EP0425271B1 - Verfahren zur Nachspülung von Phosphatumwandlungsüberzügen mit S-Triazin enthaltenden Zusammensetzungen - Google Patents

Verfahren zur Nachspülung von Phosphatumwandlungsüberzügen mit S-Triazin enthaltenden Zusammensetzungen Download PDF

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Publication number
EP0425271B1
EP0425271B1 EP90311659A EP90311659A EP0425271B1 EP 0425271 B1 EP0425271 B1 EP 0425271B1 EP 90311659 A EP90311659 A EP 90311659A EP 90311659 A EP90311659 A EP 90311659A EP 0425271 B1 EP0425271 B1 EP 0425271B1
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EP
European Patent Office
Prior art keywords
composition
triazine compound
coating
phosphate conversion
conversion coating
Prior art date
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Expired - Lifetime
Application number
EP90311659A
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English (en)
French (fr)
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EP0425271A2 (de
EP0425271A3 (en
Inventor
Ralph C. Gray
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.)
PPG Industries Inc
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PPG Industries Inc
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Filing date
Publication date
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Publication of EP0425271A3 publication Critical patent/EP0425271A3/en
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention relates to the pretreatment of a ferrous or galvanized metal surface prior to the application of a subsequently applied coating.
  • a phosphating conversion coating which is usually followed by a final rinsing or sealing step.
  • the rinsing composition usually comprises chromic acid. While effective in the rinsing step, chromic acid is, nonetheless, undesirable because of its toxicity and the attendant problems of disposal.
  • the present invention provides a process for the pretreatment of ferrous or galvanized metal surfaces prior to the application of a subsequently applied coating in which the rinsing composition is essentially free of chromic acid.
  • US-A-3,706,604 discloses an improved process for coating metal wherein a phosphate or oxalate conversion coating composition is applied to an aluminium, zinc or ferrous metal surface to form a substantially dry, uniform phosphate or oxalate conversion coating, a portion of which is water-soluble.
  • An organic containing reducing and/or esterifying fixing or immobilizing coating composition containing hexavalent chromium is then applied which reacts out the water soluble portion of the conversion coating to produce water-insoluble phosphate or oxalates and form a substantially dry, uniform composite coating. This process is said to eliminate the need for rinsing procedures.
  • US-A-2,976,193 discloses inter alia a process for producing a substantially colorless chemically bonded coating on an aluminum article, which comprises treating said article with an aqueous acid aluminum conversion coating bath, said bath comprising a halogen-containing anion, an anion including a member of the group consisting of hexavalent chromium, molybdenum, tungsten and ferricyanide, a cation of the group consisting of zinc, cadmium, mercury, vanadium, chromium, manganese, iron, cobalt, nickel and copper forming a colored conversion coating on said article, and contacting said colored conversion coating with a color discharging agent which is an aqueous solution of a soluble agent of the group consisting of a soluble thiocyanate, a soluble cyanate, thiourea, urea, cyanuric acid, thiocyanuric acid, soluble sulfur-containing compounds, soluble phosphorus-containing compounds, soluble ferrocyan
  • the present invention provides a process for rinsing a phosphate conversion coating applied to a ferrous metal or galvanized steel prior to the application of a subsequently applied coating comprising applying to the phosphate conversion coating an aqueous chromic acid free composition having a pH of 3.4 to 6.0 at a temperature of 30°C to 80°C, said composition comprising at least 0.01 percent by weight based on the total weight of the composition of an S-triazine compound having at least one hydroxyl group on a carbon atom of the triazine ring.
  • the S-triazine compound or a modification thereof which is useful herein is one that enolizes in a manner that renders the aqueous composition containing the same acidic. While not desiring to be bound to any particular theory, it is believed that the enolized form of the S-triazine compound is reactable with the metal surface.
  • the enol form of the preferred S-triazine compound is commonly referred to as cyanuric acid.
  • the S-triazine compound or a modification thereof useful herein is characterized as having at least one hydroxyl group on a carbon atom of the trizine ring.
  • the useful S-triazine compound must be compatible with an aqueous medium, i.e., it is mixable to produce an aqueous composition that can be applied to a substrate to produce a corrosion resistant surface that can adhere to a subsequently applied coating. Typically, it may have a solubility of at least about 0.01 gram per 100 grams of water at 25°C.
  • the aqueous composition can be prepared by mixing the S-triazine compound with an aqueous medium, preferably at a temperature of about 30°C to 80°C and more preferably about 40°C to 80°C.
  • an aqueous medium is meant water or water in combination with an adjuvant that can enhance the solubility of the S-triazine compound.
  • the aqueous composition may also contain an additive such as a pH buffer, phosphate, borate, potassium salt or the like or a mixture thereof.
  • the aqueous pretreating composition has a pH of about 3.4 to 6 and preferably about 4.0 to 5.0.
  • the composition may contain 0.01 to 0.2 percent by weight and preferably 0.05 to 0.15 percent by weight of the S-triazine compound based on the total weight of the composition. While higher amounts of the S-triazine compound can be employed in the aqueous composition, it does not appear that there is an improvement in performance with such a composition. However, under certain circumstances, the higher concentration in the form of a concentrate may be desirable, for reasons such as ease of handling.
  • the aqueous composition of the S-triazine compound is applied under conditions that produce a corrosion-resistant barrier which is receptive to a subsequent coating process such as a conventional coating or electrocoating.
  • the temperature of the aqueous composition at which a substrate is treated therewith is from 30°C to 80°C and preferably 40°C to 60°C.
  • the pH of the treating composition during application is 3.4 to 6 and preferably 4 to 5.0.
  • the aqueous composition of the S-triazine compound is employed in treating a ferrous metal, such as cold rolled steel, or galvanized steel, comprising a phosphate conversion coating: a zinc phosphate conversion coating is preferred herein.
  • a ferrous metal such as cold rolled steel, or galvanized steel
  • the aqueous composition containing the S-triazine compound is applied to the phosphate conversion coating by spraying, immersion or any other convenient means.
  • the metal is usually rinsed with deionized water and then coated with a surface coating, usually after it has been dried.
  • the metal to be treated is cleaned by a physical or chemical means and water rinsed in order to remove surface contamination such as grease or dirt.
  • the metal surface is then brought into contact with a phosphate conversion coating composition, rinsed with water and then rinsed with the composition of this invention.
  • the ferrous metal or galvanized steel surface can be coated by any convenient means. It has been found that the pretreatment process of the metal with the aqueous composition of the S-triazine compound imparts to the coated substrate improved adhesion and corrosion resistance properties.
  • Hot dipped galvanized steel panels were phosphated with CHEMFOS 710 zinc nickel manganese phosphating solution (from Chemfil Corporation) at an average coating weight of 2.91g/m2 (270 mg/ft2). The panels were then rinsed with water to remove residual phosphating chemicals and then immersed for 30 seconds in an aqueous solution of cyanuric acid at 48.9°C (120°F). Two concentrations of the cyanuric acid solutions were employed: 0.1 and 0.2 percent cyanuric acid in city water. The measured pH's were 4.0 and 3.4, respectively.
  • the panels were dried with a compressed air jet and primed the same day with ED315OW electrodeposition primer (from PPG Industries, Inc., herein "PPG") at about 240 volts giving about 30 to 40 ⁇ m (1.2 to 1.6 mils) dry film thickness.
  • PPG ED315OW electrodeposition primer
  • the panels were subsequently top coated with HUBC 90270 white basecoat (from PPG) at about 22.5 ⁇ m (.9 mils) and then with URC 1000 clearcoat (from PPG) at about 47.5 ⁇ m (1.9 mils).
  • the panels were then prepared for testing by scribing and abrading with steel shot according to the "CHRYSLER" chipping scab test procedure, as follows.
  • Control panels were also prepared with CHEMSEAL 20 chrome rinse (from Chemfil Corporation) and with a deionized water rinse for comparison purposes. Triplicate panels were prepared for each system and subjected to the same CHRYSLER chipping scale test as described above. The total test period was 10 weeks. The panels were evaluated according to the amount of paint removed by taping with #898 3M SCOTCH tape after the test period. The results of the tests are reported in Table I hereinbelow. TABLE I RESULTS PAINT ADHESION LOSS .1% aqueous composition of cyanuric acid rinse 4% .2% aqueous composition cyanuric acid rinse 4% CHEMSEAL 20 chrome rinse 10% Deionized water rinse 24%
  • Controls for comparison were made with CHEMSEAL 20 chrome rinse and with deionized water.
  • the series were rinsed with deionized water, dried with a compressed air jet, and primed with UNI-PRIME electrocoat (from PPG) at 240 volts for 30 ⁇ m (1.2 mils) thickness on cold rolled steel.
  • the panels were top coated with HUBC 90270 white basecoat at 25.4 ⁇ m (1.0 mils) and URC 1000 clearcoat at 40 ⁇ m (1.6 miles).
  • Triplicate panels were prepared and tested according to the CHRYSLER chipping scab test described in Example 1. The results of the test are reported in Table II hereinbelow.
  • Heavy gauge hot rolled steel panels were pretreated with CHEMFOS 86 zinc nickel phosphate coating at about 2.58 g/m2 (240 mg/ft2), rinsed with water, and immersed for 30 seconds in .1 percent aqueous composition of cyanuric acid at 48.9°C (120°F). The panels were then rinsed again with water, dried with compressed air, and then painted with a single coat of ED 4201 black electrocoat primer (from PPG) at about 20 ⁇ m (.8 mils) dry thickness.
  • Control panels were prepared with CHEMSEAL 20 chrome and with deionized water rinses. Triplicate panels were prepared for each system and tested in essentially the same manner as described in the CHRYSLER scab test cabinet for eight weeks. The results of the test are reported in Table III hereinbelow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (7)

  1. Verfahren zum Waschen von mit einer umgewandelten Posphatierungsbeschichtung versehenen Eisenmetalles oder galvanisiertem Stahl vor dem Aufbringen einer anschließend aufgebrachten Beschichtung durch Aufbringen einer wäßrigen chromsäurefreien Zusammensetzung mit einem pH von 3,4 bis 6,0 bei einer Temperatur von 30° C bis 80° C auf die umgewandelte Phosphatierungsbeschichtung, wobei die Zusammensetzung mindestens 0,01 Gew.-%, bezogen auf Gesamtgewicht der Zusammensetzung, einer S-Triazinverbindung mit mindestens einer Hydroxylgruppe an einem Kohlenstoffatomen des Triazinringes enthält.
  2. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet,
    daß die S-Triazinverbindung Cyanursäure ist.
  3. Verfahren nach Anspruch 1 oder 2,
    dadurch gekennzeichnet,
    daß der pH Wert 4 bis 5,0 ist.
  4. Verfahren nach einem der vorstehenden Ansprüche 1-3,
    dadurch gekennzeichnet,
    daß die S-Triazinverbindung in einer Menge von 0,05 bis 0,15 %, bezogen auf Gesamtgewicht der wäßrigen Zusammensetzung, vorhanden ist.
  5. Verfahren nach einem der vorstehenden Ansprüche 1-4,
    dadurch gekennzeichnet,
    daß die umgewandelte Phosphatierungsbeschichtung eine umgewandelte Zinkphosphatbeschichtung ist.
  6. Verfahren nach einem der vorstehenden Ansprüche 1-5,
    gekennzeichnet durch
    den zusätzlichen Schritt des Aufbringens einer Oberflächenbeschichtung auf den Metallträger, der zuvor mit der wäßrigen Zusammensetzung der S-Triazinverbindung in Berührung gebracht wurde.
  7. Verfahren nach Anspruch 6,
    dadurch gekennzeichnet,
    daß die Oberflächenbeschichtung durch Elektrotauchlackierung aufgebracht wird.
EP90311659A 1989-10-25 1990-10-24 Verfahren zur Nachspülung von Phosphatumwandlungsüberzügen mit S-Triazin enthaltenden Zusammensetzungen Expired - Lifetime EP0425271B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42635589A 1989-10-25 1989-10-25
US426355 1989-10-25

Publications (3)

Publication Number Publication Date
EP0425271A2 EP0425271A2 (de) 1991-05-02
EP0425271A3 EP0425271A3 (en) 1993-03-03
EP0425271B1 true EP0425271B1 (de) 1994-12-28

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EP90311659A Expired - Lifetime EP0425271B1 (de) 1989-10-25 1990-10-24 Verfahren zur Nachspülung von Phosphatumwandlungsüberzügen mit S-Triazin enthaltenden Zusammensetzungen

Country Status (9)

Country Link
EP (1) EP0425271B1 (de)
JP (1) JPH06915B2 (de)
KR (1) KR930001783B1 (de)
AT (1) ATE116382T1 (de)
CA (1) CA2027402C (de)
DE (1) DE69015570T2 (de)
DK (1) DK0425271T3 (de)
ES (1) ES2069024T3 (de)
MX (1) MX172411B (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102210349B1 (ko) * 2020-07-16 2021-01-29 한전케이피에스 주식회사 펌프/수차 너트-잭의 리프팅 에어 실린더가 구비된 에어 유닛 장치

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2898250A (en) * 1957-03-25 1959-08-04 Turco Products Inc Process for producing aluminum surface coatings
US2976193A (en) * 1959-08-03 1961-03-21 Purex Corp Ltd Process and compositions for producing aluminum surface conversion coatings
US3706604A (en) * 1971-01-20 1972-12-19 Oxy Metal Finishing Corp Process for the coating of metal
US3756864A (en) * 1971-09-07 1973-09-04 Oxy Metal Finishing Corp Cyanuric acid as a scale reducing agent in coating of zinc surfaces
SU1467058A1 (ru) * 1987-04-30 1989-03-23 Азербайджанский политехнический институт им.Ч.Ильдрыма Симметричные непредельные трис ( @ -оксиэтиловые) эфиры циануровой кислоты в качестве ингибиторов сероводородной коррозии стали

Also Published As

Publication number Publication date
CA2027402C (en) 1999-03-16
ATE116382T1 (de) 1995-01-15
DE69015570T2 (de) 1995-07-27
EP0425271A2 (de) 1991-05-02
EP0425271A3 (en) 1993-03-03
KR910008170A (ko) 1991-05-30
CA2027402A1 (en) 1991-04-26
DE69015570D1 (de) 1995-02-09
JPH03170595A (ja) 1991-07-24
MX172411B (es) 1993-12-15
ES2069024T3 (es) 1995-05-01
KR930001783B1 (ko) 1993-03-13
JPH06915B2 (ja) 1994-01-05
DK0425271T3 (da) 1995-02-20

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