WO1995004606A1 - Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces - Google Patents
Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces Download PDFInfo
- Publication number
- WO1995004606A1 WO1995004606A1 PCT/US1994/008212 US9408212W WO9504606A1 WO 1995004606 A1 WO1995004606 A1 WO 1995004606A1 US 9408212 W US9408212 W US 9408212W WO 9504606 A1 WO9504606 A1 WO 9504606A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metallic surface
- reaction rinse
- coating
- autodeposited
- salt
- Prior art date
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
- B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
- B05D7/144—After-treatment of auto-deposited coatings
Definitions
- This invention relates to the treatment of autodeposited coatings in order to retain longer or to enhance corrosion resistance of the coatings on metallic surfaces, particularly ferriferrous articles, including zinc coated (galvanized) steel, STATEMENT OF RELATED ART
- Autodeposition is a generic term used to describe the deposition of a uniform organic film on a clean metal surface without the use of electric current in the deposition process.
- Autodeposition involves the use of an aqueous resin containing coating composition of relatively low solids concentration, usually 5 to 12 %, normally less than 10 %, to form a coating of high solids concentration, usually greater than 10 %, on a metallic surface immersed therein, with the coating increasing in thickness or weight the longer the time the metallic surface is immersed in the coating composition.
- Autodeposition composition can be used to form coatings which have good aesthetic properties and which protect the underlying metallic substrate from being degraded, i.e. corroded by water. Many applications however require the autodeposited coating have par ⁇ ticularly good properties for use.
- Various means have been developed to improve the properties of autodeposited coatings including:
- An object of the present invention is to provide a process which includes a reaction rinse which will retain, or improve, the corrosion resistance properties of the autodeposited coating employing non-chromium containing materials which are environmentally friendly, raising no disposal problems.
- a further object of the present invention is to provide a single reaction rinse for coatings on both cold rolled steel and galvanized steel. In this way a single reaction rinse may be used for both steel types and coatings thereon so that simultaneous processing of cold rolled steel and galvanized steel substrates may be carried out.
- corrosion resistance is retained, or improved, by treating the uncured coating on the metallic substrate with a hydrofluorozirconic compound, either the acid per se or salts thereof, preferably the cobalt or nickel salts thereof.
- a hydrofluorozirconic compound either the acid per se or salts thereof, preferably the cobalt or nickel salts thereof.
- the coating may optionally be rinsed with water, preferably deionized water, and then cured in a low temperature oven at a temperature appropriate for the specific coating deposited on the metallic substrate.
- the ferriferrous substrate is cleaned, generally using an alkaline, commercially available cleaner.
- the cleaning is carried out either by spray application, or immersion or combination of both, after which the coated workpiece is rinsed with water to remove any residual cleaning solution, prior to deposition of the coating.
- the 5 autodeposited film is preferably applied by immersion of the substrate into a coating bath containing the desired polymer latex, emulsion or dispersion for a time sufficient to coat the substrate with a film to a thickness from about 0.3 up to about 1.0 mil, preferably in the range of about 0.6 to about 1.0 mil. Because the autodeposition process is driven chemically, rather than electrically, it coats wherever the solution wets the surface of the substrate depositing ⁇ o a relatively uniform coating on even intricate or complex shapes or designs of the substrate. The time and temperature of treatment will vary depending on the nature of the particular resins comprising the coating. After the coating is deposited, a reaction rinse is applied in the present invention to retain, or improve, the corrosion resistance of the coating.
- the autodeposition coatings useful in the present invention are poly ⁇ vinylidene chlor- i5 ide ⁇ polymers, preferably copolymers containing at least about 50 % by weight of poly ⁇ vinylidene chloride ⁇ .
- the copolymers can be prepared by copolymerizing (a) vinylidene chloride monomer with (b) monomers such as methacrylic acid, methyl methacrylate, acrylonitrile and vinyl chloride and (c) a water soluble ionic material such as sodium sulfoethyl methacrylate.
- Such copolymers are more specifically described in U.S. Patent
- the reaction rinse employed in the present invention which follows after application of the poly ⁇ vinylidene chloride ⁇ autodeposited coating, provides for retention and en ⁇ hancement of the corrosion resistance of the deposited coating.
- the reaction rinse employed 5 herein is an aqueous solution containing from about 0.05 to about 20 %, preferably about 0.05 to about 5 % by weight of hydrofluorozirconic acid, or a salt thereof, preferably a cobalt or nickel salt.
- the results achieved by the present invention are effective on both cold rolled steel and galvanized steel, thereby allowing the two types to be processed together.
- the poly ⁇ vinylidene chloride ⁇ resin coating is applied from an aqueous, acidic solution of solids concentration of about 10 %, in the conventional manner, typically by immersion, for a time sufl ⁇ cient to cause the resin polymer particles to deposit on the metallic surface in a continuous film to a dry thickness of about 0.3 mil to about 1.0 mil, preferably about 0.6 to about 1.0 mil.
- about 40 to about 120 seconds will be sufficient at immersion bath temperatures of about 20 to about 22 ° C.
- the coated metallic article is typically rinsed with tap water or deionized water by immersion prior to treatment with the hydrofluorozirconic acid reaction rinse.
- the aqueous acid reaction rinse solution is preferably adjusted to a pH of about 5 or 6 prior to treatment.
- the rinse is preferably and typically applied by immersion in the reaction rinse solution containing about 0.05 to about 5.0 % by weight of the hydrofluorozirconic acid compound for about 40 to about 120 seconds, preferably about 60 to about 90 seconds.
- the immersion bath temperature will again typically be about 20 - 22 ° C, although a temperature range of about 10 to about 35 ° C may be employed.
- the coated article is again optionally rinsed with water, either plain tap water or deionized water, prior to being cured at an elevated temperature so selected that the protective properties of the coating are fully developed but not adversely affected.
- water either plain tap water or deionized water
- the temperature and time of treatment will depend on the nature of the particular resin in the autodeposited coating and the thickness of the coating. Exemplary conditions with the poly ⁇ vinylidene chloride ⁇ coatings employed in the present invention will vary from a temperature above about 22° C up to about 120° C for times ranging from a few seconds, i.e. about 5 seconds, up to about 10 to about 30 minutes, dependent on the mass of the coated article.
- the coating is baked for a period of time until the metallic surface has reached the temperature of the heated environment, typically in a forced air baking oven.
- the dried, cured coated articles are found to retain excellent, and even enhanced corrosion resistance when tested in soak tests or the neutral salt spray ("NSS") test, such as ASTM B-l 17 and scab corrosion cycles.
- NSS neutral salt spray
- Example 1 This example illustrates the preparation of a metallic surface having an autodeposited resinous coating.
- the metallic surface comprised steel panels, both cold rolled steel (CRS) and zinc galvanized steel (GS) panels, which were cleaned with a conventional alkaline cleaner composition and rinsed with water prior to being coated by immersion in the autodepositing composition at ambient temperature (about 21 ° C) for about 90 seconds.
- the autodepositing immersion bath had the following composition:
- g L 60 grams per liter (hereinafter abbreviated as "g L") of internally stabilized copolymer of vinylidene chloride, 2.5 g/L of carbon black, 0.4 g/L of HF, 28 g/L of ferric iron, and the balance water.
- Example 2 the uncured coated panels from example 1 are treated with a reaction rinse immersion bath after first being rinsed with water.
- the reaction rinse without cobalt cations contained 0.5 % by weight of HjZrFg and was adjusted to the pH shown in the following tables with ammonia if needed.
- the concentration is shown in the tables below; the pH was 3.5 for all the concentrations shown.
- the panels were then rinsed with water (deionized) and the panels were then cured for 20 minutes in an oven at a temperature of 105 ° C.
- Example 3 This example illustrates the results of corrosion resistance testing of various panels.
- Table 1 below illustrates salt spray performance and cyclic scab performance on galvanized steel, and Tables 2 - 7 indicate performance on other tests as noted.
- the letters "GM” and the numbers and letters immediately following these letters in the headings of Tables 2 - 7 refer respectively to the General Motors Corporation and to various specific corrosion tests that are part of performance specifications at that company. Test details are readily available from General Motors. Briefly, the tests reported here are described as follows: 1. Cyclic Corrosion - GM 951 IP
- the samples are treated at 25 °C. and 50 % RH environment for 8 hours, including 4 sprays at 90 minutes intervals with a solution containing 0.9 % NaCl, 0.1 % CaCl 2 , and 0.25 % NaHCO 3 in deionized water.
- the samples are then subjected to an 8 hour fog, 100 % RH at 40° C, followed by 8 hours at 60° C and less than 20 % RH.
- the entire treatment is repeated for the desired number of cycles, usually 40 cycles.
- the samples are (1) held in a freezer at -30° C for 2 hours, fol- lowed by ambient conditions for 2 hours and subsequently (2) in an oven at 70° C for 2 hours.
- the samples are then (3) subjected to a 5 % NaCl solution salt spray for 2 hours and then (4) held in a humidity chamber at 38° C and 95 % RH for 64 hours.
- the sam ⁇ ples are then (5) held in an oven at 60° C for 1 hour followed by (6) a freezer at -30° C for 30 minutes.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Physical Vapour Deposition (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019960700593A KR960703685A (en) | 1993-08-05 | 1994-07-27 | TREATMENT TO IMPROVE CORROSION RESISTANCE OF AUTODEPOSITED COATINGS ON METALLIC SURFACES |
AU75138/94A AU676938B2 (en) | 1993-08-05 | 1994-07-27 | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces |
BR9407216A BR9407216A (en) | 1993-08-05 | 1994-07-27 | Process for maintaining or improving the corrosion resistance of a cured, self-deposited resin coating on a metal surface |
DE69421932T DE69421932T2 (en) | 1993-08-05 | 1994-07-27 | TREATMENT TO IMPROVE THE CORROSION RESISTANCE OF AUTOPHORETIC LAYERS ON METAL SURFACES |
EP94925098A EP0716627B1 (en) | 1993-08-05 | 1994-07-27 | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces |
JP7506428A JPH09501350A (en) | 1993-08-05 | 1994-07-27 | Method for improving corrosion resistance of autodeposition coating for metal surface |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/102,660 US5372853A (en) | 1993-08-05 | 1993-08-05 | Treatment to improve corrosion resistance of autodeposited coatings of metallic surfaces |
US08/102,660 | 1993-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995004606A1 true WO1995004606A1 (en) | 1995-02-16 |
Family
ID=22291000
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/008212 WO1995004606A1 (en) | 1993-08-05 | 1994-07-27 | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces |
Country Status (13)
Country | Link |
---|---|
US (1) | US5372853A (en) |
EP (1) | EP0716627B1 (en) |
JP (1) | JPH09501350A (en) |
KR (1) | KR960703685A (en) |
CN (1) | CN1066074C (en) |
AT (1) | ATE187103T1 (en) |
AU (1) | AU676938B2 (en) |
BR (1) | BR9407216A (en) |
CA (1) | CA2168367A1 (en) |
DE (1) | DE69421932T2 (en) |
ES (1) | ES2139090T3 (en) |
WO (1) | WO1995004606A1 (en) |
ZA (1) | ZA945750B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5496438B2 (en) * | 1999-01-22 | 2014-05-21 | ロード コーポレーション | Self-adhesive adhesive |
US6410092B1 (en) | 1999-05-21 | 2002-06-25 | Henkel Corporation | Autodeposition post-bath rinse process |
EP2234734A4 (en) * | 2008-01-08 | 2015-08-26 | Henkel Ag & Co Kgaa | Co-cure process for autodeposition coating |
US8518493B2 (en) | 2009-01-06 | 2013-08-27 | Henkel Ag & Co. Kgaa | Co-cure process for autodeposition coating |
DE102009029334A1 (en) * | 2009-09-10 | 2011-03-24 | Henkel Ag & Co. Kgaa | Two-stage process for the corrosion-protective treatment of metal surfaces |
EP3052674B1 (en) * | 2013-09-30 | 2018-09-26 | BASF Coatings GmbH | Method for the autophoretic coating of metallic substrates by post-treating the coating with an aqueous sol-gel composition |
CN107446456B (en) * | 2017-08-03 | 2019-04-16 | 杭州五源科技实业有限公司 | Auto-deposition coating problems agent and its preparation method and application before steel coating |
KR102164100B1 (en) * | 2018-08-31 | 2020-10-12 | 주식회사 포스코 | COMPOSITION FOR SURFACE TREATMENT OF Mg-CONTAINING GALVANIZED STEEL SHEET AND Mg-CONTAINING GALVANIZED STEEL SHEET SURFACE-TREATED USING THE SAME |
US11246251B2 (en) | 2019-05-02 | 2022-02-08 | Seagate Technology Llc | Micro-component transfer systems, methods, and devices |
US10923378B2 (en) | 2019-05-13 | 2021-02-16 | Seagate Technology Llc | Micro-component batch transfer systems, methods, and devices |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3964936A (en) * | 1974-01-02 | 1976-06-22 | Amchem Products, Inc. | Coating solution for metal surfaces |
US4636265A (en) * | 1984-11-26 | 1987-01-13 | Henkel Kommanditgesellschaft Auf Aktien | Autodeposition post-bath rinse |
US4800106A (en) * | 1987-06-19 | 1989-01-24 | Amchem Products, Inc. | Gloss enhancement of autodeposited coatings |
US4971636A (en) * | 1988-06-30 | 1990-11-20 | Nkk Corporation | Method of producing highly corrosion-resistant surface-treated steel plates |
US5164234A (en) * | 1991-01-24 | 1992-11-17 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing organophosphonate ions |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4030945A (en) * | 1966-06-01 | 1977-06-21 | Amchem Products, Inc. | Rinsing coated metallic surfaces |
US4370177A (en) * | 1980-07-03 | 1983-01-25 | Amchem Products, Inc. | Coating solution for metal surfaces |
US4719038A (en) * | 1983-12-27 | 1988-01-12 | Nippon Paint Co., Ltd. | Corrosion resistant, coated metal laminate, its preparation and coating materials |
US4617068A (en) * | 1984-05-18 | 1986-10-14 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
DE3500443A1 (en) * | 1985-01-09 | 1986-09-11 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR IMPROVING THE CORROSION PROTECTION OF AUTOPHORETICALLY DEPOSIT RESIN LAYERS ON METAL SURFACES |
US5030323A (en) * | 1987-06-01 | 1991-07-09 | Henkel Corporation | Surface conditioner for formed metal surfaces |
US5089064A (en) * | 1990-11-02 | 1992-02-18 | Henkel Corporation | Process for corrosion resisting treatments for aluminum surfaces |
WO1993005198A1 (en) * | 1991-08-30 | 1993-03-18 | Henkel Corporation | Process for treating metal with aqueous acidic composition that is substantially free from chromium (vi) |
US5242714A (en) * | 1991-12-20 | 1993-09-07 | Henkel Corporation | Process for forming protective base coatings on metals |
-
1993
- 1993-08-05 US US08/102,660 patent/US5372853A/en not_active Expired - Fee Related
-
1994
- 1994-07-27 CN CN94193278A patent/CN1066074C/en not_active Expired - Fee Related
- 1994-07-27 ES ES94925098T patent/ES2139090T3/en not_active Expired - Lifetime
- 1994-07-27 JP JP7506428A patent/JPH09501350A/en active Pending
- 1994-07-27 DE DE69421932T patent/DE69421932T2/en not_active Expired - Fee Related
- 1994-07-27 BR BR9407216A patent/BR9407216A/en not_active IP Right Cessation
- 1994-07-27 EP EP94925098A patent/EP0716627B1/en not_active Expired - Lifetime
- 1994-07-27 WO PCT/US1994/008212 patent/WO1995004606A1/en active IP Right Grant
- 1994-07-27 CA CA002168367A patent/CA2168367A1/en not_active Abandoned
- 1994-07-27 KR KR1019960700593A patent/KR960703685A/en not_active Application Discontinuation
- 1994-07-27 AT AT94925098T patent/ATE187103T1/en not_active IP Right Cessation
- 1994-07-27 AU AU75138/94A patent/AU676938B2/en not_active Ceased
- 1994-08-02 ZA ZA945750A patent/ZA945750B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3964936A (en) * | 1974-01-02 | 1976-06-22 | Amchem Products, Inc. | Coating solution for metal surfaces |
US4636265A (en) * | 1984-11-26 | 1987-01-13 | Henkel Kommanditgesellschaft Auf Aktien | Autodeposition post-bath rinse |
US4800106A (en) * | 1987-06-19 | 1989-01-24 | Amchem Products, Inc. | Gloss enhancement of autodeposited coatings |
US4971636A (en) * | 1988-06-30 | 1990-11-20 | Nkk Corporation | Method of producing highly corrosion-resistant surface-treated steel plates |
US5164234A (en) * | 1991-01-24 | 1992-11-17 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing organophosphonate ions |
Also Published As
Publication number | Publication date |
---|---|
KR960703685A (en) | 1996-08-31 |
JPH09501350A (en) | 1997-02-10 |
US5372853A (en) | 1994-12-13 |
EP0716627A4 (en) | 1996-10-23 |
ATE187103T1 (en) | 1999-12-15 |
ES2139090T3 (en) | 2000-02-01 |
EP0716627B1 (en) | 1999-12-01 |
BR9407216A (en) | 1996-09-17 |
CN1130362A (en) | 1996-09-04 |
AU676938B2 (en) | 1997-03-27 |
CN1066074C (en) | 2001-05-23 |
CA2168367A1 (en) | 1995-02-16 |
AU7513894A (en) | 1995-02-28 |
ZA945750B (en) | 1995-03-15 |
DE69421932D1 (en) | 2000-01-05 |
EP0716627A1 (en) | 1996-06-19 |
DE69421932T2 (en) | 2000-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0902844B1 (en) | Composition and method for treatment of phosphated metal surfaces | |
KR100443439B1 (en) | How to process aluminum surfaces without using chrome | |
AU735281B2 (en) | Process of treating metallic surfaces | |
JP2547456B2 (en) | Treatment method for self-deposited coating | |
JP5252925B2 (en) | Surface chemical conversion liquid and method for producing chemical conversion metal plate | |
EP0795045B1 (en) | Composition and method for treatment of conversion-coated metal surfaces | |
US3196039A (en) | Process and solution for the aftertreatment of phosphate coatings | |
JPH09501469A (en) | Compositions and methods for treating phosphated metal surfaces | |
MXPA97004031A (en) | Composition and method for the treatment of metal surfaces covered by convers | |
EP0716627B1 (en) | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces | |
EP0665772B1 (en) | Reducing or avoiding pinhole formation in autodeposition on zinciferous surfaces | |
US4186226A (en) | Autodeposited coatings with increased surface slip | |
US4181773A (en) | Process for rendering surfaces permanently water wettable and novel products thus-produced | |
JPH05214266A (en) | Self-depositing water-based coating composition | |
CA1060287A (en) | Metal coating method | |
US4657788A (en) | Process for multiple stage autodeposition of organic coatings onto metals | |
US3720547A (en) | Permanganate final rinse for metal coatings | |
GB2331942A (en) | Treating metal surfaces | |
EP0074211B1 (en) | Coated metal substrate and method of coating a metal substrate | |
US4318944A (en) | Reducing the cracking of autodeposited coatings | |
US6569498B2 (en) | Passification of zinc surfaces | |
JPH1180973A (en) | Chromate surface treating agent for alminum or aluminum alloy and method for surface treatment | |
JPH045753B2 (en) | ||
CA2204280C (en) | Composition and method for treatment of conversion-coated metal surfaces | |
JPH0242906B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 94193278.8 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK ES FI GB GE HU JP KE KG KP KR KZ LK LT LU LV MD MG MN MW NL NO NZ PL PT RO RU SD SE SI SK TJ TT UA UZ VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE MW SD AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2168367 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1994925098 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1994925098 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1994925098 Country of ref document: EP |