EP0425271B1 - Procédé de rinçage de couches de conversion au phosphate avec des compositions contenant un composé S-triazine - Google Patents
Procédé de rinçage de couches de conversion au phosphate avec des compositions contenant un composé S-triazine Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- triazine compound
- coating
- phosphate conversion
- conversion coating
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Plural Heterocyclic Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Detergent Compositions (AREA)
Claims (7)
- Procédé de rinçage d'un revêtement de conversion au phosphate appliqué à un métal ferreux ou à un acier galvanisé avant l'application d'un revêtement appliqué ultérieurement, comprenant l'application au revêtement de conversion au phosphate d'une composition aqueuse exempte d'acide chromique ayant un pH de 3,4 à 6,0, à une température de 30°C à 80°C; ladite composition comprenant au moins 0,01 pourcent en poids par rapport au poids total de la composition d'un composé de S-triazine ayant au moins un groupe hydroxyle sur un atome de carbone du cycle triazine.
- Procédé selon la revendication 1, dans lequel le composé S-triazine est l'acide cyanurique.
- Procédé selon la revendication 1 ou 2 caractérisé en ce que le pH est de 4 à 5,0.
- Procédé selon l'une quelconque des revendications 1 à 3 caractérisé en ce que le composé S-triazine est présent en une quantité de 0,05 à 0,15 pourcent par rapport au poids total de la composition aqueuse.
- Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le revêtement de conversion au phosphate est un revêtement de conversion au phosphate de zinc.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en une étape supplémentaire d'application d'un revêtement superficiel au substrat de métal que l'on a au préalable mis en contact avec la composition aqueuse du composé S-triazine.
- Procédé selon la revendication 6, dans lequel on applique le revêtement superficiel par électrodéposition.
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 (fr) | 1991-05-02 |
EP0425271A3 EP0425271A3 (en) | 1993-03-03 |
EP0425271B1 true EP0425271B1 (fr) | 1994-12-28 |
Family
ID=23690462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90311659A Expired - Lifetime EP0425271B1 (fr) | 1989-10-25 | 1990-10-24 | Procédé de rinçage de couches de conversion au phosphate avec des compositions contenant un composé S-triazine |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0425271B1 (fr) |
JP (1) | JPH06915B2 (fr) |
KR (1) | KR930001783B1 (fr) |
AT (1) | ATE116382T1 (fr) |
CA (1) | CA2027402C (fr) |
DE (1) | DE69015570T2 (fr) |
DK (1) | DK0425271T3 (fr) |
ES (1) | ES2069024T3 (fr) |
MX (1) | MX172411B (fr) |
Families Citing this family (1)
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)
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 |
-
1990
- 1990-10-11 CA CA002027402A patent/CA2027402C/fr not_active Expired - Fee Related
- 1990-10-15 MX MX022837A patent/MX172411B/es unknown
- 1990-10-24 ES ES90311659T patent/ES2069024T3/es not_active Expired - Lifetime
- 1990-10-24 AT AT90311659T patent/ATE116382T1/de active
- 1990-10-24 DK DK90311659.8T patent/DK0425271T3/da active
- 1990-10-24 DE DE69015570T patent/DE69015570T2/de not_active Expired - Fee Related
- 1990-10-24 KR KR1019900017044A patent/KR930001783B1/ko not_active IP Right Cessation
- 1990-10-24 EP EP90311659A patent/EP0425271B1/fr not_active Expired - Lifetime
- 1990-10-25 JP JP2290569A patent/JPH06915B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2027402A1 (fr) | 1991-04-26 |
DK0425271T3 (da) | 1995-02-20 |
MX172411B (es) | 1993-12-15 |
KR930001783B1 (ko) | 1993-03-13 |
DE69015570T2 (de) | 1995-07-27 |
DE69015570D1 (de) | 1995-02-09 |
KR910008170A (ko) | 1991-05-30 |
ES2069024T3 (es) | 1995-05-01 |
JPH03170595A (ja) | 1991-07-24 |
EP0425271A3 (en) | 1993-03-03 |
ATE116382T1 (de) | 1995-01-15 |
CA2027402C (fr) | 1999-03-16 |
EP0425271A2 (fr) | 1991-05-02 |
JPH06915B2 (ja) | 1994-01-05 |
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