CA2214654A1 - Composition and process for forming an underpaint coating on metals - Google Patents
Composition and process for forming an underpaint coating on metals Download PDFInfo
- Publication number
- CA2214654A1 CA2214654A1 CA002214654A CA2214654A CA2214654A1 CA 2214654 A1 CA2214654 A1 CA 2214654A1 CA 002214654 A CA002214654 A CA 002214654A CA 2214654 A CA2214654 A CA 2214654A CA 2214654 A1 CA2214654 A1 CA 2214654A1
- Authority
- CA
- Canada
- Prior art keywords
- liquid composition
- aqueous liquid
- composition according
- ppm
- magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- C23C22/362—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 also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—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
- C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
A zinc phosphating composition containing organoperoxide along with zinc ions and phosphate ions forms finely crystalline, dense, and thin conversion coatings on metal surfaces that are normally zinc phosphate conversion coated, even at coating temperatures below 50 ~C and without any "conditioning" of the surface before conversion coating by contact of the surface to be conversion coated with a conventional colloidal suspension of titanium salts.
Description
CA 022l46~4 l997-09-04 Description COMPOSITION AND PROCESS FOR FORMING AN llJNDERPAINT
COATING ON METALS
Technical Field This invention relates to a surface treatment method that can be applied to various types of metals to form thereon an undercoating film usable with a va-riety of paint systems. More specifically, this invention relates to a surface treat-s ment method of the described type that, without using a titanium colloid surface-conditioning treatment: (a) produces a dense, fine, and uniform conversion film;(b) induces the formation of fine-sized crystals in the conversion film; and (c)forms a high quality underpaint coating for electrodeposition painting, solvent based painting, powder coating, and the like.
.0 Back~round Art Zinc phosphate conversion treatments and chromate treatments are cur-rently in widespread use as underpaint coating treatments for various types of metals for the purpose of improving the post-painting corrosion resistance and paint film adherence. Zinc phosphate conversion treatments are mainly used when the metal substrate is composed of iron or is a composite of several types of materials, because it is difficult for chromate treatments to accommodate or be adapted to such substrates.
The crystals in the films afforded by zinc phosphate conversion treatment are subject to substantial variation in size as a function of the treatment condi-tions. Thick coatings of coarse crystals are ideal for plastic-working operations and rust prevention, but when such coatings are painted they may fail to providea satisfactory paint film adherence. In fact, the most demanding uses of zinc phosphate conversion coatings as underpaint coatings require the generation of thin conversion films of uniform, dense, and fine coating crystals.
Two general methods are known for generating thin zinc phosphate con-version coatings. In one method, contact with the conversion treatment bath is suspended after only partial completion of the film-deposition reactions, thereby stopping these reactions. A problem with this method is that it gives an incom-plete deposition of the conversion film and thus fails to provide complete cover-CA 022146~4 1997-09-04 W 096/27692 PCTrUS96/02677 age of the basis metal. As a result, post-conversion water rinse and drying pro-cesses can cause the substrate to rust, and the post-painting corrosion resist-ance will also be unsatisfactory.
The other general method relies on inducing fine-sized coating crystals.
In this method the hlm-deposition reactions spontaneously terminate, or at leastgreatly slow, while the film is still thin, and the completed conversion coatingcompletely covers the substrate. This method can provide both a satisfactory paint film adherence and post-painting corrosion resistance.
Immersion and spraying techniques are primarily used in the above de-.o scribed zinc phosphate conversion treatment technologies. In the absence of aprior"conditioning" treatment of the metal surfaces to be coated, immersion doesnot usually produce dense, fine coating crystals and requires a lengthy period of time for conversion treatment unless the treatment temperature is 55 ~C or great-er. Spraying does produce a somewhat better fine-crystal formation in the coat-~s ing than does immersion, but not usually enough to provide a fully satisfactorypainting performance. And again, treatment temperatures of at least 55 ~C are required in order to complete the treatment in a relatively brief period of time.
A titanium colloid surface-conditioning treatment must usually be applied to the metal surface imrnediately prior to conversion treatment in order to obtain (a) fine-crystal formation in the coating and (b) a reduction in the treatment tem-perature to 50 ~C and below. This surface-conditioning treatment activates the surface of the metal substrate, with the result that, regardless of the use of im-mersion or spraying, the treatment temperature can be lowered, the treatment time can be shortened, and a fine-sized crystalline film that provides an entirely 2s satisfactory painting performance can be obtained.
When metal surfaces are subjected to a zinc phosphate conversion treat-ment for the above-described purpose of providing an underpaint coating, the surface is ordinarily subjected to a titanium colloid surface-conditioning treatment immediately prior to the conversion treatment process. However, the titanium colloid dispersed in the surface-conditioning treatment bath aggregates with elapsed time after bath preparation, leading to a decline in the surface-condition-ing activity with continued time of use. Japanese Patent Publication Number Sho CA 022l46~4 l997-09-04 62-9190 [9,190/1987] teaches management of the Mg/P2O7 ratio in the surface-conditioning treatment bath in order to increase the stability of the titanium col-loid, while Japanese Patent Application Laid Open [Kokai or Unexamined] Num-ber Sho 63-18084 [18,0~4/1988] discloses the addition to the surface-condition-ing treatment bath of an organic material as a stabilizer for the titanium colloid.
Each of these methods, however, is less effective than would be desirable, with the result that in practice aged bath must be discharged and freshly prepared bath must be supplied on a continuous or at least frequent basis in order to cope with the decline in activity. This preparation and management of the surface-~0 conditioning treatment bath is complex and labor intensive and entails a major economic burden due to its high reagent consumption. And of course, because treatment facilities are required in order to implement the surface-conditioningtreatment, this raises costs for maintenance of the facilities and an expansion of the treatment space.
As a consequence of the various issues discussed above, there has re-cently been strong demand for the development of a surface treatment method that could omit the problematic titanium colloid surface-conditioning treatment while still being able to form on metal surfaces the uniform, fine, dense, and thin conversion films that are optimal as underpaint coatings.
Disclosure of the Invention Problems to Be Solved by the Invention This invention was developed in order to solve the above-described prob-lems that occur with the surface-conditioning treatment that is run immediately prior to zinc phosphate conversion treatment. In specific terms, this invention in-troduces a surface treatment method for the formation of underpaint coatings on metals, wherein said method, without the use of a surface-conditioning treatment, can form on the surface of various metals a uniform, fine, and dense conversion coating that provides an excellent paintability and is also able to generate fine-sized crystals in the conversion coating.
Summary of the Invention It has been found that the use of a heretofore unexamined organic oxidiz-ing agent, namely, organoperoxide, led to the deposition of a uniform, thin, finely 2 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - O 9 - O 4 PCT/US96/02677 crystalline, and dense conversion coating on the surfaces of metal substrates--and thereby yielded an eYcel'ent painting performance--even when zinc phos-phate conversion treatment was used on the metal surface directly after cleaningwithout any intervening surface-conditioning treatment. It was also discovered at the same time that the surface treatment method according to the present invention afforded the desired effects to a satisfactory degree even at relatively low conversion coating temperatures.
In specific terms, then, the surface treatment method according to the present invention for the formation of underpaint coatings on metals characterist-.0 ically comprises the formation of a conversion coating on metal surfaces by first c!eaning the surface of the metal and, without any surface conditioning treatment as is conventionally performed, thereafter bringing the said clean surface into contact with a zinc phosphate conversion treatment bath that contains zinc ions,phosphate ions, and organoperoxide.
No particular restrictions apply to the type, shape, or dimensions of metals that may be treated by the method according to the present invention. For ex-ample, the method according to the present invention can be applied to a varietyof iron and steel materials, for example, steel sheet and zinciferous metal-plated steel sheet, and to a variety of aluminum materials, for example, aluminum sheetand aluminum alloys such as aluminum-magnesium alloys and aluminum-silicon alloys.
Detailed Description of the Invention and Its Preferred Embodiments The organoperoxide concentration in the subject conversion treatment bath is preferably from 50 to 1,500 ppm, and the temperature of the conversion 2s treatment bath is preferably from 25 ~C to 50 ~C.
The surface treatment method according to the present invention requires that the zinc phosphate conversion treatment be executed on a clean metal sur-face. Accordingly, metals with already clean surfaces can be directly exposed to the conversion treatment bath without further processing. However, when the metal surface is contaminated by adhering iron powder, dust, oil, or the like, the surface contaminants must be removed by a cleaning process such as aqueous alkaline degreasing, emulsion degreasing, solvent-based degreasing, and so CA 022146~4 1997-09-04 forth. When a water-based cleaner is used, cleaning is preferably foliowed by a water rinse station where cleaning solution carried forward on the metal surface is removed.
The zinc phosphate conversion treatment bath employed by the method according to the present invention is essentially an acidic aqueous solution that '' contains zinc ions, phosphate ions, and organoperoxide. The zinc ions concen-tration in the conversion treatment bath is generally preferably from 0.5 to 5.0g/L. An adequate coating weight may not be obtained when the zinc ions con-centration is below 0.5 g/L; this leads to a decline in the coverage ratio by the re-.0 sulting conversion coating on the metal surface and thereby to an inadequate post-painting corrosion resistance. Concentrations in excess of 5.0 g/L can cause a coarsening of the coating crystals, thereby producing in particular a decline in the post-painting paint film adherence.
The phosphate ions concentration in the conversion treatment bath used by the method according to the present invention is preferably from 5.0 to 30.0 g/L. Concentrations below 5.0 g/L can make it difficult to form normal conversion coali,lgs, while concentrations in excess of 30.0 g/L do not provide any additional increments in activity and are therefore uneconomical. The phosphate ions can be formed by the addition of phosphoric acid or its aqueous solutions to the con-version treatment bath or by the dissolution of sodium phosphate, magnesium phosphate, zinc phosphate, or the like in the conversion treatment bath. The stoichiometric equivalent as phosphate ions of all such sources of phosphoric acid, condensed phosphoric acids, and salts of simple or condensed phosphoric acids in the liquid compositions used for conversion coating is to be understoodas phosphate ions for the purposes of determining these preferred concentra-tions, irrespective of the actual degree of ionization that exists in the composi-tions. Primarily for reasons of economy, orthophosphoric acid and its salts are preferred.
The conversion treatment bath used in the present invention contains at least one organoperoxide. The organoperoxide has oxidizing power, as do many other materials such as nitrite ions that are called "accelerators" and are com-monly used in prior art phosphate conversion coating forming compositions.
-CA 022l46~4 1997-09-04 W 096/27692 PCTrUS96/02677 Organoperoxide, unlike previously known accelerators, also functions to induce fine-size crystal formation in the conversion coating. This enables the surface treatment method according to the present invention to form a uniform, thin, finely crystalline, and dense conversion coating in the absence of a titanium col-loid surface-conditioning treatment. The use of an organoperoxide-containing conversion treatment bath is the most characteristic feature of the method ac-cording to the present invention.
The organoperoxide used in the subject conversion treatment bath is ex-emplified by organoperoxides, such as tert-butyl hydroperoxide, di-tert-butyl peroxide, acetylacetone peroxide, cumene hydroperoxide, tert-butylperoxymaleic acid, and so forth that have a simple peroxy moiety, and by organoperoxides thathave a percarboxylic acid moiety, such as peracetic acid, monoperphthalic acid, persuccinic acid, and so forth. When the organoperoxide has a low solubility in the treatment bath, its presence in the aforementioned conversion treatment bathcan be induced by solubilization through the addition of a relatively small amount of a water-soluble organic solvent or surfactant.
The organoperoxide is preferably added to give a concentration from 50 to 1,500 ppm in the conversion treatment bath. An organoperoxide concentration in the conversion treatment bath below 50 ppm can result in an inadequate ac-celeration of conversion coating formation and inadequate results in terms of pro-ducing fine-size crystals in the coating. Concentrations in excess of 1,500 ppm do not produce any additional increments in results and are therefore uneconom-ical.
The zinc phosphate conversion treatment bath used by the present inven-2s tion may also contain etchant, whose function is to generate a uniform etch of thesurface of the metal being treated, and non-zinc metal ions, whose function is to provide additional improvements in the painting performance.
Fluoride ions or complex fluoride ions, e.g., fluosilicate ions, can be used as the etchant. Fluorine compounds that produce these ions are exemplified by hydrofluoric acid, fluosilicic acid, and their metal salts (sodium salt, potassium salt), and the etching ions are produced by the dissolution of these compounds in the conversion treatment bath. The etching ions are preferably present in the CA 022l46~4 l997-09-04 W 096/27692 PCTrUS96/02677 conversion treatment bath at a concentration from 100 to 2,000 ppm.
Nickel ions, manganese ions, cobalt ions, rnagnesium ions, calcium ions, and the like can be employed as the non-zinc metal ions additive. Each of these kinds of ions can be fommed by ~~issolution in the conversion treatment bath of an oxide, hydroxide, carbonate, sulfate, phosphate, and/or other compound of the corresponding metal, or even of the elemental metal itself. These metal ions arepreferably present in the conversion treatment bath at a concentration from 100 to 2,000 ppm.
The conversion treatment bath used by the present invention need not 10 contain nitric acid, nitrous acid, an organic nitro compound, etc., and in conse-quence thereof can be formulated as a conversion bath that is completely free of nitrogenous compounds. This nitrogen-free formulation eliminates the need for a nitrogenous compound treatment step during effluent treatment and makes it quite easy for the surface treatment method according to the present invention to accommodate environmental regulations on the effluent levels of nitrogenous compounds.
A preferred treatment sequence in a process according to the present invention comprises, more preferably consists essentially of, or still more preferably consists of the following steps, executed in the given sequence: alka-line degreasing, water rinse, zinc phosphate conversion treatment, and waterrinse. The degreasing process and water rinses can in each case be implement-ed as single-step or m~ ~Itistep processes. The final water rinse is preferably a de-ionized water rinse. Painting can be carried out after the final water rinse without an intervening drying step or can be carried out after a drying step following the 2~ final water rinse.
Zinc phosphate conversion treatment using the surface treatment method according to the present invention is ordinarily run by immersion or spraying ora combination thereof. In practice a satisfactory conversion film can be formed using treatment times (contact time between the metal surface and conversion treatment bath) from approximately 1 minute to approximately 5 minutes. The temperature of the zinc phosphate conversion treatment bath is preferably 25~
C to 50 ~C.
WO 96/27692 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - O 9 - O 4 PCT/US96/02677 The functions and effects of the surface treatment method according to the present invention are ~iiscussed beiow with particular reference to the activity in conversion film formation of the organoperoxide present in the zinc phosphateconversion treatment bath used in the present invention.
When the metal workpiece is ferriferous, the organoperoxide used in the method according to the present invention also oxidizes dissolved divalent iron ioh to trivalent iron ions, just as do the prior-art inorganic oxidizing agents. This prevents the accumulation of divalent iron ions, which are detrimental to the con-version reactions. The trivalent iron ions afforded by oxidation react with the phosphate ions present in the conversion treatment bath to form an iron phos-phate (FePO4 ~ x H2O) sludge that is easily removed from the system.
The present invention may be further appreciated by consideration of the working examples and comparative examples of actual treatment as shown be-low; however, the present invention is not limited to the following examples.
Examples The test materials were cold-rolled steel sheet (SPCC-SD, sheet thick-ness: 0.8 mm), zinc-electroplated steel sheet (sheet thickness: 0.8 mm, plating weight: both surfaces 30 g/m2), galvannealed hot-dip zinc-plated steel sheet (sheet thickness: 0.8 mm, plating weight: both surfaces 45 g/m2), and aluminum-magnesium alloy sheet (A5052, sheet thickness: 1.0 mm). In each case they were cut to 70 x 150 mm to prepare the specimens that were then subjected to the treatments in the working and comparative examples. Each test material was coated with 2 g/m2 of a commercial cleaning/rust-preventing oil.
The treatment processes common to the working and comparative examp-2s les are given below.
(1) degreasing (FINECLEANER(I~) L4460 alkaline degreaser from Nihon Parkerizing Com-pany, Limited, solution in water of 20 grams per liter (hereinafter usually abbreviated as "g/L") of agent A and 12 g/L of agent B) 43 ~C, 120 seconds of contact time, immersion (2) tap-water rinse ambient temperature, 30 seconds, spray CA 022146~4 1997-09-04 (3) zinc phosphate conversion treatment (Specific conditions are given in the respective working and comparative examples. The treatment time was always 120 seconds.) (4) tap-water rinse ambient temperature, 30 seconds, spray (5) deionized water rinse (deionized water with a conductivity of 0.2 microsiemens/cm) ambient temperature, 20 seconds, spray (6) drain/dry: hotairat110~C, 180seconds Treatment compositions, alternatively called "baths" for brevity, numbered (1 ) to (3) as described below were used as starting points for the zinc phosphate conversion treatment baths. The type and concentration of organoperoxide or other oxidizing agent, the treatment temperature, and the treatment time are giv-en in the particuiar working and comparative examples.
~5 Conversion treatment bath (1) Phosphate ions : 15 g/L (from addition of 75 % phosphoric acid) Zinc ions : 1.3 g/L (from addition of zinc oxide) Nickel ions : 0.5 g/L (from addition of nickel carbonate) Fluorine component : 1.0 g/L (from addition of sodium fluosilicate) 2-butanol : 30g/L
Free acidity : 0.6 points (Points of free acidity are defined as the number of milliliters of 0.1N sodium hy-droxide solution in water needed to titrate a 10 milliliter sample of the composi-tion to a color change from yellow to blue, using Bromophenol Blue indicator.) Conversion treatment bath (2) Phosphate ions : 13 g/L (from addition of 75 % phosphoric acid) Zinc ions : 1.1 g/L (from addition of zinc oxide) Cobalt ions : 0.4 g/L (from addition of basic cobalt carbonate) Fluorine component: 0.4 g/L (from addition of sodium bifluoride) Free acidity : 0.4 points Conversion treatment bath (3) Phosphate ions : 17 g/L (from addition of 75% phosphoric acid) WO 96/27692 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - 0 9 - O 4 PCT/US96/02677 Zinc ions : 1.5 g/L (from addition of zinc oxide) Free acidity : 0.7 points Each of conversion treatment baths (1 ) to (3) was adjusted to the speci-fied free acidity, after adding all other ingredients as shown, by adding sodium5 hydroxide.
The coating weights were measured as follows. The weight in grams of the treated sheet after conversion treatment was measured to give "W1". The coating was then stripped off the treated sheet using the stripping solution andstripping conditions given below, and the weight in grams of the stripped sheet .0 was measured to give "W2". The coating weight in grams per square meter (hereinafter usually abbreviated as "g/m2") was then calculated using the follow-ing equation: coating weight in g/m2 = (W1 - W2)/0.021 Stripping conditions (1) Forthe cold-rolled steel sheet:
stripping solution: 5 % aqueous chromic acid stripping conditions: 75 ~C, 15 minutes, immersion (2) For the zinc-electroplated steel sheet and galvannealed hot-dip zinc-plat- ed steel sheet:
stripping solution: 2 weight % of ammonium dichromate + 49 weight %
of 28 weight % aqueous ammonia + 49 weight % of pure water stripping conditions: room temperature, 15 minutes, immersion (3) For the aluminum alloy sheet stripping solution: 5 % aqueous chromic acid stripping conditions: room temperature, 5 minutes, immersion ; The deposited coating crystals were inspected with a scanning electron microscope (hereinafter usually abbreviated as "SEM") at 1,000X. This magni-fied image was used to evaluate base metal coverage (presence/absence of ex-posed substrate) and to measure the particle size of the conversion coating crys-tals for evaluation of the extent of fine-size crystals.
The following standards were used for reporting the base metal coverage and the extent of fine-size crystals.
CA 022146~4 1997-09-04 Standards for evaluation of the crystal particles cold-rolled steel sheet:
+ less than 35 micrometers x greater than or equal to 35 micrometers s zinc-electroplated steel sheet:
+ less than 25 micrometers x greater than or equal to 25 micrometers galvannealed hot-dip zinc-plated steel sheet:
+ less than 30 micrometers .0 x greater than or equal to 30 micrometers aluminum alloy sheet:
+ less than 30 micrometers x greater than or equal to 30 micrometers ~2) Standard for evaluation of the base metal coverage For all specimens:
+ absolutely no exposure of base metal observed x some exposure of the base metal observed Conversion-treated test panels were electrodeposition painted using a cationic electrodeposition paint (ElecronTM 2000 from Kansai Paint Kabushiki Kaisha) to give a paint film with a film thickness of 20 micrometers. These paint-ed specimens were then subjected to the following painting performance tests in order to evaluate the painting performance.
(1 ) Test of the post-painting corrosion resistance A cut was introduced into the paint film on the painted sample. The paint-ed sample was thereafter immersed for 240 hours in 5 % aqueous sodium chlor-ide heated to 50 ~C, and then removed, rinsed with water, and dried. The neigh-borhood of the cut was peeled using cellophane tape, and the maximum width of paint film peeling on one side was measured after the tape peel and reported on the following scale:
30 + maximum one-side width of peel is less than 7 millimeters (hereinafter us-ually abbreviated as "mm");# : maximum one-side width of peel is at least 7 mm but less than 10 mm;
-WO 96/27692 CA 0 2 2 14 6 ~ 4 19 9 7 - O 9 - O 4 PCT/US96/02677 x : maximum one-side width of peel is at least 10 mm.
(2) Test of the water-resistant secondary adherence The painted sample was immersed for 240 hours in pure water heated at 40 ~C and then removed and dried. A cross was thereafter scribed in the paint 5 film; the center of the cut was extruded 3 mm using an Erichsen tester; and, aKer a cellophane tape peel, the paint film peel ratio (i.e., the ratio of the peeled area to the extruded area) was measured. The following scale was used for reporting:
+ : paint film peel ratio is less than 10 %
# : paint film peel ratio is at least 10 % but less than 20 %
10 x : paint film peel ratio is at least 20 %.
Two hundred (200) parts per million by weight (hereinaKer usualiy abbrevi-ated as "ppm") of tert-butyl hydroperoxide was added to Conversion treatment bath (1), which was then used to treat cold-rolled steel sheet by immersion at a15treatment temperature of 45 ~C.
E)CAMPLE 2 Eighty (80) ppm of di-tert-butyl peroxide was added to Conversion treat-ment bath (1), which was then used to treat zinc-electroplated steel sheet by im-mersion at a treatment temperature of 45 ~C.
Five hundred (500) ppm of tert-butyl hydroperoxide was added to conver-sion treatment bath (2), which was then used to treat cold-rolled steel sheet byspraying at a treatment temperature of 40 ~C.
2sOne thousand one hundred (1,100) ppm of acetylacetone peroxide was added to conversion treatment bath (2), which was then used to treat zinc-elec-troplated steel sheet by immersion at a treatment temperature of 40 ~C.
Five hundred (500) ppm of di-tert-butyl peroxide was added to conversion 30treatment bath (1), which was then used to treat cold-rolled steel sheet by immer-sion at a treatment temperature of 43 ~C.
CA 022146~4 1997-09-04 Five hundred (500) ppm of tert-butyl hydroperoxide was added to conver-sion treatment bath (3), which was then used to treat galvannealed hot-dip zinc-plated steel sheet by spraying at a treatment temperature of 33 ~C.
One hundred fifty (150) ppm of di-tert-butyl peroxide was added to conver-sion treatment bath (1), which was then used to treat aluminum-magnesium alloy sheet by spraying at a treatment temperature of 43 ~C.
COI\APARATIVE EXAMPLE 1 Two hundred (200) ppm of sodium nitrite was added to conversion treat-ment bath (1), which was then used to treat cold-rolled steel sheet by immersionat a treatment temperature of 43 ~C.
Cold-rolled steel sheet was treated by imrnersion in conversion treatment bath (1 ) heated to 43 ~C.
COI\/IPARATIVE EXAMPLE 3 Two thousand (Z,000) ppm of sodium chlorate was added to conversion treatment bath (2), which was then used to treat zinc-electroplated steel sheet by immersion at a treatment temperature of 40 ~C.
Galvannealed hot-dip zinc-plated steel sheet was sprayed with conversion treatment bath (3? heated to 33 ~c.
Aluminum-magnesium alloy sheet was sprayed with conversion treatment bath (1) heated to 43 ~C.
The treatment conditions and test results for all of the Examples are reported in Tables 1 and 2 respectively and the treatment conditions and test results for all of the Comparative Examples are reported in Tables 3 and 4 respectively.
CA 022146~4 1997-09-04 W 096127692 PCTrUS96/02677 Table 1.
Iden Met- C: l ~lion in theOxidizing Fluor- Points of Temper- Con-tifi- al C~ n Coating Bath, Agent ine Free ature in tact ca- Coat- g/Lof: Con-Acidity in ~C dur- Tech-tion ed cen- Con- ing Con- nique Phos- Zinc Other Type Ppm tra- version version phatelons Metal tion,Coating Coating lons lons g/L Bath E 1 CRS 15 1.3Ni: 0.5 A 200 1 0.6 45 Im E2 EG 15 1.3Ni: 0.5 B 80 1 0.6 45 Im E 3 CRS 13 1.1Co: 0.4 A 500 0.4 0.4 40 Sp E 4 EG 13 1. ICo: 0.4 C 1100 0.4 0.4 40 Im E 5 CRS 15 1.3Ni: 0.5 B 500 1 0.6 43 Im E 6 GA 17 1.5 - A 500 - 0.7 33 Sp E 7 AL 15 1.3Ni: 0.5 B 150 1 0.6 43 Sp Abbreviations for Table I
E = Example; CRS = cold-rolled steel sheet; EG = galvanized steel sheet; GA = galvannealed hot-dip zinc-plated steel sheet; AL = ~hlminllm-~ ..P,;l,... alloy sheet; A = tert-butyl hydroperoxide; B = di-tert-butyl peroxide; C = acetylacetone peroxide; Im = Immersion; Sp = Spray Table 2 Idcnliri ~lion Coating Mass, Test Score for Test of:
glm2 Crystal Size Base MetalPost-Painting Water-CoverageCorrosionResistant R~ t~lnceSecondary A~
Example 1 0.9 + + + +
Example 2 3.5 + + + +
Example3 1.2 + + + +
Example 4 3.2 + + + +
Example 5 1.3 + + + +
Example 6 4.3 + + # +
Example 7 2.5 + + + +
W 096t27692 PCTAUS96/02677 Table 3 Iden Met- C~a ~ Il in the O ~ Fllllor- Points Temper- Con-tifi- al Cc .~ on Coating Bath, Agent ine of Freeature in tsct ca- Coat- g/L of: Con- Acidity ~C dur- Tech-tion ed cen- in Con- ingCon- nique Phos- Zinc Other Type Ppm tra- version ~ersion phatelonsMetal tion, Coating Coating lons Ions g/L Bath C I CRS 15 1.3Ni: 0.5 D 200 1.0 0.6 43 Im C2 CRS 15 1.3Ni: 0.5 - - 1.0 0.6 43 Im C 3 EG 13 1.1Co: 0.4 E2000 0.4 0.4 40 Im C 4 GA 17 1.5 - - - - 0.7 33 Sp C 5 AL 15 1.3Ni: 0.5 - - 1.0 0.6 43 Sp Abbreviations for Table 3 C = CU~ d- i~un Example; CRS = cold-rolled steel sheet; EG = galvanized steel sheet; GA = galvannealed hot-dip zinc-plated steel sheet; AL = ~I-Imin-lm-m~gn~illm alloy sheet; D = sodium nitrite; E = sodium chlorate;
lm = Immersion; Sp = Spray.
Table 4 I~E~ ion Coating Mass, Test Score for Test of:
g/m2Crystal SizeBase MetalPost-Painting Water-Coverage Corosion Resistant Resistance Secor ~ - ry Adherence Comp. Ex. 1 4.0 x x # x Comp. Ex. 2 0.5 x x x #
Comp. Ex. 3 5.2 x + # x Comp. Ex. 4 7.3 x + x x Comp. Ex. 5 1.3 x x x #
CA 022l46~4 l997-09-04 W 096/27692 PCTrUS96/02677 Examples 1 to 7, which employed the surface treatment method according to the present invention, consisted of treatment using a conversion treatment bath that contained organoperoxide as the oxidizing agent (see Table 1). In eachcase this resulted in the deposition of a thin, uniform, finely crystalline, and dense zinc phosphate conversion coating on the surface of the metal workpiece and in an excellent pai~ lg performance (post-painting corrosion resistance and water-resistant secondary adherence). In Comparative Examples 2, 4, and 5, treat-ment was carried out using a conversion treatment bath that was entirely free ofoxidizing agent. In contrast to the examples, the oxidizing activity in these com-~O parative examples was inadequate, only coarse coating crystals were deposited,and the base metal was not uniformly covered. Comparative Examples 1 and 3 employed, respectively, a nitrite salt and chlorate salt, which are the oxidizing agents most typically used in the prior art. Finely crystalline, dense films were not deposited in these comparative examples and a satisfactory painting per-formance was therefore not obtained.E3enefits of the Invention The surface treatment method according to the present invention is able to deposit a uniform, finely crystalline, and dense zinc phosphate conversion coat-ing on metals. This coating has an excellent painting performance, as expressed in terms of the post-painting corrosion resistance and water-resistant secondaryadhesion. Moreover, the subject surface treatment method is able to do this through a very simple procedure of cleaning (degreasing) - conversion treatment - water rinse. Accordingly, the surface treatment method according to the pres-ent invention does not require the surface-conditioning treatment indispensable in the prior art for the deposition of a uniform, thin, finely crystalline, and dense conversion coating. The surface treatment method according to the present in-vention is thus quite revolutionary in that it makes possible simplification of the treatment facilities, frees the processor from a complicated management of the conversion treatment bath, and offers the economic advantage of no requirement for surface-conditioning agent.
I
COATING ON METALS
Technical Field This invention relates to a surface treatment method that can be applied to various types of metals to form thereon an undercoating film usable with a va-riety of paint systems. More specifically, this invention relates to a surface treat-s ment method of the described type that, without using a titanium colloid surface-conditioning treatment: (a) produces a dense, fine, and uniform conversion film;(b) induces the formation of fine-sized crystals in the conversion film; and (c)forms a high quality underpaint coating for electrodeposition painting, solvent based painting, powder coating, and the like.
.0 Back~round Art Zinc phosphate conversion treatments and chromate treatments are cur-rently in widespread use as underpaint coating treatments for various types of metals for the purpose of improving the post-painting corrosion resistance and paint film adherence. Zinc phosphate conversion treatments are mainly used when the metal substrate is composed of iron or is a composite of several types of materials, because it is difficult for chromate treatments to accommodate or be adapted to such substrates.
The crystals in the films afforded by zinc phosphate conversion treatment are subject to substantial variation in size as a function of the treatment condi-tions. Thick coatings of coarse crystals are ideal for plastic-working operations and rust prevention, but when such coatings are painted they may fail to providea satisfactory paint film adherence. In fact, the most demanding uses of zinc phosphate conversion coatings as underpaint coatings require the generation of thin conversion films of uniform, dense, and fine coating crystals.
Two general methods are known for generating thin zinc phosphate con-version coatings. In one method, contact with the conversion treatment bath is suspended after only partial completion of the film-deposition reactions, thereby stopping these reactions. A problem with this method is that it gives an incom-plete deposition of the conversion film and thus fails to provide complete cover-CA 022146~4 1997-09-04 W 096/27692 PCTrUS96/02677 age of the basis metal. As a result, post-conversion water rinse and drying pro-cesses can cause the substrate to rust, and the post-painting corrosion resist-ance will also be unsatisfactory.
The other general method relies on inducing fine-sized coating crystals.
In this method the hlm-deposition reactions spontaneously terminate, or at leastgreatly slow, while the film is still thin, and the completed conversion coatingcompletely covers the substrate. This method can provide both a satisfactory paint film adherence and post-painting corrosion resistance.
Immersion and spraying techniques are primarily used in the above de-.o scribed zinc phosphate conversion treatment technologies. In the absence of aprior"conditioning" treatment of the metal surfaces to be coated, immersion doesnot usually produce dense, fine coating crystals and requires a lengthy period of time for conversion treatment unless the treatment temperature is 55 ~C or great-er. Spraying does produce a somewhat better fine-crystal formation in the coat-~s ing than does immersion, but not usually enough to provide a fully satisfactorypainting performance. And again, treatment temperatures of at least 55 ~C are required in order to complete the treatment in a relatively brief period of time.
A titanium colloid surface-conditioning treatment must usually be applied to the metal surface imrnediately prior to conversion treatment in order to obtain (a) fine-crystal formation in the coating and (b) a reduction in the treatment tem-perature to 50 ~C and below. This surface-conditioning treatment activates the surface of the metal substrate, with the result that, regardless of the use of im-mersion or spraying, the treatment temperature can be lowered, the treatment time can be shortened, and a fine-sized crystalline film that provides an entirely 2s satisfactory painting performance can be obtained.
When metal surfaces are subjected to a zinc phosphate conversion treat-ment for the above-described purpose of providing an underpaint coating, the surface is ordinarily subjected to a titanium colloid surface-conditioning treatment immediately prior to the conversion treatment process. However, the titanium colloid dispersed in the surface-conditioning treatment bath aggregates with elapsed time after bath preparation, leading to a decline in the surface-condition-ing activity with continued time of use. Japanese Patent Publication Number Sho CA 022l46~4 l997-09-04 62-9190 [9,190/1987] teaches management of the Mg/P2O7 ratio in the surface-conditioning treatment bath in order to increase the stability of the titanium col-loid, while Japanese Patent Application Laid Open [Kokai or Unexamined] Num-ber Sho 63-18084 [18,0~4/1988] discloses the addition to the surface-condition-ing treatment bath of an organic material as a stabilizer for the titanium colloid.
Each of these methods, however, is less effective than would be desirable, with the result that in practice aged bath must be discharged and freshly prepared bath must be supplied on a continuous or at least frequent basis in order to cope with the decline in activity. This preparation and management of the surface-~0 conditioning treatment bath is complex and labor intensive and entails a major economic burden due to its high reagent consumption. And of course, because treatment facilities are required in order to implement the surface-conditioningtreatment, this raises costs for maintenance of the facilities and an expansion of the treatment space.
As a consequence of the various issues discussed above, there has re-cently been strong demand for the development of a surface treatment method that could omit the problematic titanium colloid surface-conditioning treatment while still being able to form on metal surfaces the uniform, fine, dense, and thin conversion films that are optimal as underpaint coatings.
Disclosure of the Invention Problems to Be Solved by the Invention This invention was developed in order to solve the above-described prob-lems that occur with the surface-conditioning treatment that is run immediately prior to zinc phosphate conversion treatment. In specific terms, this invention in-troduces a surface treatment method for the formation of underpaint coatings on metals, wherein said method, without the use of a surface-conditioning treatment, can form on the surface of various metals a uniform, fine, and dense conversion coating that provides an excellent paintability and is also able to generate fine-sized crystals in the conversion coating.
Summary of the Invention It has been found that the use of a heretofore unexamined organic oxidiz-ing agent, namely, organoperoxide, led to the deposition of a uniform, thin, finely 2 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - O 9 - O 4 PCT/US96/02677 crystalline, and dense conversion coating on the surfaces of metal substrates--and thereby yielded an eYcel'ent painting performance--even when zinc phos-phate conversion treatment was used on the metal surface directly after cleaningwithout any intervening surface-conditioning treatment. It was also discovered at the same time that the surface treatment method according to the present invention afforded the desired effects to a satisfactory degree even at relatively low conversion coating temperatures.
In specific terms, then, the surface treatment method according to the present invention for the formation of underpaint coatings on metals characterist-.0 ically comprises the formation of a conversion coating on metal surfaces by first c!eaning the surface of the metal and, without any surface conditioning treatment as is conventionally performed, thereafter bringing the said clean surface into contact with a zinc phosphate conversion treatment bath that contains zinc ions,phosphate ions, and organoperoxide.
No particular restrictions apply to the type, shape, or dimensions of metals that may be treated by the method according to the present invention. For ex-ample, the method according to the present invention can be applied to a varietyof iron and steel materials, for example, steel sheet and zinciferous metal-plated steel sheet, and to a variety of aluminum materials, for example, aluminum sheetand aluminum alloys such as aluminum-magnesium alloys and aluminum-silicon alloys.
Detailed Description of the Invention and Its Preferred Embodiments The organoperoxide concentration in the subject conversion treatment bath is preferably from 50 to 1,500 ppm, and the temperature of the conversion 2s treatment bath is preferably from 25 ~C to 50 ~C.
The surface treatment method according to the present invention requires that the zinc phosphate conversion treatment be executed on a clean metal sur-face. Accordingly, metals with already clean surfaces can be directly exposed to the conversion treatment bath without further processing. However, when the metal surface is contaminated by adhering iron powder, dust, oil, or the like, the surface contaminants must be removed by a cleaning process such as aqueous alkaline degreasing, emulsion degreasing, solvent-based degreasing, and so CA 022146~4 1997-09-04 forth. When a water-based cleaner is used, cleaning is preferably foliowed by a water rinse station where cleaning solution carried forward on the metal surface is removed.
The zinc phosphate conversion treatment bath employed by the method according to the present invention is essentially an acidic aqueous solution that '' contains zinc ions, phosphate ions, and organoperoxide. The zinc ions concen-tration in the conversion treatment bath is generally preferably from 0.5 to 5.0g/L. An adequate coating weight may not be obtained when the zinc ions con-centration is below 0.5 g/L; this leads to a decline in the coverage ratio by the re-.0 sulting conversion coating on the metal surface and thereby to an inadequate post-painting corrosion resistance. Concentrations in excess of 5.0 g/L can cause a coarsening of the coating crystals, thereby producing in particular a decline in the post-painting paint film adherence.
The phosphate ions concentration in the conversion treatment bath used by the method according to the present invention is preferably from 5.0 to 30.0 g/L. Concentrations below 5.0 g/L can make it difficult to form normal conversion coali,lgs, while concentrations in excess of 30.0 g/L do not provide any additional increments in activity and are therefore uneconomical. The phosphate ions can be formed by the addition of phosphoric acid or its aqueous solutions to the con-version treatment bath or by the dissolution of sodium phosphate, magnesium phosphate, zinc phosphate, or the like in the conversion treatment bath. The stoichiometric equivalent as phosphate ions of all such sources of phosphoric acid, condensed phosphoric acids, and salts of simple or condensed phosphoric acids in the liquid compositions used for conversion coating is to be understoodas phosphate ions for the purposes of determining these preferred concentra-tions, irrespective of the actual degree of ionization that exists in the composi-tions. Primarily for reasons of economy, orthophosphoric acid and its salts are preferred.
The conversion treatment bath used in the present invention contains at least one organoperoxide. The organoperoxide has oxidizing power, as do many other materials such as nitrite ions that are called "accelerators" and are com-monly used in prior art phosphate conversion coating forming compositions.
-CA 022l46~4 1997-09-04 W 096/27692 PCTrUS96/02677 Organoperoxide, unlike previously known accelerators, also functions to induce fine-size crystal formation in the conversion coating. This enables the surface treatment method according to the present invention to form a uniform, thin, finely crystalline, and dense conversion coating in the absence of a titanium col-loid surface-conditioning treatment. The use of an organoperoxide-containing conversion treatment bath is the most characteristic feature of the method ac-cording to the present invention.
The organoperoxide used in the subject conversion treatment bath is ex-emplified by organoperoxides, such as tert-butyl hydroperoxide, di-tert-butyl peroxide, acetylacetone peroxide, cumene hydroperoxide, tert-butylperoxymaleic acid, and so forth that have a simple peroxy moiety, and by organoperoxides thathave a percarboxylic acid moiety, such as peracetic acid, monoperphthalic acid, persuccinic acid, and so forth. When the organoperoxide has a low solubility in the treatment bath, its presence in the aforementioned conversion treatment bathcan be induced by solubilization through the addition of a relatively small amount of a water-soluble organic solvent or surfactant.
The organoperoxide is preferably added to give a concentration from 50 to 1,500 ppm in the conversion treatment bath. An organoperoxide concentration in the conversion treatment bath below 50 ppm can result in an inadequate ac-celeration of conversion coating formation and inadequate results in terms of pro-ducing fine-size crystals in the coating. Concentrations in excess of 1,500 ppm do not produce any additional increments in results and are therefore uneconom-ical.
The zinc phosphate conversion treatment bath used by the present inven-2s tion may also contain etchant, whose function is to generate a uniform etch of thesurface of the metal being treated, and non-zinc metal ions, whose function is to provide additional improvements in the painting performance.
Fluoride ions or complex fluoride ions, e.g., fluosilicate ions, can be used as the etchant. Fluorine compounds that produce these ions are exemplified by hydrofluoric acid, fluosilicic acid, and their metal salts (sodium salt, potassium salt), and the etching ions are produced by the dissolution of these compounds in the conversion treatment bath. The etching ions are preferably present in the CA 022l46~4 l997-09-04 W 096/27692 PCTrUS96/02677 conversion treatment bath at a concentration from 100 to 2,000 ppm.
Nickel ions, manganese ions, cobalt ions, rnagnesium ions, calcium ions, and the like can be employed as the non-zinc metal ions additive. Each of these kinds of ions can be fommed by ~~issolution in the conversion treatment bath of an oxide, hydroxide, carbonate, sulfate, phosphate, and/or other compound of the corresponding metal, or even of the elemental metal itself. These metal ions arepreferably present in the conversion treatment bath at a concentration from 100 to 2,000 ppm.
The conversion treatment bath used by the present invention need not 10 contain nitric acid, nitrous acid, an organic nitro compound, etc., and in conse-quence thereof can be formulated as a conversion bath that is completely free of nitrogenous compounds. This nitrogen-free formulation eliminates the need for a nitrogenous compound treatment step during effluent treatment and makes it quite easy for the surface treatment method according to the present invention to accommodate environmental regulations on the effluent levels of nitrogenous compounds.
A preferred treatment sequence in a process according to the present invention comprises, more preferably consists essentially of, or still more preferably consists of the following steps, executed in the given sequence: alka-line degreasing, water rinse, zinc phosphate conversion treatment, and waterrinse. The degreasing process and water rinses can in each case be implement-ed as single-step or m~ ~Itistep processes. The final water rinse is preferably a de-ionized water rinse. Painting can be carried out after the final water rinse without an intervening drying step or can be carried out after a drying step following the 2~ final water rinse.
Zinc phosphate conversion treatment using the surface treatment method according to the present invention is ordinarily run by immersion or spraying ora combination thereof. In practice a satisfactory conversion film can be formed using treatment times (contact time between the metal surface and conversion treatment bath) from approximately 1 minute to approximately 5 minutes. The temperature of the zinc phosphate conversion treatment bath is preferably 25~
C to 50 ~C.
WO 96/27692 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - O 9 - O 4 PCT/US96/02677 The functions and effects of the surface treatment method according to the present invention are ~iiscussed beiow with particular reference to the activity in conversion film formation of the organoperoxide present in the zinc phosphateconversion treatment bath used in the present invention.
When the metal workpiece is ferriferous, the organoperoxide used in the method according to the present invention also oxidizes dissolved divalent iron ioh to trivalent iron ions, just as do the prior-art inorganic oxidizing agents. This prevents the accumulation of divalent iron ions, which are detrimental to the con-version reactions. The trivalent iron ions afforded by oxidation react with the phosphate ions present in the conversion treatment bath to form an iron phos-phate (FePO4 ~ x H2O) sludge that is easily removed from the system.
The present invention may be further appreciated by consideration of the working examples and comparative examples of actual treatment as shown be-low; however, the present invention is not limited to the following examples.
Examples The test materials were cold-rolled steel sheet (SPCC-SD, sheet thick-ness: 0.8 mm), zinc-electroplated steel sheet (sheet thickness: 0.8 mm, plating weight: both surfaces 30 g/m2), galvannealed hot-dip zinc-plated steel sheet (sheet thickness: 0.8 mm, plating weight: both surfaces 45 g/m2), and aluminum-magnesium alloy sheet (A5052, sheet thickness: 1.0 mm). In each case they were cut to 70 x 150 mm to prepare the specimens that were then subjected to the treatments in the working and comparative examples. Each test material was coated with 2 g/m2 of a commercial cleaning/rust-preventing oil.
The treatment processes common to the working and comparative examp-2s les are given below.
(1) degreasing (FINECLEANER(I~) L4460 alkaline degreaser from Nihon Parkerizing Com-pany, Limited, solution in water of 20 grams per liter (hereinafter usually abbreviated as "g/L") of agent A and 12 g/L of agent B) 43 ~C, 120 seconds of contact time, immersion (2) tap-water rinse ambient temperature, 30 seconds, spray CA 022146~4 1997-09-04 (3) zinc phosphate conversion treatment (Specific conditions are given in the respective working and comparative examples. The treatment time was always 120 seconds.) (4) tap-water rinse ambient temperature, 30 seconds, spray (5) deionized water rinse (deionized water with a conductivity of 0.2 microsiemens/cm) ambient temperature, 20 seconds, spray (6) drain/dry: hotairat110~C, 180seconds Treatment compositions, alternatively called "baths" for brevity, numbered (1 ) to (3) as described below were used as starting points for the zinc phosphate conversion treatment baths. The type and concentration of organoperoxide or other oxidizing agent, the treatment temperature, and the treatment time are giv-en in the particuiar working and comparative examples.
~5 Conversion treatment bath (1) Phosphate ions : 15 g/L (from addition of 75 % phosphoric acid) Zinc ions : 1.3 g/L (from addition of zinc oxide) Nickel ions : 0.5 g/L (from addition of nickel carbonate) Fluorine component : 1.0 g/L (from addition of sodium fluosilicate) 2-butanol : 30g/L
Free acidity : 0.6 points (Points of free acidity are defined as the number of milliliters of 0.1N sodium hy-droxide solution in water needed to titrate a 10 milliliter sample of the composi-tion to a color change from yellow to blue, using Bromophenol Blue indicator.) Conversion treatment bath (2) Phosphate ions : 13 g/L (from addition of 75 % phosphoric acid) Zinc ions : 1.1 g/L (from addition of zinc oxide) Cobalt ions : 0.4 g/L (from addition of basic cobalt carbonate) Fluorine component: 0.4 g/L (from addition of sodium bifluoride) Free acidity : 0.4 points Conversion treatment bath (3) Phosphate ions : 17 g/L (from addition of 75% phosphoric acid) WO 96/27692 CA 0 2 2 l 4 6 ~ 4 l 9 9 7 - 0 9 - O 4 PCT/US96/02677 Zinc ions : 1.5 g/L (from addition of zinc oxide) Free acidity : 0.7 points Each of conversion treatment baths (1 ) to (3) was adjusted to the speci-fied free acidity, after adding all other ingredients as shown, by adding sodium5 hydroxide.
The coating weights were measured as follows. The weight in grams of the treated sheet after conversion treatment was measured to give "W1". The coating was then stripped off the treated sheet using the stripping solution andstripping conditions given below, and the weight in grams of the stripped sheet .0 was measured to give "W2". The coating weight in grams per square meter (hereinafter usually abbreviated as "g/m2") was then calculated using the follow-ing equation: coating weight in g/m2 = (W1 - W2)/0.021 Stripping conditions (1) Forthe cold-rolled steel sheet:
stripping solution: 5 % aqueous chromic acid stripping conditions: 75 ~C, 15 minutes, immersion (2) For the zinc-electroplated steel sheet and galvannealed hot-dip zinc-plat- ed steel sheet:
stripping solution: 2 weight % of ammonium dichromate + 49 weight %
of 28 weight % aqueous ammonia + 49 weight % of pure water stripping conditions: room temperature, 15 minutes, immersion (3) For the aluminum alloy sheet stripping solution: 5 % aqueous chromic acid stripping conditions: room temperature, 5 minutes, immersion ; The deposited coating crystals were inspected with a scanning electron microscope (hereinafter usually abbreviated as "SEM") at 1,000X. This magni-fied image was used to evaluate base metal coverage (presence/absence of ex-posed substrate) and to measure the particle size of the conversion coating crys-tals for evaluation of the extent of fine-size crystals.
The following standards were used for reporting the base metal coverage and the extent of fine-size crystals.
CA 022146~4 1997-09-04 Standards for evaluation of the crystal particles cold-rolled steel sheet:
+ less than 35 micrometers x greater than or equal to 35 micrometers s zinc-electroplated steel sheet:
+ less than 25 micrometers x greater than or equal to 25 micrometers galvannealed hot-dip zinc-plated steel sheet:
+ less than 30 micrometers .0 x greater than or equal to 30 micrometers aluminum alloy sheet:
+ less than 30 micrometers x greater than or equal to 30 micrometers ~2) Standard for evaluation of the base metal coverage For all specimens:
+ absolutely no exposure of base metal observed x some exposure of the base metal observed Conversion-treated test panels were electrodeposition painted using a cationic electrodeposition paint (ElecronTM 2000 from Kansai Paint Kabushiki Kaisha) to give a paint film with a film thickness of 20 micrometers. These paint-ed specimens were then subjected to the following painting performance tests in order to evaluate the painting performance.
(1 ) Test of the post-painting corrosion resistance A cut was introduced into the paint film on the painted sample. The paint-ed sample was thereafter immersed for 240 hours in 5 % aqueous sodium chlor-ide heated to 50 ~C, and then removed, rinsed with water, and dried. The neigh-borhood of the cut was peeled using cellophane tape, and the maximum width of paint film peeling on one side was measured after the tape peel and reported on the following scale:
30 + maximum one-side width of peel is less than 7 millimeters (hereinafter us-ually abbreviated as "mm");# : maximum one-side width of peel is at least 7 mm but less than 10 mm;
-WO 96/27692 CA 0 2 2 14 6 ~ 4 19 9 7 - O 9 - O 4 PCT/US96/02677 x : maximum one-side width of peel is at least 10 mm.
(2) Test of the water-resistant secondary adherence The painted sample was immersed for 240 hours in pure water heated at 40 ~C and then removed and dried. A cross was thereafter scribed in the paint 5 film; the center of the cut was extruded 3 mm using an Erichsen tester; and, aKer a cellophane tape peel, the paint film peel ratio (i.e., the ratio of the peeled area to the extruded area) was measured. The following scale was used for reporting:
+ : paint film peel ratio is less than 10 %
# : paint film peel ratio is at least 10 % but less than 20 %
10 x : paint film peel ratio is at least 20 %.
Two hundred (200) parts per million by weight (hereinaKer usualiy abbrevi-ated as "ppm") of tert-butyl hydroperoxide was added to Conversion treatment bath (1), which was then used to treat cold-rolled steel sheet by immersion at a15treatment temperature of 45 ~C.
E)CAMPLE 2 Eighty (80) ppm of di-tert-butyl peroxide was added to Conversion treat-ment bath (1), which was then used to treat zinc-electroplated steel sheet by im-mersion at a treatment temperature of 45 ~C.
Five hundred (500) ppm of tert-butyl hydroperoxide was added to conver-sion treatment bath (2), which was then used to treat cold-rolled steel sheet byspraying at a treatment temperature of 40 ~C.
2sOne thousand one hundred (1,100) ppm of acetylacetone peroxide was added to conversion treatment bath (2), which was then used to treat zinc-elec-troplated steel sheet by immersion at a treatment temperature of 40 ~C.
Five hundred (500) ppm of di-tert-butyl peroxide was added to conversion 30treatment bath (1), which was then used to treat cold-rolled steel sheet by immer-sion at a treatment temperature of 43 ~C.
CA 022146~4 1997-09-04 Five hundred (500) ppm of tert-butyl hydroperoxide was added to conver-sion treatment bath (3), which was then used to treat galvannealed hot-dip zinc-plated steel sheet by spraying at a treatment temperature of 33 ~C.
One hundred fifty (150) ppm of di-tert-butyl peroxide was added to conver-sion treatment bath (1), which was then used to treat aluminum-magnesium alloy sheet by spraying at a treatment temperature of 43 ~C.
COI\APARATIVE EXAMPLE 1 Two hundred (200) ppm of sodium nitrite was added to conversion treat-ment bath (1), which was then used to treat cold-rolled steel sheet by immersionat a treatment temperature of 43 ~C.
Cold-rolled steel sheet was treated by imrnersion in conversion treatment bath (1 ) heated to 43 ~C.
COI\/IPARATIVE EXAMPLE 3 Two thousand (Z,000) ppm of sodium chlorate was added to conversion treatment bath (2), which was then used to treat zinc-electroplated steel sheet by immersion at a treatment temperature of 40 ~C.
Galvannealed hot-dip zinc-plated steel sheet was sprayed with conversion treatment bath (3? heated to 33 ~c.
Aluminum-magnesium alloy sheet was sprayed with conversion treatment bath (1) heated to 43 ~C.
The treatment conditions and test results for all of the Examples are reported in Tables 1 and 2 respectively and the treatment conditions and test results for all of the Comparative Examples are reported in Tables 3 and 4 respectively.
CA 022146~4 1997-09-04 W 096127692 PCTrUS96/02677 Table 1.
Iden Met- C: l ~lion in theOxidizing Fluor- Points of Temper- Con-tifi- al C~ n Coating Bath, Agent ine Free ature in tact ca- Coat- g/Lof: Con-Acidity in ~C dur- Tech-tion ed cen- Con- ing Con- nique Phos- Zinc Other Type Ppm tra- version version phatelons Metal tion,Coating Coating lons lons g/L Bath E 1 CRS 15 1.3Ni: 0.5 A 200 1 0.6 45 Im E2 EG 15 1.3Ni: 0.5 B 80 1 0.6 45 Im E 3 CRS 13 1.1Co: 0.4 A 500 0.4 0.4 40 Sp E 4 EG 13 1. ICo: 0.4 C 1100 0.4 0.4 40 Im E 5 CRS 15 1.3Ni: 0.5 B 500 1 0.6 43 Im E 6 GA 17 1.5 - A 500 - 0.7 33 Sp E 7 AL 15 1.3Ni: 0.5 B 150 1 0.6 43 Sp Abbreviations for Table I
E = Example; CRS = cold-rolled steel sheet; EG = galvanized steel sheet; GA = galvannealed hot-dip zinc-plated steel sheet; AL = ~hlminllm-~ ..P,;l,... alloy sheet; A = tert-butyl hydroperoxide; B = di-tert-butyl peroxide; C = acetylacetone peroxide; Im = Immersion; Sp = Spray Table 2 Idcnliri ~lion Coating Mass, Test Score for Test of:
glm2 Crystal Size Base MetalPost-Painting Water-CoverageCorrosionResistant R~ t~lnceSecondary A~
Example 1 0.9 + + + +
Example 2 3.5 + + + +
Example3 1.2 + + + +
Example 4 3.2 + + + +
Example 5 1.3 + + + +
Example 6 4.3 + + # +
Example 7 2.5 + + + +
W 096t27692 PCTAUS96/02677 Table 3 Iden Met- C~a ~ Il in the O ~ Fllllor- Points Temper- Con-tifi- al Cc .~ on Coating Bath, Agent ine of Freeature in tsct ca- Coat- g/L of: Con- Acidity ~C dur- Tech-tion ed cen- in Con- ingCon- nique Phos- Zinc Other Type Ppm tra- version ~ersion phatelonsMetal tion, Coating Coating lons Ions g/L Bath C I CRS 15 1.3Ni: 0.5 D 200 1.0 0.6 43 Im C2 CRS 15 1.3Ni: 0.5 - - 1.0 0.6 43 Im C 3 EG 13 1.1Co: 0.4 E2000 0.4 0.4 40 Im C 4 GA 17 1.5 - - - - 0.7 33 Sp C 5 AL 15 1.3Ni: 0.5 - - 1.0 0.6 43 Sp Abbreviations for Table 3 C = CU~ d- i~un Example; CRS = cold-rolled steel sheet; EG = galvanized steel sheet; GA = galvannealed hot-dip zinc-plated steel sheet; AL = ~I-Imin-lm-m~gn~illm alloy sheet; D = sodium nitrite; E = sodium chlorate;
lm = Immersion; Sp = Spray.
Table 4 I~E~ ion Coating Mass, Test Score for Test of:
g/m2Crystal SizeBase MetalPost-Painting Water-Coverage Corosion Resistant Resistance Secor ~ - ry Adherence Comp. Ex. 1 4.0 x x # x Comp. Ex. 2 0.5 x x x #
Comp. Ex. 3 5.2 x + # x Comp. Ex. 4 7.3 x + x x Comp. Ex. 5 1.3 x x x #
CA 022l46~4 l997-09-04 W 096/27692 PCTrUS96/02677 Examples 1 to 7, which employed the surface treatment method according to the present invention, consisted of treatment using a conversion treatment bath that contained organoperoxide as the oxidizing agent (see Table 1). In eachcase this resulted in the deposition of a thin, uniform, finely crystalline, and dense zinc phosphate conversion coating on the surface of the metal workpiece and in an excellent pai~ lg performance (post-painting corrosion resistance and water-resistant secondary adherence). In Comparative Examples 2, 4, and 5, treat-ment was carried out using a conversion treatment bath that was entirely free ofoxidizing agent. In contrast to the examples, the oxidizing activity in these com-~O parative examples was inadequate, only coarse coating crystals were deposited,and the base metal was not uniformly covered. Comparative Examples 1 and 3 employed, respectively, a nitrite salt and chlorate salt, which are the oxidizing agents most typically used in the prior art. Finely crystalline, dense films were not deposited in these comparative examples and a satisfactory painting per-formance was therefore not obtained.E3enefits of the Invention The surface treatment method according to the present invention is able to deposit a uniform, finely crystalline, and dense zinc phosphate conversion coat-ing on metals. This coating has an excellent painting performance, as expressed in terms of the post-painting corrosion resistance and water-resistant secondaryadhesion. Moreover, the subject surface treatment method is able to do this through a very simple procedure of cleaning (degreasing) - conversion treatment - water rinse. Accordingly, the surface treatment method according to the pres-ent invention does not require the surface-conditioning treatment indispensable in the prior art for the deposition of a uniform, thin, finely crystalline, and dense conversion coating. The surface treatment method according to the present in-vention is thus quite revolutionary in that it makes possible simplification of the treatment facilities, frees the processor from a complicated management of the conversion treatment bath, and offers the economic advantage of no requirement for surface-conditioning agent.
I
Claims (35)
1. An aqueous liquid composition for forming a zinc phosphate conversion coating on a metal surface by contact therewith, said composition consisting essentially of water, zinc ions, phosphate ions, and at least one type of organoperoxide.
2. An aqueous liquid composition according to claim 1, wherein the organoperoxide concentration is from 50 to 1,500 ppm.
3. An aqueous liquid composition according to claim 2, wherein the zinc ionsconcentration is from 0.5 to 5.0 g/L.
4. An aqueous liquid composition according to claim 1, wherein the zinc ionsconcentration is from 0.5 to 5.0 g/L.
5. An aqueous liquid composition according to claim 4, wherein the phosphate ions concentration is from 5.0 to 30.0 g/L.
6. An aqueous liquid composition according to claim 3, wherein the phosphate ions concentration is from 5.0 to 30.0 g/L.
7. An aqueous liquid composition according to claim 2, wherein the phosphate ions concentration is from 5.0 to 30.0 g/L.
8. An aqueous liquid composition according to claim 1, wherein the phosphate ions concentration is from 5.0 to 30.0 g/L.
9. An aqueous liquid composition according to claim 8 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
10. An aqueous liquid composition according to claim 7 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
11. An aqueous liquid composition according to claim 6 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
12. An aqueous liquid composition according to claim 5 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
13. An aqueous liquid composition according to claim 4 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
14. An aqueous liquid composition according to claim 3 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
15. An aqueous liquid composition according to claim 2 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
16. An aqueous liquid composition according to claim 1 which includes from 100 to 2,000 ppm of fluorine from fluoride ions, complex fluoride ions, or both.
17. An aqueous liquid composition according to claim 16 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the groupconsisting of nickel, manganese, cobalt, magnesium, and calcium cations.
18. An aqueous liquid composition according to claim 15 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the groupconsisting of nickel, manganese, cobalt, magnesium, and calcium cations.
19. An aqueous liquid composition according to claim 14 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the groupconsisting of nickel, manganese, cobalt, magnesium, and calcium cations.
20. An aqueous liquid composition according to claim 13 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
21. An aqueous liquid composition according to claim 12 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
22. An aqueous liquid composition according to claim 11 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
23. An aqueous liquid composition according to claim 10 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the groupconsisting of nickel, manganese, cobalt, magnesium, and calcium cations.
24. An aqueous liquid composition according to claim 9 which includes a total of from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
25. An aqueous liquid composition according to claim 8 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
26. An aqueous liquid composition according to claim 7 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
27. An aqueous liquid composition according to claim 6 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
28. An aqueous liquid composition according to claim 5 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
29. An aqueous liquid composition according to claim 4 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
30. An aqueous liquid composition according to claim 3 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
31. An aqueous liquid composition according to claim 2 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
32. An aqueous liquid composition according to claim 1 which includes a totalof from 100 to 2,000 ppm of divalent metal cations selected from the group consisting of nickel, manganese, cobalt, magnesium, and calcium cations.
33. A process of forming a phosphate conversion coating on a metal surface, said process comprising steps of:
(I) cleaning the metal surface, and optionally, rinsing and/or drying the surface; and (II) without any intermediate conditioning treatment after step (I), bringing the cleaned surface into contact with an aqueous liquid composition according to any one of claims 1 to 32.
(I) cleaning the metal surface, and optionally, rinsing and/or drying the surface; and (II) without any intermediate conditioning treatment after step (I), bringing the cleaned surface into contact with an aqueous liquid composition according to any one of claims 1 to 32.
34. A process according to claim 33, wherein step (II) is performed at a temperature from 25 to 50 °C for a time from 1 to 5 minutes.
35. A process according to claim 34, comprising steps of:
(1.1) cleaning the metal surface with an alkaline cleaner;
(1.2) rinsing the metal surface cleaned in step 1.1 with water and, optionally, drying the rinsed metal surface; and (II) without any intermediate conditioning treatment after step (1.2), bringing the cleaned and rinsed surface into contact with an aqueous liquid composition according to any one of claims 1 to 32; and (III) removing the metal surface from the contact established in step (II) and rinsing the surface with deionized water.
(1.1) cleaning the metal surface with an alkaline cleaner;
(1.2) rinsing the metal surface cleaned in step 1.1 with water and, optionally, drying the rinsed metal surface; and (II) without any intermediate conditioning treatment after step (1.2), bringing the cleaned and rinsed surface into contact with an aqueous liquid composition according to any one of claims 1 to 32; and (III) removing the metal surface from the contact established in step (II) and rinsing the surface with deionized water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7/47605 | 1995-03-07 | ||
| JP4760595 | 1995-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2214654A1 true CA2214654A1 (en) | 1996-09-12 |
Family
ID=12779879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002214654A Abandoned CA2214654A1 (en) | 1995-03-07 | 1996-03-05 | Composition and process for forming an underpaint coating on metals |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0813620A4 (en) |
| AR (1) | AR001178A1 (en) |
| AU (1) | AU699822B2 (en) |
| BR (1) | BR9607700A (en) |
| CA (1) | CA2214654A1 (en) |
| WO (1) | WO1996027692A1 (en) |
| ZA (1) | ZA961841B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2214654A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
| DE19540085A1 (en) * | 1995-10-27 | 1997-04-30 | Henkel Kgaa | Low nitrate, manganese-free zinc phosphating |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| CN102268680A (en) * | 2011-06-24 | 2011-12-07 | 大连洁仕清洁用品有限公司 | Integrate surface treatment agent used before spraying of secondary processing casting member and preparation method |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2471908A (en) * | 1948-04-08 | 1949-05-31 | American Chem Paint Co | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
| US3161549A (en) * | 1955-04-08 | 1964-12-15 | Lubrizol Corp | Solution for forming zinc phosphate coatings on metallic surfaces |
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| JPS5339945A (en) * | 1976-09-25 | 1978-04-12 | Nippon Packaging Kk | Surface treatment of zinc or zinc alloy |
| NZ188918A (en) * | 1977-11-29 | 1981-01-23 | Ici Ltd | Applying phosphate coating to ferrous or zinciferous metal substrate and materials therefor |
| US4171231A (en) * | 1978-04-27 | 1979-10-16 | R. O. Hull & Company, Inc. | Coating solutions of trivalent chromium for coating zinc surfaces |
| DE3913089A1 (en) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS |
| DE3927614A1 (en) * | 1989-08-22 | 1991-02-28 | Metallgesellschaft Ag | METHOD OF GENERATING PHOSPHATURE SUPPLIES ON METALS |
| DE69528664T2 (en) * | 1994-12-06 | 2003-07-03 | Henkel Corp., Plymouth Meeting | COMPOSITION AND METHOD FOR THE ZINC-PHOSPHATE CONVERSION COATING |
| CA2214834A1 (en) * | 1995-03-07 | 1996-09-12 | Yasuhiko Nagashima | Composition and process for simultaneously cleaning and conversion coating metal surfaces |
| CA2214654A1 (en) * | 1995-03-07 | 1996-09-12 | Henkel Corporation | Composition and process for forming an underpaint coating on metals |
-
1996
- 1996-03-05 CA CA002214654A patent/CA2214654A1/en not_active Abandoned
- 1996-03-05 AU AU50291/96A patent/AU699822B2/en not_active Ceased
- 1996-03-05 WO PCT/US1996/002677 patent/WO1996027692A1/en not_active Application Discontinuation
- 1996-03-05 BR BR9607700A patent/BR9607700A/en not_active Application Discontinuation
- 1996-03-05 EP EP96907132A patent/EP0813620A4/en not_active Withdrawn
- 1996-03-06 ZA ZA961841A patent/ZA961841B/en unknown
- 1996-03-08 AR AR33567196A patent/AR001178A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996027692A1 (en) | 1996-09-12 |
| EP0813620A1 (en) | 1997-12-29 |
| AU699822B2 (en) | 1998-12-17 |
| AU5029196A (en) | 1996-09-23 |
| EP0813620A4 (en) | 1998-02-25 |
| BR9607700A (en) | 1998-07-07 |
| ZA961841B (en) | 1996-09-11 |
| AR001178A1 (en) | 1997-09-24 |
| MX9706315A (en) | 1997-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1404894B1 (en) | Corrosion resistant coatings for aluminum and aluminum alloys | |
| AU684399B2 (en) | Zinc phosphate coating compositions containing oxime accelerators | |
| US5397390A (en) | Composition and method for treatment of phosphated metal surfaces | |
| EP0795045B1 (en) | Composition and method for treatment of conversion-coated metal surfaces | |
| JP2680618B2 (en) | Metal phosphate treatment method | |
| PT896641E (en) | COMPOSITIONS OF ZINC CONTAINING TUNGSTEN THAT USE THROTTLE ACCELERATORS | |
| EP0181377A1 (en) | Metal treatment | |
| US4486241A (en) | Composition and process for treating steel | |
| US4110129A (en) | Post treatment of conversion-coated zinc surfaces | |
| US4600447A (en) | After-passivation of phosphated metal surfaces | |
| JPH07126859A (en) | Hexavalent chromium-free surface treating agent for chemical conversion for aluminum and aluminum alloy | |
| CA1245951A (en) | Process for the zinc/calcium phosphatizing of metal surfaces at low treatment temperatures | |
| CA2147101A1 (en) | Process for applying a coating to a magnesium alloy product | |
| JPH10500452A (en) | Iron phosphate treatment with substituted monocarboxylic acids | |
| US3720547A (en) | Permanganate final rinse for metal coatings | |
| US6179934B1 (en) | Aqueous phosphating composition and process for metal surfaces | |
| US4220486A (en) | Conversion coating solution for treating metallic surfaces | |
| WO2004046420A1 (en) | Chrome free conversion coating for aluminium | |
| US5888315A (en) | Composition and process for forming an underpaint coating on metals | |
| JP3088623B2 (en) | Method for forming zinc phosphate film on metal surface | |
| CA2277967A1 (en) | Aqueous phosphating composition and process for metal surfaces | |
| CA2214654A1 (en) | Composition and process for forming an underpaint coating on metals | |
| US4643778A (en) | Composition and process for treating steel | |
| JP3286583B2 (en) | Chemical conversion treatment composition for magnesium-containing metal, surface treatment method and surface treatment product | |
| JP3417653B2 (en) | Pretreatment method for painting aluminum material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |