz+
Compo-of: Sr none none none none 0.9 sition W04 z none none 0.3 none none Constit- NO; 8.3 7.6 9.0 8.0 7.3 uents and F- 0.1 none 0.1 none 0.1 Process NOz 0.01 none 0.01 none 0.01 Condi-tions: NHQOH none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 I 120 120 120 120 Time, ~
Seconds I
Table 15: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
NUMBER
TESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + +
+
Adherence EG + + + + + + + +
+
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot SaltEG + + + + + + + + +
Water +
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt Spray EG ++ + ++ + ++
GA ++ + ++ + ++
Tabl2 16: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant)EG x x x x x x x x x x Adherence GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot SaltEG x + x x x + x x x +
Water GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt EG x + x x x + x x x x Spray GA x x x x x x x x x x Table 17: EXAMPLES 21 To 25 with Type (4) Polymer Adhesion Promoting Agents Example Number:
PREPALENE~-ZN, none none none none none g/1 Abbreviation Zn2FeP2Zn3P2 Zn3P2 Zn2CaP2Zn2FeP2 Phosphate ParticlesParticle size,0.5 0.5 1.7 0.6 0.5 hum Concentration,5 1 1 5 10 g/1 SurfaceMonomerR' H none none CH3 none Condi-N'lth Rz CzH40Hnone none C3H,OH none Formula tinning(1) wt% in Polymer100 none none 20 none Treat-ment Other Monomer Name none maleficacrylicmaleficmethacrylic Com- Un- acid acid acid acid saturated positionMonomer~'t,o in Polymernone 80 100 80 50 Constit-uents Other Monomer Name none vinyl none none styrenesulfonic and Co- acetate acid monomer Process Wt% in Polymernone 20 none none 50 Condi-tions:Polymer 1 500 2,000 1,500 5 Concentration, ppm Chemical FormulaMgS04 az0SiOznone KOH Na3P0~
stituent(s) 7HzO ~ 5H20 12H20 Concentration,0.5 1 none 5 10 g11 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds P0,,3- 10 15 20 18 16 Znz+ 0.8 1.3 2.2 1.5 1.4 Phos- Mgz+ 2.0 none none none 2.5 phate z+
Conver- Co none 1.0 none none none sion Grams Mnz+ 0.5 none 1.0 none none Treat-per Caz+ none none none 1.5 none went Liter of:
Compo- Srz+ none none none none 0.9 Constit- ~'O4 z none none 0.3 none none uents N03 8.3 7.6 9.0 8.0 7.3 and F- 0.1 none 0.1 none 0.1 Process Condi- NOi 0.01 none 0.01 none 0.01 tions: NH40H none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 120 120 120 Time, ~
Seconds Tabl2 18: COMPARATIVE EXAMPLES 31 TO 35 Comparative Example Number:
PREPALENEO-ZN, none none none none none g/1 AbbreviationZn2FeP2Zn3P2 Zn3P2 Zn2CaP2 Zn2FeP2 Phosphate ParFlclesParticle 0.5 0.5 1.7 0.6 0.5 size, hum oncentration,5 1 1 5 10 g/1 Surface Condi-Monomer R' H none none CH; none ith Form-tioning-~ ula RZ CzH40Hnone none C3H,OH none (I) Treat- Wt% in Polymer100 none none 20 none ment Com- Other Monomer Namenone maleficacrylic malefic methacrylic positionUn- acid acid acid acid saturated ConstitAcid y - Monomer Wt% in Pol none 80 100 80 50 uents mer and Other Monomer Namenone vinyl none none styrenesul-ProcessCo- acetate fonic monomer 'acid Condi- Wt% in Polymernone 20 none none 50 dons:polymer 1 500 2,000 1,500 5 Concentration, ppm Salt Chemical M~ a~0 none NazC03 l~POd con- ) Formula 004 O z stituent(s 7Hz z oncentration,0.5 1 none 5 10 g/1 SurfactantAbbreviationnone none none none EO11NPE
Constit-uents oncentration,none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds PO4'' 11 15 1.0 18 16 Znz+ 0.1 7.0 2.0 1.5 1.4 Phos-phate Mgz+ 2.0 none none none 2.5 Convey- Coz+ none none none none none sion Mnz+ 0.6 none 1.0 1.0 none Treat-ment Grams Caz+ none none none none none Compo-Per Literz+
ition of: Sr one one one .0 .9 s WOq'z none none 0.3 none none Constit-uents NO; 8.9 7.6 9.0 8.0 7.3 and Process F- 0.1 none 0.1 none 0.1 Condi- NOz 0.01 none 0.01 none none tions:
NHQOH none 1.5 none 3.0 3.5 Treatment 40 45 50 39 20 Temperature, C
Treatment 120 120 120 ~ 120 120 Time, ~
Seconds Table 19: COMPARATIVE EXAMPLES 36 TO 40 Comparative Example Number:
PREPALENE~-ZN, 1 none none none none g/1 Surface Abbreviation none Zn2CaP2 Zn3P2 Zn2CaP2Zn2FeP2 Condi-Phosphate tinninParticlesParticle size, none 0.8 6.8 0.6 0.5 hum g Treat- Concentration, none 10 1 5 0.0001 g/1 ment MonomerRl H none none CH3 none Com- ith positionForm- Rz CZH40H none none C3H,OH none ~ ~
ula (I) Constit- Wt% in Polymer 100 none none 20 none uents Other Monomer Name none none acrylicmaleficmetha-and Un- acid acid crylic saturated acid ProcessAcid Condi-MonomerWt7o in Polymernone none 100 80 50 tions:ether Monomer Name none none none none styrenesul-Co- fonic monomer 'acid Wtlo in Polymernone none none none 50 Polymer 1 none 2,000 3,000 5 Concentration, ppm Salt Chemical FormulaM~S004 N;~H none NazC03 Ni~O~
con- 7Hz O z z stituent(s) z Concentration, 0.5 1 none 5 10 g/1 SurfactantAbbreviation none none none none EO11NPE
Constit-uents Concentration, none none none none 2.0 g/1 Treatment 20 20 20 20 40 Temperature, C
Treatment 30 30 30 30 120 Time, Seconds Phos- Znz+ 0.8 1.3 2.2 1.5 1.4 Convey- Mgz+ 2.0 none none none 2.5 sion Grams Coz+ none 1.0 none none none i per Treat-L Mnz+ 0.5 none 1.0 none none ter of:
went Compo- Caz+ none none none 1.5 none sition Srz+ none none none none 0.9 Constit-uents WOa z none none 0.3 none none and NO~ 8.3 7.6 9.0 8.0 7.3 Process F- 0.1 none 0.1 none 0.1 Condi-tions: NOz 0.01 none 0.01 none 0.01 NH40H none 1.5 none 3.0 none Treatment 40 45 50 39 43 Temperature, C
Treatment 120 120 I 120 120 120 Time, I
Seconds I
Table 20: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUBSTRATEEXAMPLE
T NUMBER
ESTED
Coating Appearance CRS + + + + +
EG + + + + +
GA + + + + +
Secondary (Water-Resistant)CRS + + + + + + + + +
+
Adherence EG ++ ++ + ++ ++
GA ++ ++ + ++ ++
CRS ++ ++ ++ ++ +
Resistance to Hot Salt Water EG ++ ++ ++ ++ ++
GA ++ ++ ++ ++ ++
CRS + ++ ++ + +
Resistance to Salt Spray EG ++ + ++ + ++
GA ++ + ++ + ++
Table 21: APPEARANCE OF THE CONVERSION COATING AND RESULTS OF PAINTING
TEST OR OTHER RATING SUB- COMPARISON
EXAMPLE
NUMBER
STRATE
CRS x + x x x + x x x x Coating Appearance EG x + x x x + x x x +
GA x + x x x + x x x +
CRS ++ + ++ ++ ++ + ++ ++ ++ +
Secondary (Water-Resistant) Adherence EG x x x x x x x x x x GA x x x x x x x x x x CRS x ++ x x x ++ x x x x Resistance to Hot Salt Water EG x + x x x + x x x +
GA x + x x x + x x x +
CRS x x x x x x x x x x Resistance to Salt Spray EG x + x x x + x x x x GA x x x x x x x x x x
Claims (4)
1. A process for forming a phosphate conversion coating on a metal substrate surface, said process comprising the following operations:
(I) contacting the metal substrate surface with an aqueous liquid surface condition-ing composition that comprises, preferably consists essentially of, or more pref-erably consists of, water and the following components:
(I.A) dispersed solid phosphate particles that:
(i) have a diameter no greater than 5 µm; and (ii) comprise at least one substance selected from the group consisting of phosphates that contain at least one type of divalent or trivalent metal cations;
and (I.B) as adhesion-promoting component, at least one selection from the group consist-ing of the following subgroups:
(1) monosaccharides, polysaccharides, and derivatives thereof;
(2) phosphorus containing solutes selected from the group consisting of orthophosphoric acid, condensed phosphoric acids, and organophos-phonic acid compounds;
(3) water-soluble polymers that are homopolymers or copolymers of vinyl acetate and derivatives of these homopolymers and copolymers; and (4) copolymers and polymers afforded by the polymerization of:
(a) at least one selection from:
-- monomers, exclusive of vinyl acetate, that conform to general chemical formula (I):
where R1 = H or CH3 and R2 = H, C1 to C5 alkyl, or C1 to C5 hydroxyalkyl; and -- other .alpha.,.beta.-unsaturated carboxylic acid monomers; and, optionally, (b) not more than 50 % by weight of monomers that are not vinyl acetate and are not within the description of part (a) immediately above but are copolymerizable with said monomers that are within the description of said part (a);
and (II) contacting the metal substrate surface as conditioned in operation (I) as de-scribed above with a nickel-free phosphate conversion treatment bath that com-prises water and the following amounts of the following components:
(II.A) from 0.5 to 5 g/l of zinc cations;
(II.B) from 5 to 30 g/l of phosphate ions; and (II.C) a component of conversion accelerator.
(I) contacting the metal substrate surface with an aqueous liquid surface condition-ing composition that comprises, preferably consists essentially of, or more pref-erably consists of, water and the following components:
(I.A) dispersed solid phosphate particles that:
(i) have a diameter no greater than 5 µm; and (ii) comprise at least one substance selected from the group consisting of phosphates that contain at least one type of divalent or trivalent metal cations;
and (I.B) as adhesion-promoting component, at least one selection from the group consist-ing of the following subgroups:
(1) monosaccharides, polysaccharides, and derivatives thereof;
(2) phosphorus containing solutes selected from the group consisting of orthophosphoric acid, condensed phosphoric acids, and organophos-phonic acid compounds;
(3) water-soluble polymers that are homopolymers or copolymers of vinyl acetate and derivatives of these homopolymers and copolymers; and (4) copolymers and polymers afforded by the polymerization of:
(a) at least one selection from:
-- monomers, exclusive of vinyl acetate, that conform to general chemical formula (I):
where R1 = H or CH3 and R2 = H, C1 to C5 alkyl, or C1 to C5 hydroxyalkyl; and -- other .alpha.,.beta.-unsaturated carboxylic acid monomers; and, optionally, (b) not more than 50 % by weight of monomers that are not vinyl acetate and are not within the description of part (a) immediately above but are copolymerizable with said monomers that are within the description of said part (a);
and (II) contacting the metal substrate surface as conditioned in operation (I) as de-scribed above with a nickel-free phosphate conversion treatment bath that com-prises water and the following amounts of the following components:
(II.A) from 0.5 to 5 g/l of zinc cations;
(II.B) from 5 to 30 g/l of phosphate ions; and (II.C) a component of conversion accelerator.
2. A process according to claim 1, wherein the phosphate conversion treatment bath also contains from 0.1 to 3.0 g/l of at least one type of ions selected from the group consisting of magnesium ions, cobalt ions, manganese ions, calcium ions, tungstate ions, and strontium ions.
3. A process according to claim 2, wherein the concentration of component (I.A) is from 0.001 to 30 g/l and the concentration of component (I.B) is from 1 to 2,000 ppm.
4. A process according to claim 1, wherein the concentration of component (I.A) is from 0.001 to 30 g/l and the concentration of component (I.B) is from 1 to 2,000 ppm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11/230060 | 1999-08-16 | ||
| JP23006099A JP3545974B2 (en) | 1999-08-16 | 1999-08-16 | Phosphate conversion treatment method for metal materials |
| PCT/US2000/022335 WO2001012341A1 (en) | 1999-08-16 | 2000-08-16 | Process for forming a phosphate conversion coating on metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2381774A1 true CA2381774A1 (en) | 2001-02-22 |
Family
ID=16901934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002381774A Abandoned CA2381774A1 (en) | 1999-08-16 | 2000-08-16 | Process for forming a phosphate conversion coating on metal |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1230033A4 (en) |
| JP (1) | JP3545974B2 (en) |
| CA (1) | CA2381774A1 (en) |
| WO (1) | WO2001012341A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5300113B2 (en) * | 2001-04-27 | 2013-09-25 | 日本表面化学株式会社 | Metal surface treatment agent, metal surface treatment method using metal surface treatment agent, and iron component subjected to surface treatment |
| KR100554740B1 (en) * | 2001-12-17 | 2006-02-24 | 주식회사 포스코 | A method for manufacturing a electro-galvanized steel sheet having the phosphated film formed thereon |
| JP4081276B2 (en) * | 2002-01-11 | 2008-04-23 | 日本パーカライジング株式会社 | Water-based surface treatment agent, surface treatment method, and surface-treated material |
| DE60311708D1 (en) * | 2002-06-13 | 2007-03-29 | Nippon Paint Co Ltd | Zinc phosphate conditioning agent for phosphate conversion coating of steel plate and corresponding product |
| ES2364405T3 (en) | 2004-02-20 | 2011-09-01 | Chemetall Gmbh | SURFACE CONDITIONER AND SURFACE CONDITIONING METHOD. |
| JP2006299379A (en) * | 2005-04-25 | 2006-11-02 | Nippon Paint Co Ltd | Surface conditioner and surface conditioning method |
| KR101068708B1 (en) | 2006-02-20 | 2011-09-28 | 수미도모 메탈 인더스트리즈, 리미티드 | Method for manufacturing hot-dip galvanized steel sheet having zinc phosphate coating |
| DE102008017523A1 (en) * | 2008-03-20 | 2009-09-24 | Henkel Ag & Co. Kgaa | Optimized electrocoating of assembled and partially pre-phosphated components |
| JP6083020B2 (en) * | 2012-10-24 | 2017-02-22 | 株式会社正信 | Surface treatment method of magnesium or magnesium alloy, acid detergent and chemical conversion treatment agent, and chemical conversion treatment structure of magnesium or magnesium alloy |
| EP3026677B1 (en) * | 2013-07-23 | 2018-04-11 | Asahi Kasei Kabushiki Kaisha | Copper and/or copper oxide dispersion, and method for electroconductive film using dispersion |
| US20170306497A1 (en) * | 2016-04-25 | 2017-10-26 | Ppg Industries Ohio, Inc. | System for nickel-free zinc phosphate pretreatment |
| KR102450429B1 (en) | 2016-08-12 | 2022-10-04 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Pretreatment composition |
| US20180044796A1 (en) * | 2016-08-12 | 2018-02-15 | Ppg Industries Ohio, Inc. | Two-step pretreatment system and method |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
| HUE047403T2 (en) * | 2017-04-21 | 2020-04-28 | Henkel Ag & Co Kgaa | Sludge-free zinc phosphate coating forming method for metallic components in series |
| EP3392376A1 (en) * | 2017-04-21 | 2018-10-24 | Henkel AG & Co. KGaA | Method for forming zinc phosphate coatings on metallic components in series |
| JP7390318B2 (en) * | 2018-06-11 | 2023-12-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Aqueous dispersion for metal surface activation and method for phosphate treatment of metal surfaces |
| EP3964606A1 (en) * | 2020-09-04 | 2022-03-09 | Henkel AG & Co. KGaA | Single stage zinc phosphating method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1084017A (en) * | 1963-09-30 | 1967-09-20 | Jawata Iron & Steel Co Ltd | Pretreating process for phosphate-treating steel sheets or plated steel sheets |
| US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
| US5326408A (en) * | 1993-06-15 | 1994-07-05 | Henkel Corporation | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
| EP0717788B1 (en) * | 1993-09-17 | 1997-07-30 | Brent International Plc. | Pre-rinse for phosphating metal surfaces |
| US5494504A (en) * | 1994-09-12 | 1996-02-27 | Ppg Industries, Inc. | Liquid rinse conditioner for phosphate conversion coatings |
| JP3451334B2 (en) * | 1997-03-07 | 2003-09-29 | 日本パーカライジング株式会社 | Pretreatment liquid for surface conditioning before phosphate conversion treatment of metal and surface conditioning method |
| JPH116076A (en) * | 1997-06-13 | 1999-01-12 | Nippon Parkerizing Co Ltd | Phosphate treatment of steel material |
-
1999
- 1999-08-16 JP JP23006099A patent/JP3545974B2/en not_active Expired - Fee Related
-
2000
- 2000-08-16 CA CA002381774A patent/CA2381774A1/en not_active Abandoned
- 2000-08-16 WO PCT/US2000/022335 patent/WO2001012341A1/en not_active Application Discontinuation
- 2000-08-16 EP EP00955545A patent/EP1230033A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP3545974B2 (en) | 2004-07-21 |
| EP1230033A4 (en) | 2004-12-08 |
| EP1230033A1 (en) | 2002-08-14 |
| WO2001012341A1 (en) | 2001-02-22 |
| JP2001049451A (en) | 2001-02-20 |
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