AU670076B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU670076B2 – Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method
– Google Patents

AU670076B2 – Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method
– Google Patents
Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method

Download PDF
Info

Publication number
AU670076B2

AU670076B2
AU38080/93A
AU3808093A
AU670076B2
AU 670076 B2
AU670076 B2
AU 670076B2
AU 38080/93 A
AU38080/93 A
AU 38080/93A
AU 3808093 A
AU3808093 A
AU 3808093A
AU 670076 B2
AU670076 B2
AU 670076B2
Authority
AU
Australia
Prior art keywords
solution
metallic substrate
activating agent
acid
percent
Prior art date
1992-04-02
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.)

Ceased

Application number
AU38080/93A
Other versions

AU3808093A
(en

Inventor
Ralph C Gray
Charles F. Ii Kahle
Michael J Pawlik
Paul J Prugnal
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.)
1992-04-02
Filing date
1993-03-12
Publication date
1996-07-04

1993-03-12
Application filed by PPG Industries Inc
filed
Critical
PPG Industries Inc

1993-11-08
Publication of AU3808093A
publication
Critical
patent/AU3808093A/en

1996-07-04
Application granted
granted
Critical

1996-07-04
Publication of AU670076B2
publication
Critical
patent/AU670076B2/en

1999-07-08
Assigned to PPG INDUSTRIES OHIO, INC.
reassignment
PPG INDUSTRIES OHIO, INC.
Alteration of Name(s) in Register under S187
Assignors: PPG INDUSTRIES, INC.

2013-03-12
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

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

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

C23C22/05—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 using aqueous solutions

C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6

C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates

C—CHEMISTRY; METALLURGY

C23C22/82—After-treatment

C23C22/83—Chemical after-treatment

C—CHEMISTRY; METALLURGY

C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Abstract

A method of treating a nonferrous metal substrate such as aluminum with an acid activating agent such as HF followed by treating with an organophosphate or organophosphonate. The treatment provides for improved adhesion and flexibility as well as resistance to humidity, salt spray corrosion and detergents of subsequently applied coatings.

Description

-w I OPI DATE 08/11/93 APPLN. ID 38080/93 If»IIIIIll AOJP DATE 13/01/94 PCT NUMBER PCT/US93/02326 I AU9338080
(PCT)
(51) International Patent Classification 5 (11) International Publication Number: WO 93/20258 C23C 22/07, 22/34, 22/48 Al (43) International Publication Date: 14 October 1993 (14.10.93) (21) International Application Number: PCT/US93/02326 (74) Agents: UHL, William, J. et al.; PPG Industries, Inc., One PPG Place, Pittsburgh, PA 15272 (US).
(22) International Filing Date: 12 March 1993 (12.03.93) (81) Designated States: AU, BR, CA, Fl, JP, KR, NO, Euro- Priority data: pean patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, 07/862,143 2 April 1992 (02.04.92) US IE, IT, LU, MC, NL, PT, SE).
(71) Applicant: PPG INDUSTRIES, INC. [US/US]; One PPG Published Place, Pittsburgh, PA 15272 With international search report.
With amended claims, (72) Inventors: GRAY, Ralph, C. 137 West Cruikshank Road, Butler, PA 16001 PAWLIK, Michael, J. 2605 Mt.
Royal Boulevard, Glenshaw, PA 15116 KAHLE, Charles, II 8466 Coventry Drive, Allison Park, PA 15101 PRUGNAL, Paul, J. 538 Guylyn Drive, Pittsburgh, PA 15235 (US).
(54)Title: METHOD OF TREATING NONFERROUS METAL SURFACES BY MEANS OF AN ACID ACTIVATING AGENT AND AN ORGANOPHOSPHATE OR ORGANOPHOSPHONATE AND SUBSTRATES TREATED BY SUCH METHOD (57) Abstract A method of treating a nonferrous metal substrate such as aluminum with an .cid activating agent such as HF followed by treating with an organophosphate or organophosphonate. The treatment provides for improved adhesion and flexibility as well as resistance to humidity, salt spray corrosion and detergents of subsequently applied coatings.
.1 1 Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method Background of the Invention a I I t (I t C( Li Cii a 4 it ii I ta ti Ii I ciii Ce t C( Ir trir i C *3 t C aI I The present invention relates to metal pretreatment methods which do not involve the use of chromium compounds and, in particular, such methods which are useful in treating nonferrous metal surfaces and particularly aluminum, zinc and aluminumzinc alloy surfaces.
15 Brief Description of the Prior Art It is known to treat nonferrous metals and particularly aluminum, zinc and aluminum-zinc alloys with chromium compounds such as chromic acid to inhibit corrosion and promote adhesion with coatings. While effective, the chromium compounds, nonetheless, are undesirable because of their toxicity and the attendant problems of disposal.
Hence, considerable work has been done in finding a replacement for the chromium in metal pretreatment. The present invention provides a treatment method which does not involve the use of chromium compounds.
Summary of the Invention The invention encompasses a method of treating a nonferrous metallic substrate including the steps of: contacting the metallic substrate with a solution of an acid activating agent so as to dissolve metal oxide film which may form on the nonferrous metallic substrate; followed by FHPMELCD\96113019.9 2 contacting the metallic substrate with a solution of a compound selected from a group comprising phosphoric acid esters of epoxy compounds and phosphonic acid esters of epoxy compounds.
The invention also encompasses a nonferrous metallic substrate treated by such method.
The term «nonferrous» is meant to include metals other than iron, such as aluminum and zinc and alloys of aluminum and zinc, as well as alloys containing minor portions of up to percent by weight iron. Preferably, the nonferrous metallic substrate contains no iron.
Detailed Description of the Invention The acid activating agent is necessary to prepare the substrate for the subsequent treatment with the phosphoric or phosphonic esters of epoxy compounds. It is believed that the acid activating step dissolves metal oxide films which may form on the nonferrous metal surface making the surface more receptive to the subsequently applied phosphoric or phosphonic esters of epoxy compounds.
15 The acid activating agent is desirably applied by contacting the metallic substrate such as by immersion or spraying at a temperature of from 50°F. (10 0 to 180°F. (82 0 S. preferably 65’F. to 80 0 F. (27 0 Usually it will have a pH of from 2.4 to 4.0 and preferably from 3.0 to 3.7. The activating agent is preferably an aqueous solution of an acidic fluoride compound. Examples of acidic fluoride compounds are hydrofluoric acid, fluorosilicic acid, sodium hydrogen fluoride and potassium hydrogen fluoride. The acid activating agent can be a mixture of a fluorosilicate such as fluorosilicic acid and an alkali fluoride such as sodium fluoride. The pH can be adjusted by the addition of base such as sodium hydroxide. The acidic fluoride compound is preferably used in amounts to provide a concentration of from 100 to 5200 ppm fluoride and more preferably a concentration of from 600 to 2600 ppm fluoride.
,i After contacting the nonferrous metallic surface or substrate with the acid activating agent and before contacting with the phosphoric or phosphonic esters of epoxy coit iOnds, the substrate may optionally be contacted with an aqueous solution of complex I fluorotitanium or fluorozirconium compound. Examples of such complex compounds are 30 fluorotitanic acid, fluorozirconic acid, sodium hexafluorotitanate, potassium hexafluorotitanate and potassium hexafluorozirconate. Such complex compounds are preferably used in amounts to provide a concentration of from 100 to 800 ppm titanium and/or zirconium.
The useful phosphoric or phosphonic esters of epoxy compounds are compatible with an aqueous medium, soluble or dispersible to the extent of at least .05 gram per 100 grams of water 25°C. The aqueous solution can be prepared by mixing the phosphoric FHPMELCD\96113019.9 3 or phosphonic esters of epoxy compounds with an aqueous medium, preferably at a temperature of about 50°F. to 150°F. (66 0 and more preferably at about 60 0
F.
(16 0 to 80°F. By an aqueous medium is meant water or water in combination with cosolvent such as an alkyl ether of a glycol, such as 1-methoxy-2-propanol, dimethylformamide or a base such as an amine that can partially neutralize the phosphoric or phosphonic esters of epoxy compounds to enhance the solubility of these compounds.
Examples of suitable phosphonic acids are methylene phosphonic acids, particularly alpha-aminomethylene phosphonic acids containing at least one group of the structure: 0
I)
N CH2 P (OH) 2 and alpha-carboxymethylene phosphonic acids having a group of the structure: o•0 Examples of specific phosphonic acids include benzylaminobis(methylenephosphonic) acid, 4 4 4 II 4 4 4 becocoaminobis(methylenephosphonic) acid, triethylsilylpropylaminobis(methylenephosphonic) acid and carboxyethyl phosphonic acid.
Examples of epoxy compounds are 1,2-epoxy compounds and include polyglycidyl ethers of polyhydric phenols such as the polyglycidyl ether of 2,2-bis(4hydroxyphenyl)propane, bisphenol A, and l,l-bis(4-hydroxyphenyl)isobutane. Also, l. the epoxy compound may be a monoglycidyl ether of a monohydric phenol or alcohol such as phenyl glycidyl ether and butyl glycidyl ether. Also, mixtures of epoxy compounds may be used.
Examples of suitable phosphoric or phosphonic esters of epoxy compounds include phosphoric acid ester of bisphenol A diglycidyl ether; benzylaminobis- (methylenephosphonic) acid ester of bisphenol A diglycidyl ether; carboxyethyl phosphonic acid ester of bisphenol A diglycidyl ether and of phenylglycidyl ether and of R 4/ butyl glycidyl ether; carboxyethyl phosphonic acid mixed ester of bisphenol A diglycidyl t if FHPMELCD\96113019.9 7- i 4 ether and butylglycidyl ether; triethoxyl silyl propylaminobis-(methylenephosphonic) acid ester of bisphenol A diglycidyl ether and cocoaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether.
The phosphoric or phosphonic esters of epoxy compounds are applied to the metallic substrate under conditions that produce a corrosion-resistant barrier which is receptive to a subsequent coating process such as a spray, dip or roll coating. The phosphoric or phosphoric esters of epoxy compounds are applied to the metal surface by contacting the metal surface with the solution by spraying or immersion techniques. The temperature of the solution is typically from about 50 0 F. (10 0 to 150 0 F. (66 0 and preferably about 60°F. (16 0 to 80 0 F. The pH of the preferred treating composition during application is typically about 3.5 to 7.0 and preferably about 4.0 to The phosphoric or phosphonic esters of epoxy compounds are typically present in the solution in amounts of about 0.05 to 7.0 percent and preferatly about 0.65 to 0.80 percent; the percentage being by weight based on weight of solution. After the aqueous composition has been applied, the metal is usually rinsed with deionized water, dried with heat to preferably 40 0 C. to 130 0 C. and more preferably from 60 0 C. to 115 0 C. and then coated with a surface coating.
a In a typical treatment process, the nonferrous metal substrate is first cleaned by a physical or chemical means and rinsed with water followed by contacting the metallic 20 substrate with the acid activating agent and optionally the complex fluorotitanium or fluorozirconium compound as described above. The metallic substrate is then rinsed with water and then contacted with the phosphoric or phosphonic esters of epoxy compounds as described above. The metallic substrate can *oC 6 3 i.
.e C4 a *o FHPMELCD\963019.9 i F*MLD9131. II WO 93/20258 PCT/US93/02326 5 then be given a final deionized water rinse and the substrate dried by heating followed by the application of a coating composition by conventional means such as spraying or roll coating. The pretreatment process of the invention results in improved adhesion and flexibility and resistance to humidity, salt spray corrosion and detergents of subsequently applied coatings.
The invention is further illustrated by the following non-limiting examples. All parts are by weight unless otherwise indicated.
EXAMPLE A A solution of an acid activating agent was made by adding 1.06 grams of sodium fluoride in one liter of deionized water followed by the addition of 2.19 g of 40% by weight aqueous sodium hydroxide solution and 11.75 g of 23% by weight aqueous fluorosilicic acid solution. The solution had a pH of 3.0 and a fluoride concentration of 2600 ppm.
EXAMPLE B A complex fluorotitanium compound solution was made by adding 1.94 g of 53% by weight aqueous fluorotitanic acid to one liter of deionized water. The solution had a pH of 2.1 and a titanium concentration of 300 ppm.
EXAMPLE C The N,N-dimethylethanolamine salt of benzylaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether was made by first heating a solution containing 779.1 g of phosphorous acid (9.5 mole) and 592.2 g of 1-methoxy-2-propanol to 85*C. under a nitrogen atmosphere. Next, 567.1 g of benzylamine (5.3 mole) and 779.1 g of a 37 percent by weight solution of formaldehyde in water (9.6 mole formaldehyde) were added simultaneously as separate feeds over 3.3 hours to this solution. The resulting reaction mixture was held for 4 hours at i 35 95°C. A solution of 1345.6 g bisphenol A diglycidyl ether (3.6 mole)
«-A
WO 93/20258 PCT/US93/02326 6 (EPON 828 from Shell Chemical Company) and 343.5 g l-methoxy-2-oropanol was added over 1 hour and the resulting reaction mixture was heated to 90 0 C. for 1.5 hours. The reaction mixture was then allowed to cool to 50’C. and 437.2 g of N,N-dimethylethanolamine (4.9 mole) was added. The resulting product was a homogeneous liquid with a total solids content of 66.4 percent by weight, 3.405 milliequivalents of acid and 1.448 milliequivalents of base per gram of liquid.
EXAMPLE D Carboxyethyl phosphonic acid mixed ester of bisphenol A diglycidyl ether and phenylglycidyl ether was made by charging to a 1 liter, 4 neck, round bottom flask fitted with a Friedrich condenser, thermometer, nitrogen inlet and heating mantle, 180 g carboxyethyl phosphonic acid and 116 g dimethylformamide (DMF) solvent. When a clear solution was obtained by stirring at 50*C., 168 g of phenylglycidyl ether was added over 15 minutes while cooling with an ice bath to maintain a temperature of 50-57*C. After stirring for 2% hours at 500C., all the epoxy groups had reacted. A solution of 95 g of EPON 828 in 95 g DMF was added over 30 minutes and the solution heated to 100*C. After 8Y3 hours at 100*C., the mixture was cooled at which point a potentiometrically determined acid value of 227 at 58.5 percent solids was measured. The product had a solution viscosity of W-X (Gardner-Holdt) and a hydroxyl value of 147. No unreacted epoxy groups could be detected.
EXAMPLE E The diisopropylamine salt of the phosphoric acid ester of bisphenol A diglycidyl ether was made by first charging 67.6 g k 30 percent phosphoric acid into a 2-liter flask under a nitrogen blanket which was maintained throughout the reaction. l-Methoxy-2-propanol (67.6 g) was then added. The mixture was heated to 120’C. followed by the addition of 332.4 g EPON 828 premixed with the 1-methoxy-2-propanol (85 to 15 weight ratio) over 30 minutes. The temperature of the reaction mixture was maintained at 120*C. When WO 93/20258 PCT/US93/02326 7 the addition was complete, the temperature was held at 120*C. for another 30 minutes followed by the addition of 63.4 g deionized water over a 5-minute period. When the water addition was completed, the mixtu «l was held for 2 hours at reflux (1060C.) followed by cooling to 70′. Premelted diisopropanolamine (100.6 g) was then added to the reaction mixture at 700C. and the reaction mixture stirred for minutes. The pH of the reaction mixture was adjusted to 6.0 by adding the small amounts of additional diisopropanolamine. The reaction mixture was then further thinned with an additional 309.7 g of deionized water.
EXAMPLE F The diisopropanolamine salt of carboxyethyl phosphonic acid mixed ester of bisphenol A diglycidyl ether and butylglycidyl ether was made by first charging the following to a 3 liter, 4 neck, round bottom flask fitted with a thermometer, stainless steel stirrer, nitrogen inlet, heating mantle and reflux condenser: Carboxyethyl phosphonic acid 145 g Dimethylformamide 145 g When a clear solution was obtained at 50*C., a mixture of 190 g of the diglycidyl ether of bisphenol A and 130 g of butylglycidyl ether was added over Yi hours while controlling the reaction exotherm to 55-60’C. with an ice bath. The solution was heated to 100*C. and held at 100*C. for 5Y hours after which a measured epoxy equivalent weight of 2176 was obtained. After sitting overnight at ambient (t temperature, an additional 6 hours of heating at 1100C. gave an epoxy equivalent weight of 9680. The resin was thinned with a mixture of 47.6 g diisopropanolamine, 227 g deionized water and 320 g of the 1-methoxy-2-propanol. This procedure gave a final product with a non-volatile content of 38.6 percent and a final acid value of 67.4.
The pH was 4.0 (42 percent of total theoretical neutralization).
EXAMPLE G The N,N-dimethylethanolamine salt of cocoaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether was prepared as follows:
I
-L
WO 93/20258 PCT/US93/02326 -8 A solution containing 98.0 g of phosphorous acid (1.19 mole) and 75.0 g of l-methoxy-2-propanol was heated to 85°C. under a nitrogen atmosphere. Next, 130.0 g of cocoamine (ARMEEN CD from Armak Chemicals, a division of AKZO Chemie America) (0.66 mole, having an amine equivalent weight of 196) and 98.0 g of a 37 percent by weight solution of formaldehyde in water (1.20 mole formaldehyde) were added simultaneously as separate feeds over 1.5 hours to this solution. The resulting reaction mixture was held for 4 hours at reflux temperature (98-100*C.), whereupon a mixture containing 116.2 g of EPON 828 (0.30 mole) and 30.0 g of 1-methoxy-2-propanol was added over 1 hour, after which the reaction mixture was held at reflux for 1.5 hours. The resulting product was cooled to 60 0 C. and then neutralized by the addition of 55.0 g of N,N-dimethylethanolamine (0.62 mole) over 15 minutes after which the resulting product was allowed to cool to room temperature. The resulting reaction product had a Gardner-Holdt bubble tube viscosity of X, a total solids content of 67 percent by weight, and a pH of 5.35.
BAMPLE H An aqueous solution of the organophosphonate of Example C was prepared by adding with stirring 12.04 g of the reaction product of Example C to one liter of deionized water. The concentration of the solution was 0.8 percent by weight of organophosphonate based on weight of solution.
EXAMPLE I An aqueous solution of the organophosphonate of Example D was prepared by adding with stirring sufficient reaction product of a t 30 Example D to one liter of deionized water to form a solution containing 0.1 percent by weight of the organophosphonate based on weight of solution.
EXAMPLE J An aqueous solution of the organophosphate of Example E was prepared by adding with stirring sufficient reaction product of
I!
WO 93/20258 PCT/US93/02326 -9 Example E to one liter of deionized water to form a solution containing 5 percent by weight of the organophosphate based on weight of solution.
EXAMPLE
An aqueous solution of the organophosphonate of Example F was prepared by adding with stirring sufficient reaction product of Example F to one liter of deionized water to form a solution containing 0.1 percent by weight of the organophosphonate based on weight of solution.
EXAMPLE L An aqueous solution of the organophosphonate of Example G was prepared by adding with stirring sufficient reaction product of Example G to one liter of deionized water to form a solution containing 0.1 percent by weight of the organophosphonate based on weight of solution.
Aluminum panels were subjected to an alkaline cleaning procedure by immersion in a 1.5 percent by weight bath of CHEMKLEEN 49D which is available from Chemfil Corp. at a temperature of 140F.
(600C.) for 60 seconds. The panels were removed from the alkaline cleaning bath, rinsed with water, followed by immersion in a bath of 2 the acid activating agent of Example A for 60 seconds at 140 0
F.
The panels were then removed, rinsed with water and immersed in the fluorotitanium compound solution (140°F. of Example B for 60 seconds. The panels were removed from this solution, rinsed with water and then immersed in the aqueous solution of an organophosphonate of Example H for 60 seconds at The panels were removed from the aqueous solution, rinsed with water and dried with warm air at 104’F. for 3 minutes and then oven baked for 1 minute at 115’C. The panels were then topoated with the clear powder coating composition based on an epoxy resin and a polyanhydride curing agent available froJ PPG Industries,
J
WO 93/20258 PCT/US93/02326 10 Inc. as PCC 10103. The clear coated panels which had a coating thickness of 2 to 4 mils were subjected to General Motors Corp.
thermal shock test (GM9525P) for paint adhesion. The thermal shock test was conducted by immersing the coated panels in a 38°C. water bath for 3 hours followed immediately by placement into freezer at -29°C. for a minimum of 3 hours. Within 60 seconds of removal from freezer, the panels were scribed with an across the entire panel and blasted with high pressure (37.9 kPa) steam at a 450 angle and mm distance with respect to the scribe lines. Performance was measured with respect to paint loss from scribe line(s). Little or no paint loss (0 to 1 mm) was evidenced. Untreated control panels resulted in a 100 percent paint loss when tested in this manner.
EXAMPLE 2 Example 1 was repeated except that the fluorotitanium treatment was omicted and times and temperatures of the other treatments were modified as follows. The alkaline cleaning was conducted by immersion for 10 seconds at 140 0 F. (60C0.). The acid activation step was conducted on two different panels by immersion for 10 and 30 seconds, respectively, at 140’F. (60 The organophosphonate application was conducted by immersion for 10 and seconds, respectively, at 70*F. Also, the panels were topcoated with a coil primer and topcoat available from PEG Industries, Inc. as 4PLY41250 and 1LW4842, respectively. The primer was based on chromate containing acrylic latex and had a film thickness of 0.2 mils. The topcoat was based on an acrylic latex available from PPG Industries, Inc. under the trademark ENVIRON and had a thickness of 0.8 mils.
The coated panels were tested for flexibility via a T-bend’ S 30 test, for pencil hardness, for water soak recovery time and for percent water absorption.
The T-bend test was conducted by cutting a 2-inch strip from a coated panel and bending it back upon itself. A 3T bend means the diameter of the bend is three times the thickness of the panel. A 2T bend means the diameter of the bend is two times the A iJur ~L L ilL1 j~n WO 93/20258 PCT/US93/02326 11 thickness of the panel. A OT bend means that the panel is bent back over itself 180 degrees and compressed flat. The coating was observed visually for cracking and for removal of film after a piece of adhesive tape was pressed down onto the coating and then rapidly pulled off the panel at right angles to the plane of the surface being tested. Each bend is then examined and rated both for paint «pickoff» and paint cracking. Ratings were given at the bend at which no pickoff (NP) is seen and at the bend at which no cracking (NC) is seen. Lower values correspond to the most severe/stressful bends and are therefore indicative of the greater flexibility imparted by the coating pretreatment system. The pencil hardness test was conducted by abrading a pencil of a given hardness (2H>H>F>HB>B>2B) with emery cloth to form a sharp edge. Holding a pencil at a 450 angle to the coating surface, the pencil was pushed through the coating. This was repeated with progressively softer pencils until a given pencil does not cut through the coating.
Hardness was denoted by the hardest pencil that does not cut through the coating. The water soak test was conducted by immersing panels for 24 hours at 100 0 F. in a deionized water bath. Upon removal from the bath, panels were immediately tested for pencil hardness as described above and every two minutes thereafter until the film fully recovers (to initial hardness). The amount of water absorbed (percent water absorption) by the panels was determined gravimetrically. Fast recovery times and low percent absorption were indicative of strong adhesive interactions at the pretreatment-coating interface. The results of tests at 10 and second treatments are shown in Table I.
TABLE I Acid Activation Treatment Pretreatment T-Bend Pencil Water Soak Water (time) (time) NPN Initial Recovery Time Absorption 10 seconds 10 seconds 2T/3T B 0 minutes 2.3 seconds 30 seconds OT/2T B 0 minutes 2.8 r :-h I ‘1 WO 93/20258 12 12 PC;T/US93/02326 EXAMPLE 3 Example 1 was repeated except that the fluorotitanium treatment was omitted and the acid activation was conducted via immersion for 60 seconds at 120’F. Also, the panels were topcoated with an aminoplaat cured polyester topcoat available from PPG as POLYCRON III. The topcoat had a thickness of 1.0 mils. The panels were tested for film adhesion, impact resistance, detergent resistance and corrosion (salt spray and humidity) resistance as specified by the AAMA 603.8-85 publication. The results of the tests as well as those for an untreated control are shown in Table II below.
EXAMPLES 4-7 Example 3 was repeated except that the organophosphonate treatment was conducted with the organophosphonates and organophosphate solutions of Examples I, J, K and L. The results of the testing is shown in Table II below.
j; i! i j r p i -ti.-LL TABLE II Organophosphonate or Impact 2 Eample Organophosphate Solution Wet Adhesioni Resistance Control none 0 F 3 Example H 5 P 4 ExamplIel1 5 P Example J 5 6 Example K 5P 7 Example L 4 P Detergent 3 Salt Spray 4 Humidity Reii’ance Resisance 4 Resistance F 4/6 D# 6 P 9/10 clean P 9/9 F#8 P 10/10 clean P 7/8 D/16 P 8/9 clean
V
I i~ WO 93/20258 PCF/US93/02326 li– NOTE: The use of a ruled plastic grid is recommended as an aid in evaluating this type of failure. A b.4m- /4i) grid is suggested as most practical for the usual specimen. In using the grid the number of squares in which one or more points of failure are found is related to the total number of squares covering the significant area of the specimen to get a percentage figure as used in the tabulation. In some instances, the rating numbers may be used as factors with exposure time intervals related thereto to produce a performance index number which very accurately indicates relative quality.
Humidity resistance is determined by exposing the coated panel in a controlled heat and humidity cabinet for 1000 hours at 100*F. and 100″ relative humidity with the cabinet operated in accordance with ASTM D-2247. A rating of «clean» indicates no formation of blisters. In the above evaluations, indicates «few» and indicates «dense». In the size of the blisters, 6>8>10.

Claims (23)

1. A method of treating a nonferrous metallic substrate including the steps of: contacting the metallic substrate with a solution of an acid activating agent so as to dissolve metal oxide film which may form on the nonferrous metallic substrate; followed by contacting the metallic substrate with a solution of a compound selected from a group comprising phosphoric acid esters of epoxy compounds and phosphonic acid esters of epoxy compounds.

2. The method of claim 1 wherein in step the activating agent has a temperature of from about 50°F. to about 180°F.

3. The method of claim 1 or claim 2 wherein in step the activating agent 15 has a pH of from about 2.4 to about

4. The method of any one of claims 1 to 3 wherein in step the activating agent has a pH of from about 3.0 to about 3.7.

5. The m ethod of any one of claims 1 to 4 wherein in step the activating i, agent is an acid fluoride.

6. The method of any one of claims 1 to 5 wherein the activating agent is P present in the solution in a concentration of from about 100 to about 5200 ppm fluoride. i

7. The method of any one of claims 1 to 6 wherein the activating agent is present in a concentration of from about 600 to 2600 ppm fluoride. t t I

8. The method of any one of claims 1 to 7 wherein between step and step there is an additional step in which the metallic substrate is contacted with a solution of fluorotitanic or fluorozirconic compound. A LU FHPMELCD\96113019.9 29 April 1996 (17:17) 16 ti e r c

9. The method of any one of claims 1 to 8 wherein the nonferrous metallic substrate is selected from a group comprising aluminum, zinc and aluminum-zinc alloys. The method of any one of claims 1 to 9 wherein in step the solution is at a temperature of from about 50°F.

(10 0 to about 150°F. (66 0

11. The method of any one of claims 1 to 10 wherein in step the solution is at a temperature of from about 60’F. (16 0 to about 80°F.

12. The method of any one of claims 1 to 11 wherein in step the solution has a pH of from about 3.5 to about

13. The method of any one of claims 1 to 12 wherein in step the solution has a pH of from about 4.0 to about

14. The method of any one of claims 1 to 13 wherein in step the compound is present in a concentration of from about 0.05 percent to 7.0 percent by weight based on weight of solution.

15. The method of any one of claims 1 to 14 wherein in step the compound is present in a concentration of about 0.65 percent to about 0.8 percent by weight based on weight of solution.

16. The method of any one of claims 1 to 16 wherein the phosphonic acid ester 25 is an aminobis(methylenephosphonic) acid ester of an epoxy compound.

17. The method of any one of claims 1 to 16 wherein after step the substrate is rinsed with water. 6 tt C I t C I t I t t It*4 a IC CII (IC £1 IC It C *4

18. A nonferrous metallic substrate treated by the method of any one of claims 1 to 17. FHPMELCD\96113019.9 29 April 1996 (17:17) S j

19. The nonferrous metallic substrate of claim 18 which is selected from a group comprising aluminum, zinc and aluminum-zinc alloys.

The method of any one of claims 1 to 17 wherein the solution in step is an aqueous solution.

21. The method of any one of claims 1 to 17 wherein the solution in step is an aqueous solution. 0

22. A method of treating a nonferrous metallic substrate or a nonferrous metallic substrate treated by said method, substantially as hereinbefore described with reference to the Examples. 4*44 4 4 4444 4r 444! 4I 4t 4 44 44 4 41 4 4t 4.t 4 44 44 4 V St PPG Industries, Inc. By Their Registered Patent Attorneys FREEHILL PATENT TRADE MARK SERVICES April, 1996
113019.9 30 April 1996 (9:39) F i 1L K ‘p AT r 4~ INTERNATIONAL SEARCH REPORT lawruamesed Anlanase No PCT/US 93/02326 i. aLAsslFcAfloN OF SUDJEC MATIU of sww d-dftwm symbols qay, Iiawe awl) Midh* to latuuaonaj Powa Clside MP) or to bobh Nedm Clagifleiom ad tIC nt .Cl. 5 C23C22/07; C23C22/ 34; C23C22/4S B. FIELDS SLARaIED Mimimm Docessntson SearhoO’ Ciam ltiom system ascadesl symbols Int.Cl. 5 C23C DOmmmNN~fill Swsked othe 60a2 MibM= DOinmmAllmm to the Ealine that such Douamets ane laded in the Flods Smrehed UL DOCUMEMIT C01BWfh TO 3U aELVANT 9 c’ePA0’ya CliatlonsflDoomeinU wh limfiaim, weemdate, of herolmatplam,.U lilemat to Cli No.U V FR,A,2 443 514 (NIHON PARKERIZING CO) 1,2,5,6, 4 July 1980 9,10,12, 14,15, 18-22 A see claims 1,7; example 1 8 Y FR,A,2 340 380 (SOCICT9 CONTINENTALE 1,2,5,6, PARKER) 9,10,12, 2 September 1977 14,15, 18-22 A see claims 1-4,9,10; example 8 A FR,A,2 398 811 (CENTRE DE RECHERCHES METALLURGIQUES)

23 February 1979 see page 4, line 25 page 5, line 7; claims 1,2; table Speal of~im ml sk doomess :10 orW him gmnt powjhed after the isaed Auglm «a ml pillty daet daim cafut With the Aadet ba ,e dom ddhiat tha eom smlso the an vhis ix Ma tM~ prieciple or themuy diag the coodd to be it pual ewae uMaE deveses hal PmM~d or 3Mhw the tatern or dammint lpsmaalmo h Claimed isIadem ffllag ml mwi bemei mebe mme onaifee to f dmam whs my thaw disisn iek Clai(s) w iveo isvesve ap whikindt oO te Cliiifamdw t damminst of pattll Nlwe the Cldelamde dades er ath. speml mai (a am»ii be ,o bmimly ma ,as»v m u h ‘0 deamwo rofui tan ma l diodkm vs% 4hAdl=e w damal is mowad wit M .1 mm ether thdar other mm mo, sk iamaea hag e te a Pum skille Ir doomm palmed pete to tile beernmal M»la dat* ha bt the arL *d thea uis»lt date Claimed 4 domsm amber of the sme PaLM kfaml WV. X1CeiiATION Dale of the M Cemhla~n of Iaeamtlmml Soft Jns of Mafta of this Iomm aw* Rip»n 09 JUNE 1993 2 3. 93 EUROPEAN PATENT OFFCZ LAt4OAIS A.MN. W PCT/US 93/02326 Iinmmeta Anileadm No HL. DOCUMENilS CONSIDERE TO Ui EFIZANT (CONINUED FROM THE SECOND SO= I am. of Doa. Wit Wd~,4 Whwo @WGrPam, of theWA Puvma R dat to (im NIL GB,A,2 032 963 (DART INDUSTRIES) 14 May 1980 US,A,,4 339 310 (NOBUVUKI ODA) 13 July 1982 -IR iNG Mmdf 0ama1 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. us SA 9302326 71680 Thin mmmatbf te .Pon Iany M~w rwofta to ds pub dcssW ci U the abv~udwd lowmsaw Uith nat. MhUin~w we wo omaj in the Fiurspw Pam~ n M EDP Wie.» Thu Fw mv PsMumO~m aUmOway hUM. row hmpiadmimu ulin maw m iy pvm for B purpum hi fwdem 09/06/93 P~tm docuan pwwmwm Polaw fi=l ~MS ck»in sew~ «Wpin dam _Mh FR-A-2443514 04-07-80 None FR-A-2340380 02-09-77 US-A- 4111722 05-09-78 AU-B- 5 MZ,66 17-07-80 AU-A- 2205677 17-08-78 BE-A- 851186 08-08-77 CA-A- 1094430 27-01-81 OEm-A 2700642 11-08-77 GB-A- 1504502 22-03-78 JP-A- 52128848 28-10-77 NL-A- 7614586 11-08-77 SE-A- 7701464 10-08-77 FR-A-2398811 23-02-79 LU-A- 77873 26-03-79 BE-A- 869330 3.-11-78 DE-A- 2832994 08-02-79 GB-A,B 2004569 04-04-79 GB-A-2032963 14-05-80 US-A- 4222779 16-09-80 CA-Am 1134727 02-11-82 DE-Am 2943833 08-05-80 FR-A,B 2440412 30-05-80 NL-A- 7907961 02-05-80 CA-A- 1134725 02-11-82 CA-Am 1134726 02-11-82 DE-A- 2943834 08-05-80 DE-A- 2943835 08-05-80 FR-A,B 2440411 30-05-80 FR-A,B 2440413 30-05-80 GB-A,B 2032465 08-05-80 GB-A,B 2032466 08-05-80 JP-A- 55062176 10-05-80 JP-A- 55079875 16-06-80 JP-A- 55062177 10-05-80 NI-A- 7907960 02-05-80 NI-A- 7907964 02-05-80 US-A-4339310 13-07-82 Nonwa ?lFwwrvd»kdmMd6 :w0M Jowed slow Ewqpm room OMW% No. 13fia

AU38080/93A
1992-04-02
1993-03-12
Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method

Ceased

AU670076B2
(en)

Applications Claiming Priority (3)

Application Number
Priority Date
Filing Date
Title

US862143

1992-04-02

US07/862,143

US5306526A
(en)

1992-04-02
1992-04-02
Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method

PCT/US1993/002326

WO1993020258A1
(en)

1992-04-02
1993-03-12
Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method

Publications (2)

Publication Number
Publication Date

AU3808093A

AU3808093A
(en)

1993-11-08

AU670076B2
true

AU670076B2
(en)

1996-07-04

Family
ID=25337783
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU38080/93A
Ceased

AU670076B2
(en)

1992-04-02
1993-03-12
Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method

Country Status (13)

Country
Link

US
(1)

US5306526A
(en)

EP
(1)

EP0633949B1
(en)

JP
(1)

JP2843439B2
(en)

KR
(1)

KR0160819B1
(en)

AT
(1)

ATE143063T1
(en)

AU
(1)

AU670076B2
(en)

BR
(1)

BR9306246A
(en)

CA
(1)

CA2130114C
(en)

DE
(1)

DE69304902T2
(en)

DK
(1)

DK0633949T3
(en)

ES
(1)

ES2094533T3
(en)

MX
(1)

MX9301812A
(en)

WO
(1)

WO1993020258A1
(en)

Families Citing this family (48)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US5294265A
(en)

1992-04-02
1994-03-15
Ppg Industries, Inc.
Non-chrome passivation for metal substrates

DE19654642C2
(en)

1996-12-28
2003-01-16
Chemetall Gmbh

Process for treating metallic surfaces with an aqueous solution

US6096813A
(en)

1997-09-24
2000-08-01
Ppg Industries Ohio, Inc.
N-acyl amino acid compositions and their use as adhesion promoters

US5858282A
(en)

1997-11-21
1999-01-12
Ppg Industries, Inc.
Aqueous amine fluoride neutralizing composition for metal pretreatments containing organic resin and method

GB9821984D0
(en)

1998-10-08
1998-12-02
Thorstone Business Man Ltd
Adhesive promotion

US6312812B1
(en)

1998-12-01
2001-11-06
Ppg Industries Ohio, Inc.
Coated metal substrates and methods for preparing and inhibiting corrosion of the same

US6440580B1
(en)

1998-12-01
2002-08-27
Ppg Industries Ohio, Inc.
Weldable, coated metal substrates and methods for preparing and inhibiting corrosion of the same

US6410926B1
(en)

1999-10-01
2002-06-25
Ppg Industries Ohio, Inc.
Coating with optical taggent

US6488990B1
(en)

2000-10-06
2002-12-03
Chemetall Gmbh
Process for providing coatings on a metallic surface

US6689831B1
(en)

2000-11-01
2004-02-10
Mcmillen Mark
Chromium-free, curable coating compositions for metal substrates

US6863738B2
(en)

2001-01-29
2005-03-08
General Electric Company
Method for removing oxides and coatings from a substrate

US6750274B2
(en)

2001-02-08
2004-06-15
Ppg Industries Ohio. Inc.
Weldable coating of phosphated epoxy polymer, curing agent and electroconductive pigment

DE10114980A1
(en)

2001-03-27
2002-10-17
Henkel Kgaa

Adhesion promoter for paints and adhesives on metals

US6774168B2
(en)

2001-11-21
2004-08-10
Ppg Industries Ohio, Inc.
Adhesion promoting surface treatment or surface cleaner for metal substrates

US6749939B2
(en)

2002-02-19
2004-06-15
Ppg Industries, Ohio, Inc.
Composition having sealing and sound dampening properties and methods related thereto

US6841251B2
(en)

2002-02-19
2005-01-11
Ppg Industries Ohio, Inc.
Composition having sealing and sound dampening properties and methods related thereto

US7147897B2
(en)

2002-11-06
2006-12-12
Ppg Industries Ohio, Inc.
Weldable compositions comprising a conductive pigment and silicon and methods for using the same

US20040086718A1
(en)

2002-11-06
2004-05-06
Pawlik Michael J
Corrosion and alkali-resistant compositions and methods for using the same

US7345101B2
(en)

2002-11-06
2008-03-18
Ppg Industries Ohio, Inc.
Aqueous composition of reaction product of epoxy and phosphorus materials with curing agent

US20050043207A1
(en)

2003-06-30
2005-02-24
Eric Aubay
Cleaning composition and method for removal of polysilicate residue

US7745010B2
(en)

2005-08-26
2010-06-29
Prc Desoto International, Inc.
Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods

US8758888B2
(en)

2007-04-27
2014-06-24
Valspar Sourcing, Inc.
Crosslinkable imide polyester coating

US8173221B2
(en)

2008-03-18
2012-05-08
MCT Research & Development
Protective coatings for metals

US20120024703A1
(en)

2010-07-28
2012-02-02
Ppg Industries Ohio, Inc.
Compositions useful for electrocoating metal substrates and electrodeposition processes using the coatings

US8574396B2
(en)

2010-08-30
2013-11-05
United Technologies Corporation
Hydration inhibitor coating for adhesive bonds

US9080004B2
(en)

2010-10-07
2015-07-14
Prc-Desoto International, Inc.
Diethylene glycol monomethyl ether resistant coating

US20130146460A1
(en)

2011-12-13
2013-06-13
Ppg Industries Ohio, Inc.
Resin based post rinse for improved throwpower of electrodepositable coating compositions on pretreated metal substrates

MX360882B
(en)

2012-06-18
2018-11-20
Ppg Ind Ohio Inc
Dual-cure compositions useful for coating metal substrates and processes using the compositions.

US20140255608A1
(en)

2013-03-11
2014-09-11
Ppg Industries Ohio, Inc.
Coatings that exhibit a tri-coat appearance, related coating methods and substrates

US20150072161A1
(en)

2013-09-11
2015-03-12
Prc-Desoto International, Inc.
Compositions comprising magnesium oxide and amino acid

EP3191302A4
(en)

2014-09-08
2018-05-02
MCT Research and Development
Silicate coatings

WO2016178963A1
(en)

2015-05-01
2016-11-10
Novelis Inc.
Continuous coil pretreatment process

EP3303483B1
(en)

2015-05-29
2019-07-17
PRC-Desoto International, Inc.
Multilayer coated metal substrates

US11554385B2
(en)

2015-11-17
2023-01-17
Ppg Industries Ohio, Inc.
Coated substrates prepared with waterborne sealer and primer compositions

US10767073B2
(en)

2016-10-18
2020-09-08
Ppg Industries Ohio, Inc.
Curable film-forming compositions containing hydroxyl functional, branched acrylic polymers and multilayer composite coatings

US10370555B2
(en)

2017-05-16
2019-08-06
Ppg Industries Ohio, Inc.
Curable film-forming compositions containing hydroxyl functional acrylic polymers and bisurea compounds and multilayer composite coatings

CA3069525C
(en)

2017-07-14
2022-04-19
Ppg Industries Ohio, Inc.
Curable film-forming compositions containing reactive functional polymers and polysiloxane resins, multilayer composite coatings, and methods for their use

US10773243B2
(en)

2017-09-07
2020-09-15
Ppg Industries Ohio, Inc.
Thermolatent catalyst and its use in curable compositions

EP3480261A1
(en)

2017-11-03
2019-05-08
PPG Industries Ohio, Inc.
Aqueous coating compositions and processes of forming multi-component composite coatings on substrates

WO2019125482A1
(en)

2017-12-22
2019-06-27
Ppg Industries Ohio, Inc.
Thermally curable film-forming compositions providing benefits in appearance and sag control performance

US10697081B2
(en)

2018-06-22
2020-06-30
Ppg Industries Ohio, Inc.
Method of improving the corrosion resistance of a metal substrate

US20200325289A1
(en)

2019-04-15
2020-10-15
Ppg Industries Ohio, Inc.
Curable film-forming compositions containing rheology modifiers comprising non-aqueous dispersions

CA3207768A1
(en)

2021-03-02
2022-09-09
Victor Franklin GEORGIC
Corrosion inhibiting coatings comprising aluminum particles, magnesium oxide and an aluminum and/or iron compound

CN117098817A
(en)

2021-03-02
2023-11-21
Prc-迪索托国际公司
Corrosion inhibiting coating comprising magnesium oxide and aluminum or iron compounds

AU2022229530A1
(en)

2021-03-05
2023-10-12
Prc-Desoto International, Inc.
Corrosion inhibiting coating compositions

CA3209180A1
(en)

2021-03-05
2022-09-09
Elizabeth Anne FURAR
Coating compositions comprising a polysulfide corrosion inhibitor

CA3218328A1
(en)

2021-05-25
2022-12-01
Prc-Desoto International, Inc.
Composite structures comprising metal substrates

CA3218854A1
(en)

2021-06-24
2022-12-29
Elizabeth Anne FURAR
Systems and methods for coating multi-layered coated metal substrates

Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US4111722A
(en)

1976-02-09
1978-09-05

Oxy Metal Industries Corporation

Tannin treatment of aluminum with a fluoride cleaner

FR2443514A1
(en)

1978-12-07
1980-07-04

Nihon Parkerizing

SURFACE TREATMENT SOLUTION AND SURFACE TREATMENT OF AN ALUMINUM OR ALUMINUM ALLOY SUBSTRATE

AU2884192A
(en)

1991-10-29
1993-06-07

Henkel Corporation

Treatment for the formation of a corrosion resistant film on metal surfaces

Family Cites Families (31)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US630246A
(en)

1898-09-03
1899-08-01
Frank S Loeb
Preparation of aluminium for electroplating.

NL129564C
(en)

1960-04-16
1900-01-01

NL285361A
(en)

1961-11-13
1900-01-01

US3482951A
(en)

1967-07-19
1969-12-09
Robertson Co H H
Porcelain enameled aluminum articles

GB1276822A
(en)

1969-09-05
1972-06-07
Monsanto Co
Organo-phosphonic acids

US4051110A
(en)

1971-07-06
1977-09-27
Petrolite Corporation
Methylene phosphonates of polymerized polyalkylenepolyamines

GB1441588A
(en)

1972-10-04
1976-07-07
Unilever Ltd
Rinse composition

US4122215A
(en)

1976-12-27
1978-10-24
Bell Telephone Laboratories, Incorporated
Electroless deposition of nickel on a masked aluminum surface

US4180603A
(en)

1977-01-31
1979-12-25
Oxy Metal Industries Corporation
Coating bath composition and method

LU77873A1
(en)

1977-07-29
1979-03-26
Centre Rech Metallurgique

METHOD FOR PREPARING THE SURFACE OF GALVANIZED STEEL PRODUCTS

GB2032963B
(en)

1978-10-30
1982-09-29
Dart Ind Inc
Non-chromate conversion coating solutions

US4312922A
(en)

1980-01-11
1982-01-26
Olin Corporation
Lubricated cupreous sheet comprising an organophosphonate layer and process therefor

CA1162504A
(en)

1980-11-25
1984-02-21
Mobuyuki Oda
Treating tin plated steel sheet with composition containing titanium or zirconium compounds

US4391652A
(en)

1982-01-29
1983-07-05
Chemical Systems, Inc.
Surface treatment for aluminum and aluminum alloys

GB8308003D0
(en)

1983-03-23
1983-04-27
Albright & Wilson
Phosphonates

PL143722B1
(en)

1984-01-17
1988-03-31
Ici Plc
Milk weighing balance

US4786336A
(en)

1985-03-08
1988-11-22
Amchem Products, Inc.
Low temperature seal for anodized aluminum surfaces

JPH0627358B2
(en)

1985-03-11
1994-04-13
株式会社日立製作所

Coated steel and its manufacturing method

GB8507048D0
(en)

1985-03-19
1985-04-24
Int Paint Plc
Paint

AT386000B
(en)

1985-06-20
1988-06-10
Vianova Kunstharz Ag

METHOD FOR STABILIZING ALUMINUM PIGMENTS

US4735649A
(en)

1985-09-25
1988-04-05
Monsanto Company
Gametocides

US4705703A
(en)

1986-06-30
1987-11-10
Nalco Chemical Company
Method of preventing corrosion of uncoated aluminum sheet or beverage cans in a brewery pasteurizer water system

JPS63109175A
(en)

1986-10-27
1988-05-13
Kawasaki Steel Corp
Phosphating method giving superior adhesion to paint

JPS63219587A
(en)

1987-03-10
1988-09-13
Kawasaki Steel Corp
Manufacture of galvanized steel sheet excellent in adhesive strength of paint

US4777091A
(en)

1987-04-28
1988-10-11
The Dow Chemical Company
Metal substrates treated with aminophosphonic acid compounds and products resulting from coating such substrates

US4781984A
(en)

1987-04-28
1988-11-01
The Dow Chemical Company
Aromatic polyether resins having improved adhesion

US4902535A
(en)

1987-12-31
1990-02-20
Air Products And Chemicals, Inc.
Method for depositing hard coatings on titanium or titanium alloys

DE3820650A1
(en)

1988-06-18
1989-12-21
Henkel Kgaa

METHOD FOR COMPRESSING ANODIZED OXIDE LAYERS ON ALUMINUM AND ALUMINUM ALLOYS

US5034556A
(en)

1989-04-03
1991-07-23
Ppg Industries, Inc.
Reaction products of alpha-aminomethylene phosphonic acids and epoxy compounds and their use in coating compositions

US4992116A
(en)

1989-04-21
1991-02-12
Henkel Corporation
Method and composition for coating aluminum

US4988396A
(en)

1989-04-26
1991-01-29
Sanchem, Inc.
Corrosion resistant aluminum coating composition

1992

1992-04-02
US
US07/862,143
patent/US5306526A/en
not_active
Expired – Lifetime

1993

1993-03-12
EP
EP93907494A
patent/EP0633949B1/en
not_active
Expired – Lifetime

1993-03-12
AT
AT93907494T
patent/ATE143063T1/en
not_active
IP Right Cessation

1993-03-12
ES
ES93907494T
patent/ES2094533T3/en
not_active
Expired – Lifetime

1993-03-12
BR
BR9306246A
patent/BR9306246A/en
not_active
IP Right Cessation

1993-03-12
DK
DK93907494.4T
patent/DK0633949T3/da
active

1993-03-12
KR
KR1019940703455A
patent/KR0160819B1/en
not_active
IP Right Cessation

1993-03-12
DE
DE69304902T
patent/DE69304902T2/en
not_active
Expired – Lifetime

1993-03-12
CA
CA002130114A
patent/CA2130114C/en
not_active
Expired – Lifetime

1993-03-12
WO
PCT/US1993/002326
patent/WO1993020258A1/en
active
IP Right Grant

1993-03-12
AU
AU38080/93A
patent/AU670076B2/en
not_active
Ceased

1993-03-12
JP
JP5517468A
patent/JP2843439B2/en
not_active
Expired – Fee Related

1993-03-30
MX
MX9301812A
patent/MX9301812A/en
unknown

Patent Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US4111722A
(en)

1976-02-09
1978-09-05
Oxy Metal Industries Corporation
Tannin treatment of aluminum with a fluoride cleaner

FR2443514A1
(en)

1978-12-07
1980-07-04
Nihon Parkerizing

SURFACE TREATMENT SOLUTION AND SURFACE TREATMENT OF AN ALUMINUM OR ALUMINUM ALLOY SUBSTRATE

AU2884192A
(en)

1991-10-29
1993-06-07
Henkel Corporation
Treatment for the formation of a corrosion resistant film on metal surfaces

Also Published As

Publication number
Publication date

KR0160819B1
(en)

1999-01-15

DK0633949T3
(en)

1997-03-17

DE69304902T2
(en)

1997-04-03

JPH07501585A
(en)

1995-02-16

EP0633949B1
(en)

1996-09-18

BR9306246A
(en)

1998-06-30

ES2094533T3
(en)

1997-01-16

EP0633949A1
(en)

1995-01-18

US5306526A
(en)

1994-04-26

KR950701011A
(en)

1995-02-20

WO1993020258A1
(en)

1993-10-14

JP2843439B2
(en)

1999-01-06

CA2130114A1
(en)

1993-10-14

ATE143063T1
(en)

1996-10-15

CA2130114C
(en)

1999-12-21

DE69304902D1
(en)

1996-10-24

AU3808093A
(en)

1993-11-08

MX9301812A
(en)

1993-10-01

Información de contacto