CA2027402C - Pretreating composition containing s-triazine compound - Google Patents

Pretreating composition containing s-triazine compound

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Publication number
CA2027402C
CA2027402C CA002027402A CA2027402A CA2027402C CA 2027402 C CA2027402 C CA 2027402C CA 002027402 A CA002027402 A CA 002027402A CA 2027402 A CA2027402 A CA 2027402A CA 2027402 C CA2027402 C CA 2027402C
Authority
CA
Canada
Prior art keywords
composition
triazine compound
coating
panels
aqueous composition
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 - Fee Related
Application number
CA002027402A
Other languages
French (fr)
Other versions
CA2027402A1 (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 Ohio Inc
Original Assignee
PPG Industries Inc
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 PPG Industries Inc filed Critical PPG Industries Inc
Publication of CA2027402A1 publication Critical patent/CA2027402A1/en
Application granted granted Critical
Publication of CA2027402C publication Critical patent/CA2027402C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting 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
    • C23F11/14Nitrogen-containing compounds
    • C23F11/149Heterocyclic compounds containing nitrogen as hetero atom

Abstract

Disclosed herein is an aqueous composition containing an S-triazine compound having at least one hydroxyl group composition adapted for use in pretreating a ferrous or non-ferrous metal surface.

Description

'~ -1- 20 27402 PRETREATING COMPOSITION CONTAINING S-TRIAZINE COMPOUND

Background of the Inv~ntion 4 Field of the Invention: The present invention relates to a pretreatment composition whlch i5 free of chromic acid; said compositlon 6 is particularly useful as a final rinse in a metal pretreatment process.

8 Brief DescriRtion of the Prior Art In the metal pretreatment process, it is known to employ a 10 phosphating conversion coating which is usually followed by a final rinsing or sealing step. The rinsing composition usually comprises 12 chromic acld. While effective in the rinsing step, chrom~c acid is, nonetheles6, undesirable because of its toxicity and the attendant 14 problems of disposal.
Hence, considerable work has been done in finding a 16 replacement for chromic acid in the final rinsing step. The present invention pro~ides a pretreatment compo6ition which is essentially free 18 of chromic acid.

Summary of the Invention In accordance with the foregoing, the present invention 22 encompasses an aqueous composition comprising an S-triazine having at least one hydroxyl group on a carbon atom of the triazine ring 24 (hereinafter "S-triazine compound") adapted for use for pretreating a ferrous or non-ferrous metal surface. The aqueous composltion of the 26 S-triazine compound contains at least about O.Ol percent by weight or higher of the S-triazine compound based on the total weight of the 28 composition, and can have a pH of about 3.4 to 6 and a temperature typically from about 30~C to 80~C. The S-triazine compound is preferably cyanuric acid.
The in~ention further encompa6ses a process of pretreat~ng a metal 6urface comprlsing applying an effective aqueous composition of 32 the S-triazlne compound to the metal surface to produce a corrosion re6istant surface that can adhere to a subsequently applied coating.
34 Preferably, the aqueous composition of the S-triazine compound is employed as a final rinse o~er a metal surface comprising a conversion 36 coating such as a phosphate conversion coating.

20~7~02 ._ Detailed Description of the Invention 2 The S-triazine compound or a modification thereof which, useful herein, is one that enolizes in a manner that renders the aqueous 4 composition containing the same acidic. While not desiring to be bound to any particular theory, it is believed that the enolized form of the 6 S-triazine compound is reactable with the metal surface. The enol form of the preferred S-triazine compound is commonly referred to as cyanuric 8 acid. In accordance with this invention, the S-triazine compound or a modification thereof useful herein is characterized as having at least 10 one hydroxyl group on a carbon atom of the triazine ring.
The useful S-triazine compound must be compatible with an 12 aqueous medium, i.e., it is mixable to produce an effective aqueous composition that can be applied to a substrate to produce a corrosion 14 resistant surface that can adhere to a subsequently applied coating.
Typically, it must have solubility of at least about 0.01 gram per 100 16 grams of water at 25~C. The aqueous composition of this invention can be prepared by mixing the S-triazine compound with an aqueous medium, 18 preferably at a temperature of about 30~C to 80~C and more preferably about 40~C to 80~C. By an aqueous medium is meant water or water in 20 combination with an adjuvant that can enhance the solubility of the S-triazine compound. The aqueous composition may also contain an 22 additive such as a pH buffer, phosphate, borate, potassium salt or the like or a mixture thereof.
24 Accordingly, the aqueous pretreating composition of this invention can have a pH of about 3.4 to 6 and preferably about 4.0 to 26 5Ø The composition can contain about 0.01 to 0.2 percent by weight and preferably about 0.05 to 0.15 percent by weight of the S-triazine 28 compound based on the total weight of the composition. While higher amounts of the S-triazine compound can be employed in the aqueous 30 composition, it does not appear that there is an improvement in performance of such a composition. However, under certain 32 circumstances, the higher concentration in the form of a concentrate may be desirable, for reasons such as ease of handling.

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The aqueous composition of the S-triazine compound i8 applied 2 under conditions that produce a corrosion-resistant barrier which is receptive to a subsequent coating process such as a conventional coating 4 or electrocoating. The temperature of the aqueous compo6ition at ~hich a substrate i8 treated therewith is typically from about 30~C to 80~C
6 and preferably about 40~C to 60~C. The pH of the-treating composition during application i8 typically about 3.4 to 6 and preferably about 4 8 to 5Ø
In the process of this invention, the aqueous composition of 10 the S-triazine compound iB employed in treating a ferrous or non-ferrous metal such a8 cold rolled steel, galvanized steel or the like.
12 Preferably, the aqueous composition is applied to a metal surface comprising a conversion coating such as a phosphated conversion 14 coating; a zinc phosphate conver~ion coating is preferret herein. The aqueous composition contn~n~ng the S-triazine compound i8 applied to 16 the metal surface by spraying, immersion or any other convenient means. After the aqueous composition has been applied, the metal is 18 usually rinsed with deionized water and then coated with a surface coating, usually after it has been dried.
In a typical pretreatment process, the metal to be treated i8 cleaned by a physical or chemical means and water rinsed in order to 22 remove surface contamination such as grease or dirt. The metal surface iB then brought into contact with a conversion coating composition, 24 rinsed with water and then rinsed with the composition of this invention. After the application of the aqueous solution of the 26 S-triazine compound with rinsing and drying, the ferrous or non-ferrous metal can be coated by any convenient means. It has been found that 28 the pretreatment process of the metal with the aqueous composition of the S-triazine compound imparts to the coated substrate improved 30 adhesion and corrosion resistance properties.
The invention iB further illustrated by the following 32 non-limiting examples.

~ ' _ 2 ~ ~ 7 4 ~

2 Hot dipped galvanized steel panels were phosphated with CHEMFOS 710 zinc nickel manganese phosphating solution (from Chemfil 4 Corporation) at an average coating weight of 270 mg/ft2. The panels were then rinsed with water to remove residual phosphating chemicals 6 and then immersed for 30 seconds in an aqueous solution of cyanuric acid at 120~F. Two concentrations of the cyanuric acid solutions were 8 employed: 0.1 and 0.2 percent by weight cyanuric acid in city water. The measured pH's were 4.0 and 3.4, respectively. The panels were dried 10 with a compres6ed air jet and primed the same day with ED3150W
electrodeposition primer (from PPG Industries, Inc., herein "PPG") at 12 about 240 volts giving about 1.2 to 1.6 mils dry film thickness. The panels were 6ubsequently top coated with HUBC 90270 white basecoat 14 (from PPG) at about .9 mils and then with URC 1000 clearcoat (from PPG) at about 1.9 mils. The panels were then prepared for testing by 16 scribing and abrading with steel shot according to the "CHRYSLER"
chipping scab test procedure, as follows.
18 1) 4" x 12" test panels were coated as described above.
2) The top half of the panel was scribed with a 12 cm (4.7") '~" scribe. A strip of pull tape was firmly applied to one side of the "X" and removed in a rapid vertical motion.
22 Repeat of this procedure was conducted with the other side of the '~-"
24 3) The air pressure of the gravelometer (from the Q-Panel Compan~) was adjusted to 205 kPa (30 psi).
26 4) The air valve of the gravelometer was shut off and 200 ml (32 oz.) of steel shot was collected.
28 5) A test panel was placed in the panel holder with the coated side facing the gravel projecting mechanism of the gravelometer. The lid of the test chamber was then closed.
6) The air valve was opened to let the pressure stabilize.
32 Two h~ndred milliliters (200 ml) (32 oz.) of shot was poured into the hopper. The air was turned off when all of the shot 34 had been spent.

*Trade mark ~B''i - s ~ 7 ~ ~ ~
7) The panel was placed in S percent by weight salt solution (pH of 2 about 6.6 to 7.1) for a ;n~-, of lS minutes.
8) The panel was removed and allowed to recover at lab 4 conditions for 1 hour and lS minutes and then placed in humidity cablnet for 22.5 hours.
6 An "accelerated" test was conducted as follows:
a) The humidity cabinet was set at 85 percent relative 8 humidity and 60~C (140~F).
b) A cycle program as outlined in steps 7 to 8 was run over a period of four days.
c) Thereafter (on the fifth day), the panel was removed 12 from the humidity cabinet and within 30 minutes, steps 3 to 8, as set forth above, were followed.
14 d) At the conclusion of a five-week cycle of steps a - c (after step 6), the panels were washed with sponge and 16 water (a mild detergent could be used). Excess water was removed and the panel(s) were allowed to recover for 18 30 minutes.
e) The target areas was covered with pull tape and removed as outlined in step 2.
f) The percent paint loss in the target area was 22 estimated.
CONTROL: Control panels were also prepared wlth CHEMSEAL 20 24 chrome rinse (from Chemfil Corporation) and with a deionized water rinse for comparison purposes. Triplicate panels were prepared for 26 each system and subjected to the same CHRYSLER chipping scale test as described above. The total test period was 10 weeks. The panels were 28 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 30 reported in Table I hereinbelow.

*Trade mark B~

_ - 6 -7 4 ~ ~
TABLE I

~F~uLTsPAINT ADHESION LOSS
4 .1% aqueous composition of cyanuric acid rinse 4%
.2% aqueous composition 8 cy~n~ric acid rinse 4%
C~M.~AT. 20 chrome rinse 10%
12 Deionized water rinse 2470 16 Cold rolled steel (CRS) and hot dipped galvanized (HDG) panels were phosphated with CHEMFOS 86 zinc nickel phosphate (from 18 Chemfil Corporation) at about 230 mg/ft2. After rinsing with water, the panels were immersed for 30 seconds in a .1 percent by weight solution of 20 cyanuric acid in water at 120~F, pH at 4.1.
Control6 for comparison were made with CHEMSEAL 20 chrome 22 rinse and with deionized water. The series were rinsed with deionized water, dried with a compressed air jet, and primed with UNI-PRIME
24 electrocoat (from PPG) at 240 volts for 1.2 mils thicknes6 on cold rolled steel. The panels were top coated with HUBC 90270 white 26 ba6ecoat at 1.0 mils and URC 100~ clearcoat at 1.6 mils. Triplicate panels were prepared and tested according to the CHRYSLER chipping scab 28 test described in Example 1. The results of the test are reported in Table II hereinbelow.

TABLE II

RESULTS PAINT ADHESION LOSS ON:

34 HDGl cRs2 .1% aqueous composition of 36 cyanuric acid rinse 6% 1770 38 CHEMSEAL 20 Rinse .5% 24%
Deionized Water Rinse 12% 24%
42 (1) Hot dipped galvanized steel.
(2) Cold rolled steel.

*Tràde mark B~

7 ~ 4 ~ ~

2 Heavy gauge hot rolled steel panel6 were pretreated with CHEMFOS 86 zinc nickel pho6phate coating at about 240 mg/ft2, rinsed 4 with water, and immersed for 30 seconds in .1 percent by weight aqueous composition of cyanuric acid at 120~F. The panels were then rinsed 6 again with water, dried with compressed air, and then painted with a single coat of ED 4201 black electrocoat primer (from PPG) at about .8 8 mil6 dry thickness.
Control panels were prepared with CHEMSEAL 20 chrome and with 10 deionlzed water rin6es. Triplicate panels were prepared for each system and tested in essentially the same manner a6 described in the 12 CHRYSLER scab test cabinet for eight weeks. The results of the test are reported in Table III hereinbelow.

TABLE III

SCRIBE CREEPAGE FACE CORROSION
18 RESULTS (ASTM D610-85~*
.1% by weight Cyanuric Acid Rinse 1/4 inch 7 22 CHEMSEAL 20 Rinse 5/16 " 6 24 Deionized Water Rinse 1/2 + " 7 *The numerical rating for this aspect of the te6t is ba6ed on a scale 28 of 0 to 10, with 10 indicating no failure and 0 indicating the total failure from rusting accompaning blistering which is not initially 30 evidenced by vi6ible rust.
32 While the illustrative embodiments of the invention have been described hereinabove, it will be understood that various modifications 34 will be apparent to and can be made by those skilled in the art without departing from the scope or spirit of the invention. Accordingly, it 36 is intended that the claims directed to the invention be construed as encompassing all aspects of the invention which would be treated as 38 equivalents by those skilled in the art to which the invention pertains.

*Trade mark . ~ ' . ~

Claims (7)

1. A process of pretreating a metal surface which comprises applying to said surface an aqueous composition having a pH of about 3.4 to 6.0 at a temperature of about 30°C.
to 80°C., said composition comprising at least 0.01 percent by weight based on the total weight of the composition of a cyanuric acid.
2. The process of claim 1 wherein the pH is about 4 to 5Ø
3. The process of claim 1 wherein the cyanuric acid is present in an amount of about 0.05 to 0.15 percent by weight based on the total weight of the composition.
4. The process of claim 1 wherein the metal surface comprises a phosphate conversion coating.
5. The process of claim 4 wherein the conversion coated metal surface comprises a zinc phosphate coating.
6. The process of any one of claims 1, 2, 3, 4 or 5 characterized in an additional step of applying a surface coating to the metal substrate which has been previously contacted with the aqueous composition of a cyanuric acid.
7. The process of claim 6 in which the surface coating is applied by electrodeposition.
CA002027402A 1989-10-25 1990-10-11 Pretreating composition containing s-triazine compound Expired - Fee Related CA2027402C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42635589A 1989-10-25 1989-10-25
US426,355 1989-10-25

Publications (2)

Publication Number Publication Date
CA2027402A1 CA2027402A1 (en) 1991-04-26
CA2027402C true CA2027402C (en) 1999-03-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (9)

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102210349B1 (en) * 2020-07-16 2021-01-29 한전케이피에스 주식회사 Pump/Turbine Nut-Jack Lifting Air Cylinder Air Unit Device

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 (en) * 1987-04-30 1989-03-23 Азербайджанский политехнический институт им.Ч.Ильдрыма Symmetrical nonsaturated tris-(beta-oxyethyl) esters of cyanuric acid as inhibitors of hydrigene sulfide-induced corrosion of steel

Also Published As

Publication number Publication date
KR910008170A (en) 1991-05-30
DE69015570T2 (en) 1995-07-27
DK0425271T3 (en) 1995-02-20
EP0425271A2 (en) 1991-05-02
MX172411B (en) 1993-12-15
JPH06915B2 (en) 1994-01-05
ES2069024T3 (en) 1995-05-01
JPH03170595A (en) 1991-07-24
CA2027402A1 (en) 1991-04-26
EP0425271B1 (en) 1994-12-28
KR930001783B1 (en) 1993-03-13
ATE116382T1 (en) 1995-01-15
DE69015570D1 (en) 1995-02-09
EP0425271A3 (en) 1993-03-03

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