EP1047508A1 - Procede ameliorant la resistance a la corrosion d'une surface metallique - Google Patents

Procede ameliorant la resistance a la corrosion d'une surface metallique

Info

Publication number
EP1047508A1
EP1047508A1 EP99903009A EP99903009A EP1047508A1 EP 1047508 A1 EP1047508 A1 EP 1047508A1 EP 99903009 A EP99903009 A EP 99903009A EP 99903009 A EP99903009 A EP 99903009A EP 1047508 A1 EP1047508 A1 EP 1047508A1
Authority
EP
European Patent Office
Prior art keywords
post
resin
coating
treatment
treatment solution
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.)
Withdrawn
Application number
EP99903009A
Other languages
German (de)
English (en)
Inventor
Takumi Honda
Mutsumi Yanagi
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 Corp
Original Assignee
Henkel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP1047508A1 publication Critical patent/EP1047508A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/088—Autophoretic paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B05D7/144—After-treatment of auto-deposited coatings

Definitions

  • This invention relates to a method for coating metal surfaces in order to impart corrosion resistance thereto. More particularly, the invention relates to a method for the
  • Japanese Patent Application Laid Open (Kokai or Unexamined) Number Sho 52- 68240 (68,240/1977) teaches that the post-drying corrosion resistance of the resin coating can be improved by exposing the uncured autodeposited resin coating prior to its thermal drying to an aqueous dispersion or aqueous solution whose base component is 5 to 100 g/L nitrogenous organic compound, for example, at least 1 selection from the group consisting of amines, the amine salts of carboxyiic acids, amino acids, melamine, and amides.
  • the post-treatment of autodeposited resin coatings with a nitrogenous organic compound is an effective means for improving the corrosion resistance and adherence of the ultimately obtained resin coating.
  • autodeposition coating is typically implemented by dipping or immersion, the acid component and/or metal ions component (for example, the iron ions) present in the uncured autodeposited resin coating will elute into the treatment solution used as the post-treatment agent (the post- treatment solution). Since this will frequently cause a loss of stability of the post- treatment solution, this approach may not always be acceptable when viewed from the perspective of producing a resin coating that evidences a continuously stable product quality.
  • the present invention provides a method for the anticorrosion coating of metal surfaces that produces an excellent adherence and resistance to corrosion and that maintains its ability to generate these properties even after its post-treatment solution has been used to treat a substantial amount of metal surface.
  • a high-quality autodeposited resin coating can be obtained by forming an uncured resin coating on a metal surface by bringing the metal surface into contact with an autodepositing coating composition; by then executing a post-treatment on the uncured resin coating prior to its thermal drying using a post- treatment solution that contains as its essential components a water-soluble amino resin bearing specific reactive functional groups and an amine compound; and by thereafter drying and curing the post-treated resin coating.
  • the solution for the post-treatment of aqueous autodepositing resin compositions according to the present invention preferably contains its water soluble amino resin and its other amine compound as described above in a weight ratio from 2.0 : 1.0 to 200 : 1.0, or more preferably from 5.0 : 1.0 to 50 : 1.0.
  • the post-treatment agent and post-treatment solution contain less than the specified amount of water-soluble amino resin
  • the ultimately obtained resin coating will usually exhibit an inadequate corrosion resistance and adherence.
  • the effects provided by the water-soluble amino resin do not increase at amounts in excess of the specified upper limit, and such amounts are also problematic because they cause the content of the amine compound to be too low on a relative basis. More specifically, a too low content of amine compound causes the resulting post-treatment solution to have an unsatisfactory stability during continuous use; this results in variations in the quality of the resin coating product.
  • a too high content of the amine compound causes the content of the water-soluble amino resin to be too low on a relative basis, resulting in an unsatis- factory corrosion resistance and adherence.
  • Each molecule of the water-soluble amino resin used by the present invention preferably contains at least two reactive functional groups represented by at least one OF the following chemical moiety formulas (1), (2), and (3): (1)
  • the water-soluble amino resin used in the present invention can be selected from methylated melamine resins (the degree of methylation is not critical and highly methylated melamine resins and partially methylated melamine resins can be used), imino-type methylmelamine resins, imino-type methylated melamine resins, methylolated melamine resins, benzoguanamine resins, and glycoluryl resins.
  • the amine compound in the post-treatment agent and post-treatment solution used in the present invention can be selected from the group consisting of monoalkyla- mines, dialkylamines, trialkylamines, monoalkenylamines, dialkenylamines, trialkenyl- amines, monoaikanolamines, dialkanolamines, and trialkanolamines, as preferably exemplified by ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, allylamine, diallylamine, triallylamine, dimethylethanolamine, diethylethanolamine, ethanoiamine, diethanolamine, and triethanoiamine.
  • Each of the alkyl, alkenyl, and alkanol groups in the subject alkylamines, alkenylamines, and alkanolamines independently preferably contains from 1 to 15 carbon atoms, or more preferably, with increasing preference in the order given, not more than 10, 8, 6, or 4 carbon atoms.
  • the amine compound used in the post-treatment solution in a method accord- ing to the present invention for the anticorrosion coating of metal surfaces is most preferably selected from the group consisting of ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tripropylamine, allylamine, diallylamine, triallylamine, dimethylethanolamine, diethylethanolamine, ethanoiamine, diethanolamine, and triethanoiamine.
  • the post-treatment solution used in the present invention may also optionally contain one or more ammonium salts.
  • Preferred ammonium salts can be selected from those taught in Japanese Patent Application Laid Open (Kokai or Unexamined) Number Hei 3-505841 (505,841/1991) and Japanese Patent Application Laid Open (Kokai or Unexamined) Number Hei 5-186889 (186,889/1993), for example, ammonium bicarbonate and ammonium hydroxide.
  • the aqueous autodepositing resin composition used in the method of the present invention contains metal ions, oxidizing agent, acid, and water-dispersible or water-soluble coating-forming organic resin that contains the product of the polymerization of at least one selection from carboxyl-functional monomers and hydroxyl- functional monomers.
  • Carboxyl-functional monomers employed in the production of the coating- forming organic resin used in a method according to the present invention are ethylenically unsaturated carboxylic acid monomers, for example, acrylic acid, methacryl- ic acid, maleic acid, itaconic acid, and fumaric acid.
  • Hydroxyl-functional monomers employed in the production of the coating-forming organic resin used by the method according to the present invention are ethylenically unsaturated hydroxylated monomers, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.
  • the polymerization that produces the coating-forming organic resin used in the method according to the present invention may also employ one or more other ethylenically unsaturated monomers.
  • these other ethylenically unsaturated monomers can be selected from, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate.
  • the film-forming organic resin used in the method according to the present invention can also be selected from polyester polyol compounds as afforded by the polyesterification of poiyhydric alcohol molecules bearing at least two hydroxyl groups each with organic acid molecules bearing at least two carboxyl groups each.
  • the former are exemplified by ethylene glycol, propylene glycol, and 1 ,6-hexanediol, while the latter can be exemplified by phthalic acid, isophthalic acid, and terephthalic acid.
  • the coating- forming organic resin used by the method according to the present invention will comprise at least one selection from the above-described polymers, copolymers, and polyester polyols.
  • the molecular weight of the coating-forming organic resin used in the invention method is not critical, molecular weights of, for example, 20,000 to 1 ,000,000 are preferred and molecular weights of 100,000 to 1 ,000,000 are particularly preferred. This molecularweight can be measured by gel permeation chromatography in tetrahydrofuran using polyethylene or polyacrylate ester as the reference material.
  • the coating-forming organic resin employed by the invention is preferably used in the form of an aqueous emulsion, which in many cases can be prepared by a conventional emulsion polymerization technique. However, this aqueous emulsion can also be prepared by taking a coating-forming organic resin prepared by another polymerization technique and emulsifying the resin in water.
  • an emulsion of the coating-forming resin can be prepared by running a polymerization reaction in a mixture comprising at least water, anionic and/or nonionic surfactant, monomer for the resin component as described above, and polymerization initiator.
  • the autodepositing resin composition used by the present invention can be prepared by mixing coating-forming organic resin obtained as described above, acid, oxidizing agent, and optionally a compound capable of furnishing metal ions and by then also adding water as necessary or desired.
  • the acid used in the subject autodepositing resin composition preferably is at least one selection from fluorozirconic acid, fluorotitanic acid, fluorosilicic acid, fluoroboric acid, hydrofluoric acid, phosphoric acid, and nitric acid.
  • the use of hydrofluoric acid is most preferred.
  • the oxidizing agent preferably is hydrogen peroxide, potassium permanganate, or sodium nitrite; the use of hydrogen peroxide is most preferred.
  • the compound capable of furnishing metal ions is not critical as long as this compound is stable in the resin composition.
  • This compound preferably is ferric fluoride, ferric nitrate, ferrous phosphate, or cobaltous nitrate, with ferric fluoride being most pre- ferred.
  • the aqueous autodepositing resin composition used by the method of the present invention preferably contains from 5 to 550 g/L and more preferably from 50 to 100 g/L of the above-described coating-forming organic resin, in each case measured as the concentration of resin solids.
  • the acid concentration is preferably from 0.1 to 5.0 g/L and more preferably from 0.5 to 3.0 g/L
  • the oxidizing agent concentration is preferably from 0.01 to 3.0 g/L and more preferably from 0.03 to 1.0 g/L.
  • a metal ions source compound need not be present, but the use of this compound is preferred, in which event its concentration is preferably no greater than 50 g/L and more preferably is from 1.0 to 5.0 g/L.
  • the aqueous autodepositing resin composition used in a method of the present invention may contain optional components in addition to the components described above.
  • this composition may contain a coalescing agent such as, for example, trialkylpentanediol isobutyrate or alkyi carbitol, and pigment such as, for example, carbon black, phthalocyanine blue, phthalocyanine green, quinacridone red, Hansa yellow, and benzidine yellow.
  • the coalescing agent functions to lower the minimum temperature for coating formation during formation of the deposited resin coating and thereby further facilitates melt-bonding of the deposited resin.
  • the technique for effecting contact between the metal surface and the aqueous autodepositing resin composition is not critical to the method according to the present invention. Dipping, applicator methods, and spraying can be used, with dipping being preferred. Nor are the treatment temperature and treatment time critical to the instant method. In the case of dipping, the metal stock is generally preferably dipped in the composition at room temperature, for example, 18 to 25 °C, for from 30 to 300 seconds and preferably from 90 to 180 seconds.
  • the extent of resin coating formation on the metal surface is also not critical, but dried film thicknesses of 10 to 40 micrometers are preferred and dried film thicknesses of 20 to 30 micrometers are particularly preferred.
  • the metal surface is preferably degreased and then rinsed with water prior to its contact with the resin composition.
  • One of the most significant features of the invention is the excellent stability of the post-treatment solution. If the amino resin component were used by itself, the hydrofluoric acid (acid component) and iron ions (metal ions) eluting and admixing into the post-treatment solution during post-treatment of the resin coating with the post- treatment solution would cause the coagulation of the water-soluble amino resin component present in the post-treatment solution and hence would cause a substantial decline in the stability of the post-treatment solution. This in turn would lead to variations in the quality of the post-treated coating. However, the amino compound present in the treatment solution, which can neutralize the eluting acid component and complex the iron ions, inhibits adverse effects on the water-soluble amino resin and stabilizes the post- treatment solution.
  • the temperature of the post-treatment solution is preferably from 10 to 40 °C as a general rule and is particularly preferably from 20 to 25 °C, and the treatment time is preferably in the range from 20 to 180 seconds.
  • Solution temperatures below 10 °C result in a pronounced tendency for the resin coating to crack during the thermal drying step, while temperatures in excess of 40 °C tend to produce an undesirable appearance of the coating due to a pronounced tendency for the coating to whiten after thermal drying.
  • the effects from the post-treatment normally will be inadequate at treatment times of less than 20 seconds, while treatment times greater than 180 seconds have a tendency to impair the adherence of the coating and the uniformity of appearance of the coating.
  • the resin coating is submitted to drying and curing.
  • the conditions used in the drying and curing process will vary as a function of the type of coating-forming organic resin used in the autodepositing resin composition, but thermal drying will generally be carried out at from 110 to 200 °C for a time that is from 5 to 30 seconds. This invention will be illustrated in greater detail below by working and comparative examples.
  • a monomer component of 5 parts of methacrylic acid, 5 parts of 2-hydroxyethyl methacrylate, 12 parts of styrene, 40 parts of acrylonitrile, and 38 parts of ethyl acrylate was mixed with 1 part of acrylate ester-type reactive surfactant, 0.3 part of ammonium persulfate, and 398.7 parts of water.
  • the resulting mixture was emulsion-polymerized at 75 °C to give a coating-forming organic Resin (A) with a resin solids content of 20 %.
  • Resin (B) A monomer component of 8 parts of methacrylic acid, 12 parts of methyl methacrylate, 40 parts of acrylonitrile, 20 parts of ethyl acrylate, and 20 parts of butyl acrylate was mixed with 1 part of acrylate ester-type reactive surfactant, 0.3 part of ammonium persulfate, and 398.7 parts of water. The resulting mixture was emulsion- polymerized at 75 °C to give a coating-forming organic Resin (B) with a resin solids con- tent of 20 %.
  • Preliminarily cleaned cold-rolled steel sheets (70 * 150 x 1 millimeters, hereinafter usually abbreviated as "mm") were coated by dipping for 180 seconds into a treatment bath comprising Autodepositing Resin Composition (1) described below while the bath temperature was maintained at 20 to 22 °C. After a water rinse, the resulting uncured autodeposited resin coating was then dipped in Post-treatment Solution (A) at
  • PMMR means “partially methylated melamine resin” (88 % solids, from Mitsui Cytec Ltd.).
  • HMMR means “highly methylated melamine resin” (100 % solids, from Mitsui Cytec Ltd.).
  • ⁇ m means “micrometres”.
  • a resm-coated sheet was prepared generally as described in Example 1 but in this example the uncured autodeposited resm coating afforded by Autodepositing 15 Coating Composition (1) was dipped at 24 °C in Post-treatment Solution (B) with tne composition reported in Table 1. This was followed by drying in a convection oven at 80 °C for 20 minutes and suDmission to the various coating performance tests.
  • Example 3
  • a resm-coated sheet was prepared generally as described in Example 1 , but in 20 this example coating was run using Autodepositing Coating Compositton (2) with the composition described below The resulting uncured autodeposited resin coating was dipped at 24 "C in Post-treatment Solution (C) with the composition reported in Taoie 1 This was followed by drying in a convection oven at 180 °C for 20 minutes and submission to the various coating performance tests 25 Autodepositing Coating Composition (2)
  • a resin-coated sheet was prepared generally as in Example 1 , but in this example
  • Resin-coated sheets were prepared generally as described in Example 3, but using the above-described Autodepositing Coating Composition (2).
  • the resulting uncured autodeposited resin coatings were dipped at 24 °C in one of the Post-treatment Solutions (E) to (G) with the compositions reported in Table 1. This was followed by drying in a convection oven at 180 °C for 20 minutes and submission to the various coating performance tests.
  • Comparative Example 4 A resin-coated sheet was prepared generally as in Example 1 using the above- described autodepositing coating composition (1).
  • the resulting uncured autodeposited resin coating was then dried, without post-treatment, in a convection oven at 180 °C for 20 minutes and submitted to the various coating performance tests.
  • the coating performance tests were as follows. (1 ) Coating thickness
  • the thickness was measured at three locations (upper, middle, and lower regions) on the sample sheet, and the average of these values is reported in Table .
  • test coupon was immersed in warm water (40 °C) for 240 hours. Both before and after this immersion, a 100-square grid (1-mm intervals) was scribed in the test coupon, pressure-sensitive adhesive tape was applied to the grid, the tape was peeled off, and the number of remaining squares of the coating was counted. The results before and after immersion are reported in Table 1.
  • the method according to the present invention for the anticorrosion coating of metal surfaces through its use of the specific post-treatment solution according to the present invention, provides a highly corrosion-resistant and strongly adherent autodeposited resin coating and does so at a continuously stable quality level.
  • the post-treatment solution used in the method of the invention is very stable and can therefore be used for the continuous post-treatment of resin coatings.
  • Post-treatment was run in Examples 2 and 3 at the rate of 2.0 m 2 of surface area per 1 L of post-treatment solution, and the resulting resin coatings were submitted to the coating performance tests described above.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention consiste à former sur une surface métallique un revêtement en résine, au moyen d'une composition de résine aqueuse à auto-déposition, contenant un agent oxydant, un acide et une résine soluble ou dispersible dans l'eau, à fonction carboxyle et/ou hydroxyle, et éventuellement, des ions métalliques. Le revêtement ainsi obtenu, alors qu'il est encore à l'état non durci, est soumis à un post-traitement avec une solution aqueuse contenant entre 0,5 et 5,0 g/L d'une amine et entre 10 et 100 g/l (solides) de molécules de résine aminique solubles dans l'eau, portant au moins deux groupes alcoxyméthylamino, méthylolamino et/ou imino. Le revêtement est ensuite séché et durci. Ce procédé permet d'obtenir sur le métal un revêtement hautement anticorrosion, et contrairement à un procédé analogue dans lequel la solution de post-traitement contient une résine aminique mais pas d'amine, cette solution de post-traitement reste stable et assure une efficacité de revêtement continue, de haute qualité, même après qu'on ait traité une surface métallique très importante par volume unitaire de solution de post-traitement.
EP99903009A 1998-01-14 1999-01-13 Procede ameliorant la resistance a la corrosion d'une surface metallique Withdrawn EP1047508A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP00607898A JP3736958B2 (ja) 1998-01-14 1998-01-14 金属表面の耐食被覆方法
JP607898 1998-01-14
PCT/US1999/000377 WO1999036192A1 (fr) 1998-01-14 1999-01-13 Procede ameliorant la resistance a la corrosion d'une surface metallique

Publications (1)

Publication Number Publication Date
EP1047508A1 true EP1047508A1 (fr) 2000-11-02

Family

ID=11628541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99903009A Withdrawn EP1047508A1 (fr) 1998-01-14 1999-01-13 Procede ameliorant la resistance a la corrosion d'une surface metallique

Country Status (8)

Country Link
EP (1) EP1047508A1 (fr)
JP (1) JP3736958B2 (fr)
KR (1) KR19990067884A (fr)
AU (1) AU2313099A (fr)
CA (1) CA2318442A1 (fr)
TW (1) TW464545B (fr)
WO (1) WO1999036192A1 (fr)
ZA (1) ZA99221B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3860693B2 (ja) * 1999-12-17 2006-12-20 日本パーカライジング株式会社 自己析出型被覆組成物、金属表面の被覆方法及び被覆処理金属材料
US6780922B2 (en) 2002-01-17 2004-08-24 Honeywell International Inc. Adhesion promoters with epoxy-reactive groups
JP4449468B2 (ja) * 2003-01-31 2010-04-14 Ｊｆｅスチール株式会社 黒色亜鉛系めっき鋼板
EP2126156A4 (fr) * 2006-12-01 2012-03-07 Henkel Kgaa Bain d'auto-dépôt à teneur élevée en peroxyde
BRPI0906510A2 (pt) * 2008-01-08 2015-07-14 Henkel Ag & Co Kgaa Processo para tratar um artigo, artigo de fabricação, e, artigo revestido.
US8518493B2 (en) 2009-01-06 2013-08-27 Henkel Ag & Co. Kgaa Co-cure process for autodeposition coating

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5033940A (fr) * 1973-07-28 1975-04-02
CS233998B1 (cs) * 1983-12-06 1985-03-14 Zivan Behal Termoreaktivní protikorozní impregnační prostředky
DE3720217A1 (de) * 1987-06-17 1988-12-29 Metallgesellschaft Ag Verfahren zur erzeugung elektrisch isolierender ueberzuege auf metalloberflaechen
US5164234A (en) * 1991-01-24 1992-11-17 Henkel Corporation Treating an autodeposited coating with an alkaline solution containing organophosphonate ions
US5667845A (en) * 1993-08-05 1997-09-16 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9936192A1 *

Also Published As

Publication number Publication date
WO1999036192A1 (fr) 1999-07-22
CA2318442A1 (fr) 1999-07-22
KR19990067884A (ko) 1999-08-25
JPH11197597A (ja) 1999-07-27
AU2313099A (en) 1999-08-02
TW464545B (en) 2001-11-21
JP3736958B2 (ja) 2006-01-18
ZA99221B (en) 1999-07-14

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