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EP0977908A1 - Conditionnement de surfaces metalliques prealablement a la phosphatation - Google Patents

Conditionnement de surfaces metalliques prealablement a la phosphatation

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Publication number
EP0977908A1
EP0977908A1 EP98908792A EP98908792A EP0977908A1 EP 0977908 A1 EP0977908 A1 EP 0977908A1 EP 98908792 A EP98908792 A EP 98908792A EP 98908792 A EP98908792 A EP 98908792A EP 0977908 A1 EP0977908 A1 EP 0977908A1
Authority
EP
European Patent Office
Prior art keywords
phosphate
pretreatment composition
microparticulate
composition according
concentration
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.)
Granted
Application number
EP98908792A
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German (de)
English (en)
Other versions
EP0977908A4 (fr
EP0977908B1 (fr
Inventor
Takaomi Nakayama
Yasuhiko Nagashima
Kensuke Shimoda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel Corp
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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
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals

Definitions

  • This invention relates to a surface conditioning pretreatment bath and surface conditioning process for use prior to the phosphate conversion coating treatments that are executed on the surfaces of metals such as iron and steel, zinc-plated steel sheet,
  • the subject surface conditioning pretreatment bath and process have the effect of accelerating the conversion reactions and shortening the reaction time in the ensuing conversion treatment, while also producing finer crystals in the phosphate coating.
  • the purpose of the surface conditioning step is to activate the metal surface and produce nuclei for deposition of the phosphate coating crystals in order to ultimately produce fine-sized, dense crystals in the phosphate coating.
  • a typical phosphate conversion coating process that produces fine-sized, dense phosphate coating crystals can be
  • the surface conditioning step is carried out in order to render the phosphate coating crystals fine-size and dense.
  • Compositions for this purpose are known, for example, from United States Patent Numbers 2,874,081 , 2,322,349, and 2,310,239.
  • the main constituents of the surface conditioner are titanium, py- rophosphate ions, orthophosphate ions, sodium ions, and the like.
  • These surface condi- tioning compositions known as Jernstedt salts, provide titanium ions and colloidal titanium in their aqueous solutions.
  • the colloidal titanium becomes adsorbed to the metal surface when the degreased and water-rinsed metal is dipped in an aqueous solution of such a surface conditioning composition or when the metal is sprayed with the surface conditioning pretreatment bath.
  • the adsorbed colloidal titanium functions in the ensuing phosphate conversion coating treatment step as nuclei for deposition of the phosphate coating crystals, thereby accelerating the conversion reactions and causing the phosphate coating crystals to be finer-sized and denser.
  • the surface conditioning compositions in current industrial use all employ Jernstedt salts. However, the use in the surface conditioning step of colloidal titanium generated from Jernstedt salts is associated with a variety of problems.
  • the first problem is a deterioration with time in the surface conditioning pretreatment bath. While the heretofore employed surface conditioning compositions do provide remarkable fine-sizing and densifying effects on the phosphate coating crystals immediately after preparation of the aqueous solution of the composition, this activity can be lost several days after preparation because of aggregation of the colloidal titanium. This loss in activity, which manifests as a coarsening of the phosphate coating crystals, occurs regardless of whether the surface conditioning pretreatment bath has actually been used during this several day period.
  • Japanese Patent Application Laid Open (Kokai or Unexamined) Number Sho 63-76883 (76,883/1988) teaches a process for managing and maintaining the surface conditioning activity by measuring the average particle size of the colloidal titanium in the surface conditioning pretreatment bath and continuously discarding bath so as to keep the average particle size below a prescribed value.
  • Fresh surface conditioning composition is also supplied to make up for the discarded portion.
  • This method does permit a quantitative management of the factors related to the activity of the surface conditioning pretreatment bath, but at the same time this method requires that large amounts of the surface conditioning pretreatment bath be discarded in order to maintain an activity level equal to that of the initially prepared aqueous solution. This creates an additional problem with respect to the waste water treatment capacity of the plant where the process is carried out. In sum, the activity is maintained by the combination of continuously discarding the surface conditioning pretreatment bath and make up of the entire quantity.
  • the second problem is that the activity and life of the surface conditioning pre- treatment bath are substantially affected by the quality of the water used for bath buildup.
  • Industrial-grade water is generally used to make up the surface conditioning pretreatment bath.
  • industrial-grade water contains cationic components which are a source of total hardness, e.g., magnesium and calcium, and the content of these components varies as a function of the source of the industrial- grade water used for bath buildup.
  • colloidal titanium which is the principal component of the heretofore used surface conditioning pretreatment baths, bears an anionic charge in aqueous solution and that the resulting mutual electrical repulsion prevents its sedimentation and supports the maintenance of its disperse state.
  • a fourth problem concerns the limitation on the degree of fine-sizing of the phosphate coating crystals that can be achieved through the activity of the surface conditioning pretreatment bath.
  • the surface conditioning activity is generated by the adsorption of colloidal titanium on the metal surface, which creates nuclei for the deposition of the phosphate coating crystals.
  • the phosphate coating crystals become denser and finer as the number of colloidal titanium particles adsorbed on the metal surface during the surface conditioning step increases. This would upon initial analysis lead to the idea of increasing the number of colloidal titanium particles in the surface conditioning pretreatment bath, i.e., increasing the colloidal titanium concentration.
  • the current normally used upper limit on the colloidal titanium concentration is 100 parts by weight of colloidal titanium (measured as its stoichiometric equivalent as elemental titanium) per million parts of the total composition, a concentration unit that may be used hereinafter for any ingredient in any mixture and is usually abbreviated as "ppm", in the surface conditioning pretreatment bath, and the prior art has been unable to provide finer-sized phosphate coating crystals by increasing the colloidal titanium concentration above this limit.
  • Japanese Patent Publication (Kokoku) Number Sho 40-1095 (1 ,095/ 1965) teaches a surface conditioning process in which galvanized steel sheet is dipped in a highly concentrated suspension of an insoluble phosphate of a divalent or trivalent metal.
  • the working examples provided for this process are limited to galvanized steel sheet, and in addition this process uses a highly concentrated insoluble phosphate suspension with a minimum concentration of 30 grams of insoluble phosphate particles per liter of total suspension, a concentration unit that may be used hereinafter for other materials in addtion to colloidal phosphates that are dissolved or dispersed in any liquid phase and is generally abbreviated "g/L".
  • Jernstedt salts suffer from a variety of drawbacks, a more effective technology that can replace Jernstedt salts has yet to appear.
  • An object of the present invention is to solve the problems described above for the prior art by providing a novel surface conditioning pretreatment bath that evidences an excellent stability overtime, that can accelerate the conversion reactions and shorten the conversion reaction time in an ensuing phosphate conversion coating treatment, and/or that can provide finer-sized crystals in the ultimately obtained phosphate coating.
  • An additional object of the invention is to provide a surface conditioning process with these same features.
  • the concentration of the ⁇ 5- ⁇ m particles is preferably from 0.001 to 30 g/L, and the aforesaid divalent or trivalent metal is preferably at least one selection from Zn, Fe, Mn, Ni, Co, Ca, and Al.
  • the aforesaid alkali metal salt or ammonium salt independently is preferably at least one salt selected from the orthophosphates, metaphosphates, or- thosilicates, metasilicates, carbonates, bicarbonates, and borates and independently is preferably present in a concentration of 0.5 to 20 g/L.
  • the bath preferably additionally contains at least one selection from the group consisting of water-soluble anionic organic polymers, water-soluble nonionic organic polymers, anionic surfactants, nonionic surfactants, and microparticulate oxides that disperse in an anionically charged state.
  • This microparticulate oxide that disperses in an anionically charged state preferably has an average particle size ⁇ 0.5 ⁇ m and is preferably present in a concentration from 0.001 to 5 g/L.
  • the subject microparticulate oxide that disperses in an anionically charged state is desirably at least one selection from the oxides of Si, B, Ti, Zr, Al, Sb, Mg, Se, Zn, Sn, Fe, Mo, and V.
  • a metal surface conditioning process according to the present invention that precedes phosphate conversion coating treatment is characterized by contacting the metal surface with the surface conditioning pretreatment bath described above. Because a surface conditioning pretreatment bath according to the present invention has a much better stability at high pH's and high temperatures than the prior art products, it can be combined with builder and nonionic or anionic surfactant(s) or mixtures thereof and used to effect a process that can simultaneously clean and activate the metal surface.
  • Phosphates containing at least one divalent or trivalent metal are an essential component in the present invention. These dispersed divalent or trivalent metal phosphate particles with a suitable particle size, through adsorption on the surface of the workpiece from an aqueous solution containing other specific ingredients, form nuclei for ensuing phosphate coating crystal deposition and also increase the rate of the phosphate conversion reactions.
  • the particle size of the divalent and trivalent metal phosphate particles dispersed in a pretreatment composition according to the invention preferably is not more than, with increasing preference in the order given, 4.5, 3.5, 2.5, 1.5, 0.50, 0.40, 0.25, or 0.10 ⁇ m.
  • the corrosion resistance after zinc phosphating and painting is better, the smaller the particle size of dispersed phosphate used in a composition according to the invention, and the phosphate coating weight is smaller when smaller particle size phosphate dispersates are used.
  • the dispersed phosphate particles preferably contains at least some of the same chemical type(s) of divalent or trivalent metal cation(s) as does the phosphate coating to be formed after the pretreatment according to the invention is used.
  • zinc cations preferably predominate also among the cations in the phosphates dispersed in a pretreatment composition according to this invention.
  • a manganese phosphate conversion coating is to be used, predominantly manganese phosphates are preferably used as the dispersates in a pretreatment composition according to the invention.
  • divalent or trivalent metal phosphate component resembles one component in phosphate conversion treatment baths and phosphate conversion coatings
  • another advantage of the subject divalent or trivalent metal phosphate is that it will not negatively affect the conversion treatment bath when carried over into that bath and will not adversely affect the performance of the phosphate conversion coating when taken into the conversion coating as nuclei.
  • the divalent or trivalent metal phosphate used in the present invention is exemplified by the following: Zn 3 (PO 4 ) 2 , Zn 2 Fe(PO 4 ) 2 , Zn 2 Ni(PO 4 ) 2 , Ni 3 (PO 4 ) 2 , Zn 2 Mn(PO 4 ) 2 , Mn 3 (PO 4 ) 2 , Mn 2 Fe(PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Zn 2 Ca(PO 4 ) 2 , FePO 4 , AIPO 4 , CoPO 4 , and Co 3 (PO 4 ) 2 .
  • the presence of divalent or trivalent metal phosphate particles with sizes in excess of 5 ⁇ m in the surface conditioning pretreatment bath according to the present invention does not harm the advantageous effects of the present invention, provided that the concentration of the ⁇ 5- ⁇ m microparticles in the surface conditioning aqueous composition is suitable.
  • the average size of the ultimately produced phosphate coating crystals can be controlled in the present invention by adjusting the average particle size of the divalent or trivalent metal phosphate particles that are less than 5 ⁇ m in size.
  • the use of very finely divided divalent or trivalent metal phosphate will cause the deposition of very finely-sized phosphate crystals.
  • the divalent or trivalent metal phosphate concentration preferably falls in the range from 0.001 to 30 g/L.
  • the divalent or trivalent metal phosphate concentration is below 0.001 g/L, usually so little divalent or trivalent metal phosphate becomes adsorbed on the metal surface that accelerating the phosphate conversion reactions hardly occurs.
  • little or no additional acceleration of the phosphate conversion reactions is obtained at divalent or trivalent metal phosphate concentrations in excess of 30 g/L; this makes such concentrations uneconomical.
  • the concentration of dispersed divalent or trivalent phosphate particles in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.010, 0.10, 0.50, 0.75, 1.0, 1.2, 1.6, or 1.8 g/L and independently preferably is not more than, with increasing preference in the order given, 25, 20, 15, 10, 7.5, 5.0, 4.0, 3.5, 3.0, or 2.5 g/L.
  • alkali metal salt or ammonium salt or mixture thereof is the alkali metal salt or ammonium salt or mixture thereof (abbreviated below simply as the "alkali metal salt or ammonium salt”).
  • alkali metal salt or ammonium salt As explained above with reference to the prior art, surface conditioning by blowing insoluble divalent or trivalent metal phosphate under elevated pressure has already been pursued in a previously disclosed process. However, this previously
  • the present inventors have discovered that, in the presence of dissolved alkali metal salt or ammonium salt, surface conditioning activity can be generated even by dipping in low concentrations of the insoluble divalent or trivalent metal phosphate and s without the application of physical force to the metal surface.
  • the present invention requires nothing more than simple contact between the workpiece and the surface conditioning pretreatment bath and thus has a reaction mechanism completely different from that in the prior art. It is for this reason that the alkali metal salt or ammonium salt is an essential component.
  • the particular alkali metal salt or ammonium salt is not crucial as long as it is selected from the group consisting of orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, and borates. Combinations of two or more of these alkali metal salts or ammonium salts may also be used unproblematically.
  • the desirable concentration range for the alkali metal salt or ammonium salt is 5 from 0.5 to 20 g/L. Concentrations below 0.5 g/L often fail to provide surface conditioning activity by simple contact between the workpiece and surface conditioning pretreatment bath. Concentrations in excess of 20 g/L do not provide additional benefits and are therefore uneconomical.
  • the concentration of dis- 0 solved alkali metal or ammonium salt in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.010, 0.10, 0.50, 1.0, 2.0, 3.0, 4.0, or 4.9 g/L and independently preferably is not more than, with increasing preference in the order given, 25, 20, 15, 10, 7.5, or 5.5 g/L.
  • the surface conditioning pretreatment bath according to the present invention must be adjusted into the pH range from 4.0 to 13.0. At a pH below 4.0, the metal usually corrodes in the surface conditioning pretreatment bath with the production of an oxide coating, which raises the possibility of defective phosphate conversion treatment. At a pH in excess of 13.0, neutralization of the acidic phosphate conversion bath by surface conditioning pretreatment bath carried over into the phosphate conversion treatment step can throw the phosphate conversion bath out of balance.
  • the pH value in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, or 7.5 and independently preferably is not more than, with increasing preference in the order given, 12.0, 11.0, 10.5, 10.0, 9.5, 9.0, or 8.5.
  • microparticulate oxide that disperses in an anionically charged state is preferred for a composition according to this invention.
  • the microparticulate oxide adsorbs to the metal surface with the formation of nuclei that can function as microcathodes for phosphate crystal deposition, and thus forms a starting point for the phosphate conversion reactions.
  • the microparticulate oxide functions to improve the dispersion stability of the divalent or trivalent metal phosphate in the surface conditioning pretreatment bath.
  • the microparticulate oxide either by adsorbing to the divalent or trivalent metal phosphate dispersed in the surface conditioning pretreatment bath or by preventing collisions among the divalent or trivalent metal phosphate particles, improves the stability by preventing the aggregation and precipitation of the divalent or trivalent metal phosphate.
  • the particle size of the microparticulate oxide must be smaller than the particle size of the divalent or trivalent metal phosphate.
  • the microparticulate oxide preferably has a particle size ⁇ 0.5 ⁇ m.
  • microparticulate oxide used by the present invention is not crucial as long as the microparticulate oxide satisfies the particle size and anionicity conditions.
  • An initially cationic microparticulate oxide can be used after its surface charge has been converted to anionic by a surface treatment.
  • the same increase in the dispersion stability of the divalent or trivalent metal phosphate in the surface conditioning pretreatment bath according to the present invention can be obtained using anionic water-soluble organic polymer, nonionic water-solu- ble organic polymer, anionic surfactant, or nonionic surfactant.
  • the concentration of the microparticulate oxide is preferably from 0.001 to 5 ppm.
  • a microparticulate oxide concentration below 0.001 ppm cannot usually provide the increase in dispersion stability by the divalent or trivalent metal phosphate in the sur-
  • 5 face conditioning pretreatment bath that is the main purpose for using the microparticulate oxide in the present invention.
  • An economically motivated upper concentration limit can be established at 5 g/L because concentrations in excess of 5 g/L provide no additional increase in the dispersion stability of the divalent or trivalent metal phosphate.
  • the concentration of microparticulate oxide particles in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.003, 0.005, 0.007, or 0.009 ppm and independently preferably is not more than, with increasing preference in the order given, 4.0, 3.0, 2.0, 1.5, 1.0, 0.50, 0.25, 0.12, 0.080, 0.060, 0.040, or 0.020 ppm.
  • the surface conditioning pretreatment bath according to the present invention retains its activity regardless of its use conditions.
  • the surface conditioning pretreatment bath according to the present invention offers the following advantages over the prior art technology: (1) It has a long storage stability; (2) its activity is not impaired by the admixture of hardness components o such as Ca, Mg, and the like; (3) it can be used at high temperatures; (4) it tolerates the addition of various alkali metal salts; (5) it is very stable over a broad pH range; and (6) it provides for adjustment of the size of the ultimately obtained phosphate crystals.
  • the bath according to the present invention can also be used as a simultaneous cleaner/degreaser and surface conditioner, whereas the prior technology 5 in this area has been unable to continuously maintain stable quality.
  • the known inorganic alkali builders, organic builders, surfactants, and the like may be added in this application in order to improve the cleaning capacity in the degreasing and surface conditioning step.
  • the known chelating agents, condensed phosphates, and 0 the like that are used for degreasing/cleaning may be added to a conditioning composition according to this invention in order to negate the effects of cationic components that may be carried into the surface conditioning pretreatment bath.
  • a surface conditioning process according to the present invention involves simply contacting the metal surface with the surface conditioning pretreatment bath.
  • the contact time and bath temperature are not critical.
  • the surface conditioning process according to the present invention can be applied to any metal on which a phosphate treatment can be executed, e.g., iron, steel, galvanized steel sheet, aluminum, and aluminum alloys.
  • a phosphate treatment e.g., iron, steel, galvanized steel sheet, aluminum, and aluminum alloys.
  • the advantageous effects from application of the surface conditioning pretreatment bath according to the present invention will be illustrated in greater detail through the working and comparative examples that follow. While an automotive-grade zinc phosphate treatment is provided as an example of the phosphate treatment, the use of a surface conditioning pretreatment bath according to the present invention is not limited to this type of phosphate conversion treatment.
  • GA steel panel hot-dip galvanized and galvannealed on both sides, zinc coating weight 45 g/m 2 .
  • Zinc phosphate treatment dipping, 42 °C, 120 seconds
  • FINECLEANER® L4460 concentrate (commercially available from Nihon Parker- izing Company, Limited), diluted to 2 % with tapwater to provide a concentration of 2 % of the concentrate in the diluted working degreasing solution, was used in the working and comparative examples.
  • Surface conditioner
  • compositions of the surface conditioning pretreatment baths used in the working examples are reported in Table 1.
  • compositions of the surface conditioning pretreatment baths used in the comparative examples are reported in Table 2.
  • the time-elapsed testing was run after holding the surface conditioning pretreatment bath at room temperature for one week after preparation.
  • Example 14 the bath composition of the surface conditioning pretreatment bath was the same as in Example 2, but the treatment temperature was 40 °C.
  • Example 15 the already specified active ingredients of the surface conditioning pretreatment bath and the treatment temperature were the same as in Example 14, but 2 g/L of a surfactant (ethoxylated nonylphenol with an average of 1 1 molecules of ethylene oxide per nonyl phenol molecule was also added.
  • a surfactant ethoxylated nonylphenol with an average of 1 1 molecules of ethylene oxide per nonyl phenol molecule was also added.
  • the bath composition of the surface conditioning pretreatment bath was the same as in Comparative Example 1, but the treatment temperature was 40°C.
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the trisodium phosphate reagent (an alkali metal salt) to the concentration-
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 1 minute in a mortar and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper.
  • Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 4.2 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phos- phate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phos- phate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 1 hour in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.09 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • a precipitate was produced by alternately adding 100 milliliters (hereinafter usu- ally abbreviated as "mL”) of a 1 mole per liter (hereinafter usually abbreviated as "mol/L”) zinc sulfate solution and 100 mL of a 1 mol/L sodium monohydrogen phosphate solution to 1 liter (hereinafter usually abbreviated as "L") of a 0.5 mol/L iron(ll) sulfate solution heated to 50 °C.
  • the aqueous solution containing the precipitate was then heated at 90 °C for 1 hour in order to ripen the precipitate particles. This was followed by washing 10 times by decantation.
  • the precipitate was recovered by filtration and dried and then analyzed by x-ray diffraction. The results indicated that the precipitate was primarily phosphophyllite (i.e., Zn 2 Fe(PO 4 ) 2 -4H 2 O) containing some trivalent iron phosphate. This phosphophyllite was ground for 10 minutes in a ball mill using zirconia o beads and was then used as the divalent metal phosphate. This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.29 ⁇ m.
  • a submicron particle analyzer Coulter Model N4 from the Coulter Company
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • This Zn x Mn ⁇ (PO 4 ) 2 was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This o divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.32 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • a precipitate was produced by the addition of 200 mL of a 1 mol/L zinc nitrate solution and then 200 mL of a 1 mol/L sodium monohydrogen phosphate solution to 1 L of a 0.1 mol/L calcium nitrate solution heated to 50 °C.
  • the aqueous solution containing the precipitate was then heated at 90 °C for 1 hour in order to ripen the precipitate particles. This was followed by washing 10 times by decantation.
  • the precipitate was recovered by filtration and dried and was analyzed by x-ray diffraction. The results indicated that the precipitate was scholzite (Zn 2 Ca(PO 4 ) 2 -4H 2 O).
  • This scholzite was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.30 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 0.02 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the ZrO 2 sol (microparticulate oxide, NZS-30B from Nissan Kagaku Kogyo Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • ZrO 2 sol microparticulate oxide, NZS-30B from Nissan Kagaku Kogyo Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 30 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the Sb 2 O 5 sol (microparticulate oxide, A-1530 from Nissan Kagaku Kogyo Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • Sb 2 O 5 sol microparticulate oxide, A-1530 from Nissan Kagaku Kogyo Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the sodium metasilicate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • sodium metasilicate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the sodium sesquicarbonate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • sodium sesquicarbonate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • Example 13 Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate. This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper.
  • Example 15 The surface conditioning pretreatment was run using the treatment bath described in Example 2 at a treatment temperature of 40 °C.
  • Example 15 The surface conditioning pretreatment was run using the treatment bath described in Example 2 at a treatment temperature of 40 °C.
  • Example 16 Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate. The concentration of this divalent metal phosphate was brought to 2 g/L.
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 2 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value. Comparative Example 7
  • Zn 3 (PO 4 ) 2 -4H 2 O reagent was used as the divalent metal phosphate.
  • This divalent metal phosphate was made into a suspension and the suspension was filtered through 5- ⁇ m filter paper. The particles remaining on the filter paper were redispersed in water to prepare a suspension. Measurement of the average particle size in the suspension using a Coulter Counter (Coulter Company) gave a value of 6.5 ⁇ m. The concentration of the divalent metal phosphate in the suspension was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 2 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • Comparative Example 8 Zn 3 (PO 4 ) 2 -4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate. This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper.
  • PALBOND® L3020 concentrate (commercially available from Nihon Parkerizing Company, Limited), diluted with tapwater to give 4.8 % of the concentrate in the diluted solution and to adjust total acidity, free acidity, and accelerator concentration to the concentrations in general use for automotive zinc phosphate treatment, was used as the zinc phosphate treatment bath.
  • the weight of the conversion-treated panel was measured to give W1 (g).
  • the coating on the conversion-treated panel was then stripped (stripping bath and conditions given below) and the weight was again measured to give W2 (g).
  • stripping bath 5 % aqueous chromic acid solution stripping conditions: 75 °C, 15 minutes, dipping
  • the deposited coating crystals were inspected using a scanning electron microscope (SEM) at 1 ,500 X in order to determine crystal size. (4) P ratio
  • this value was determined only on the SPC steel panels by measuring the x-ray intensity of the phosphophyllite crystals (P) and x-ray intensity of the hopeite crystals (H) in the zinc phosphate conversion coating using an x-ray diffraction instrument.
  • the middle-coated test panels were then painted with a topcoat (Automotive Topcoat Paint from Kansai Paint) so as to provide a topcoat thickness of 40 ⁇ m and were baked at 140 °C for 30 minutes.
  • the cross-enscribed electrodeposition-painted panel was sprayed with 5 % salt water for 960 hours. After termination of the spray, evaluation was carried out by measuring the maximum one-side width of the rust around the enscribed cross.
  • the cross-enscribed electrodeposition-painted panel was dipped in 5 % salt water for 240 hours. After termination of dipping, evaluation was carried out by measuring the maximum one-side width of the rust around the enscribed cross.
  • a 100-square checkerboard pattern with 2-mm sided squares was scribed in the tricoated panel using a sharp cutter. Pressure-sensitive adhesive tape was then applied to the checkerboard and peeled off, after which the number of peeled off paint squares was counted.
  • the tricoated panel was dipped in deionized water at 40 °C for 240 hours. After the end of dipping, a checkerboard peel test was carried out as described above for the primary adhesiveness evaluation and the number of peeled off paint squares was counted.
  • Table 3 reports the properties of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the working ex- amples
  • Table 4 reports the properties of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the comparative examples.
  • Table 5 reports the results for evaluation of the post-paint performance of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the working examples
  • Table 6 reports the results for evaluation of the post-paint performance of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the comparative examples.
  • Tables 3 and 4 confirm a major improvement in the storage time stability of the surface conditioning pretreatment baths according to the present invention.
  • the storage time stability has been a problem with prior art products.
  • Examples 1 and 2 confirm the effect of the microparticulate oxide on the timewise stability. Furthermore, the effects did not vary even in the face of changes in the type of microparticulate oxide and alkali metal salt and in the treatment temperature, and in each case fine-sized, dense crystals were obtained that were equal or superior to those afforded by the prior art products.
  • Tables 5 and 6 confirm that the surface conditioning pretreatment baths according to the present invention gave a paint performance equal or superior to that of the prior art products.

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Abstract

La présente invention concerne un prétraitement préalable à la phosphatation que l'on réalise en mettant un substrat de métal à enduire en contact avec une composition de prétraitement dont le pH est compris entre 4 et 13, et qui contient en dispersion de fines particules de sels de métaux alcalins ou d'ammonium et des phosphates de métaux divalents ou trivalents. Le conditionnement réalisé est aussi bon qu'avec les sels conventionnels de Jernstedt, les compositions de prétraitement de l'invention étant plus stable au stockage.
EP98908792A 1997-03-07 1998-03-09 Conditionnement de surfaces metalliques prealablement a la phosphatation Revoked EP0977908B1 (fr)

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JP05218197A JP3451334B2 (ja) 1997-03-07 1997-03-07 金属のりん酸塩皮膜化成処理前の表面調整用前処理液及び表面調整方法
JP5218197 1997-03-07
PCT/US1998/003934 WO1998039498A1 (fr) 1997-03-07 1998-03-09 Conditionnement de surfaces metalliques prealablement a la phosphatation

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DE102011087314A1 (de) 2011-11-29 2013-05-29 Henkel Ag & Co. Kgaa Verfahren zur Regeneration wässriger Dispersionen sowie Zellpaket für die Elektrodialyse
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MY124633A (en) 2006-06-30
CA2283387C (fr) 2007-07-03
ID20532A (id) 1999-01-07
KR19980079984A (ko) 1998-11-25
EP0977908A4 (fr) 2000-06-07
EP0977908B1 (fr) 2003-09-03
JPH10245685A (ja) 1998-09-14
CN1198958C (zh) 2005-04-27
KR100473603B1 (ko) 2005-08-29
JP3451334B2 (ja) 2003-09-29
ES2205456T3 (es) 2004-05-01
ZA981796B (en) 1998-09-07
DE69817803D1 (de) 2003-10-09
TW371675B (en) 1999-10-11
CN1197849A (zh) 1998-11-04
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AU6673698A (en) 1998-09-22
CA2283387A1 (fr) 1998-09-11

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