CA1078267A - Treatment of metal surfaces with aqueous solution of melamine-formaldehyde composition - Google Patents
Treatment of metal surfaces with aqueous solution of melamine-formaldehyde compositionInfo
- Publication number
- CA1078267A CA1078267A CA201,516A CA201516A CA1078267A CA 1078267 A CA1078267 A CA 1078267A CA 201516 A CA201516 A CA 201516A CA 1078267 A CA1078267 A CA 1078267A
- Authority
- CA
- Canada
- Prior art keywords
- melamine
- metal
- treated
- metal object
- formaldehyde
- 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
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
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31688—Next to aldehyde or ketone condensation product
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract of the Disclosure:
Metal surfaces are treated, preferably after phos-phating, with an aqueous solution (preferably acidic) of a melamine-formaldehyde composition and are subsequently dried, preferably by heating. The treatment is a suitable substitute for the conventional chromate rinse.
Metal surfaces are treated, preferably after phos-phating, with an aqueous solution (preferably acidic) of a melamine-formaldehyde composition and are subsequently dried, preferably by heating. The treatment is a suitable substitute for the conventional chromate rinse.
Description
- This invention relates to methods of treating metal surfaces and compositions for use thereinO More par-ticularly, it relates to a method of treating ~ metal obJect which comprises contacting the surface of said object with an aqueous solution comprising a melamine-formaldehyde com-position and subsequently drying said object.
It has been the practice for many years to form conversion coatings on metal surfaces by treatment with aqueous solutions of various chemicals. These chemicals react with the metal surface to form a coating which pro-tects the metal against corrosion and also serves as a paint baseO The most commonly used conversion coating com~
positions are phosphate and chromate compositions, and many of these are known in the art~ Frequently, a phosphate con-version coating is formed on the metal surface and is sub-sequently treated with a chromate solution as a post-rinse, which improves the corrosion resistance and paint adhesion of the coated metalO
`~ ~ Recent emphasis on water pollution problems has drawn attention to the fact that chromate-containing7 effluents are serious pollutantsO To meet water-quality standards, it is frequently necessary to go through a multi-stage purification se~uence in order to remove chro-;~ mates from the process effluent. Typical steps in this sequence include reduction of the hexavalent chromium to trivalent chromium and precipitation w1th lime or some '~ similar chemicalO The result is that the chromium content '~ of the effluent water is substantially decreased, but the e~pense of the treatment sequence to the user is quite high.
.~ .
~' ~
~' .
To alleviate this problem, interest has turned to the development of metal treatment methods which do not involve chromium chemicals. A nu~ber of these have been tried but nor.e has come into su~stantial use because they do not give the desired level of protection of the metal surface.
A principal object of the present invention, there-fore, is to develop new methods and compositions for treatment of metal surfaces to increase corrosion resistance and paint ; 10 adhesion A further object is to provide a metal surface i treatment system which can be used as a post-rinse following ,, the deposition of a phosphate coating on the metal.
, Still another object is to provide a chromium-free',. metal treatment system.
~,, A still further object is to develop a system for ~,, metal treatment which will not result in substantial water ~ pollution.
"' Other objects will in part be obvious and will in ,1 20 part appear hereinafter.
,~ - .
!. The present invention provides a method of treating ; ferrous metal objects, galvanized and aluminum objects which comprises ccntacting the surface of said objects with an '-~' ( aqueous solution comprising about 0.05-0.75% by weight of at least one melamine-formaldehyde composition, and subse-quently drying said object. The melamine-formaldehyde ~,~ compositions employed in the method of the invention are , known in the art and many are commercially available. They ;
'' are typically formed by the reaction of melamine with formal-,' 30 dehyde, often in the presence of a lower alkanol (preferably ~' methanol). The principal constituents of these compositions are polymethylolmelamines, especially tetramethylolmelamine, ' pentamethylolmelamine and hexamethylolmel-,' , . ' a 2 r ~ .
.
amine; lower alkyl ethers thereof such as hexamethoxy-methylmelamine; and condensation products of these materials.
The substances are often referred to in the art as melamine-formaldehyde or alkylated melamine-formaldehyde "resins", but it should be noted that the compositions contemplated herein are not always resinous, and they are water-soluble whether monomeric or polymeric.
The preparation of melamine-formaldehyde compo-sitions useful in the method of this in~ention is illustrated by the following examplesO
':
Example 1 : - A mixture of 504 grams (4 moles) of melamine, 1312 ¦ ~ grams of "Methyl Formcel'~(a olution of formaldehyde in a mixture of methanol and water, said solution containing about 55~ formaldehyde) (containing 24 moles of formaldehyde) and 944 grams (29~5 moles) of methanol is heated under reflux for 1-1/2 hours. Acetic acid, 8 mlO, is added and the mixture is refluxed for an additional 3 hours, a further 4 ml, of acetic acid is then added and refluxing is con-- ~ 20 tinued for an additional 1/2 hourO The solution is cooled to room temperature and adjusted by the addition of 10~
alcoholic potassium hydroxide to a pH of 1005. It is thén ~; concentrated by heating at 65C. under vacuum to yield an ." .
` 80~ solution, in a mixture of methanol and water, of the desired melamine-formaldehyde compositionO
Example 2 " ~
Following the procedure of Example 1, a product - is prepared from 126 grams (1 mole) of melamine, 273 grams .;: .~ ... . .
of Methyl Formcel (containing 5 moles of formaldehyde) and 261 grams (8,15 moles) of methanolO
de rnark , Example 3 Following the procedure of Example 1, a product is prepared from 63 grams (0.5 mole) of melamine, 168.5 grams of Methyl Formcel (containing 3 moles of formaldehyde) and 274.6 grams (3.7 moles) of n-butyl alcohol.
Example 4 Following the procedure of Example 1, a product is prepared from 126 grams (1 mole) of melamine, 437 grams of Methyl Formcel (containing 8 moles of formaldehyde) and 187 grams (5.84 moles) of methanol.
Example 5 A commercially available hexamethoxymethylmelamine composition, "Cymel 303" (50 parts by weight), is diluted with 25 parts of water and 25 parts of isopropanol to produce a clear solution.
Example 6 A commercially available methylated melamine-formaldehyde "resin", "Cymel 481", is diluted with a methanol-water (1:4 by weight) mixture to 60% solids. A clear solution 20 is obtained.
The method of this invention may be used for treating ferrous metal, galvanized and aluminum surfaces, with steel and galvanized steel surfaces being preferred. In general, the use of solutions containing very small amounts of the active ingredient is contemplated; preferably the concentration of the melamine-formaldehyde composition in the metal treatment solution is about 0.05-0.75% by weight, ~ more preferably about 0.05-0.5%. The pH of the metal ,~
~ * trade marks 1~78Zi~;7 treatment solution is ordinarily within the acidic range, typically about ~-6 and preferably about ~-5, with the lower pH values being especially preferred for the treat-ment of galvanized metalO The acid used to adjust the pH
may be a mineral acid such as sulfuric, hydrochloric or phosphoric acid, or an organic acid such as acetic acid.
Phosphoric acid is preferredO
The metal treatment solution is applied to the ~ surface of the metal article by any of the usual techniques -~ lO such as brushing, dipping, spraying, roller coating and thelike. Following such application, the mekal surface may be rinsed again with water although omission of this rinse is preferred, and is then dried by conventional means, usually !~ by air-drying at ambient temperature and/or heating to a temperature high enough to remove volatile materials (includ-ing water and alcohol used as solvent). Ternperatures of about 150-200C, are preferred during at least part of the drying operationO It is believed that the melamine-formaldehyde composition on the metal surface cures when dried to form a very thin resin coatingO
In a preferred embodiment of the method of this . - , .
invention, the metal object is initially cleaned and a phos-phate conversion coating is deposited thereonO The phosphate coating may be any of the known types such as iron phosphate, ., .
zinc phosphate, manganese phosphate, calcium- and/or mag-nesium-modified zinc phosphate, etc., and its application is accomplished by any of the methods known to those skilled in the art. Following the phosphating treatment, the metal object is usually rinsed again and is then treated as ~0 described hereinabove.
.. ~ . . .
.
The method of this invention is illustrated by a series of tests in which cold~rolled steel panels are cleaned and treated with the composition described in Example 6, diluted to about 005~ solids (by weight) to provide a coating weight of 20 mg. per square foot. The panels are air-dried at room temperature and finally dried at 176C., after which they are coated with a white alkyd baking enamelO The paint film on each panel is ruptured down to the bare metal by scoring a 6-inch line on the surface of the panel and the scored panel is placed in a cabinet containing a 5~ aqueous sodium chloride solution at 95F. Air is bubbled through the solution to produce a corrosive salt atmosphere which acts on the surface of the test panels, suspended above the level of the salt solutionO
The panels remain in this atmosphere for 168 hours after which they are removed, washed with water and dried with a cloth, A pressure-sensitive tape is then applied to each panel and removed suddenly. This procedure is repeated until no more paint can be removed in this manner. The loss of adhesion caused by corrosion from the scribed line is measured in thirty-seconds of an inch.
When test~d in this way, a panel treated with the composition of Example 6 had a loss of adhesion of 0-2 thirty-seconds of an inch. A control panel, which was merely cleaned and rinsed with water prior to paintingJ
showed complete loss of edhesion.
It has been the practice for many years to form conversion coatings on metal surfaces by treatment with aqueous solutions of various chemicals. These chemicals react with the metal surface to form a coating which pro-tects the metal against corrosion and also serves as a paint baseO The most commonly used conversion coating com~
positions are phosphate and chromate compositions, and many of these are known in the art~ Frequently, a phosphate con-version coating is formed on the metal surface and is sub-sequently treated with a chromate solution as a post-rinse, which improves the corrosion resistance and paint adhesion of the coated metalO
`~ ~ Recent emphasis on water pollution problems has drawn attention to the fact that chromate-containing7 effluents are serious pollutantsO To meet water-quality standards, it is frequently necessary to go through a multi-stage purification se~uence in order to remove chro-;~ mates from the process effluent. Typical steps in this sequence include reduction of the hexavalent chromium to trivalent chromium and precipitation w1th lime or some '~ similar chemicalO The result is that the chromium content '~ of the effluent water is substantially decreased, but the e~pense of the treatment sequence to the user is quite high.
.~ .
~' ~
~' .
To alleviate this problem, interest has turned to the development of metal treatment methods which do not involve chromium chemicals. A nu~ber of these have been tried but nor.e has come into su~stantial use because they do not give the desired level of protection of the metal surface.
A principal object of the present invention, there-fore, is to develop new methods and compositions for treatment of metal surfaces to increase corrosion resistance and paint ; 10 adhesion A further object is to provide a metal surface i treatment system which can be used as a post-rinse following ,, the deposition of a phosphate coating on the metal.
, Still another object is to provide a chromium-free',. metal treatment system.
~,, A still further object is to develop a system for ~,, metal treatment which will not result in substantial water ~ pollution.
"' Other objects will in part be obvious and will in ,1 20 part appear hereinafter.
,~ - .
!. The present invention provides a method of treating ; ferrous metal objects, galvanized and aluminum objects which comprises ccntacting the surface of said objects with an '-~' ( aqueous solution comprising about 0.05-0.75% by weight of at least one melamine-formaldehyde composition, and subse-quently drying said object. The melamine-formaldehyde ~,~ compositions employed in the method of the invention are , known in the art and many are commercially available. They ;
'' are typically formed by the reaction of melamine with formal-,' 30 dehyde, often in the presence of a lower alkanol (preferably ~' methanol). The principal constituents of these compositions are polymethylolmelamines, especially tetramethylolmelamine, ' pentamethylolmelamine and hexamethylolmel-,' , . ' a 2 r ~ .
.
amine; lower alkyl ethers thereof such as hexamethoxy-methylmelamine; and condensation products of these materials.
The substances are often referred to in the art as melamine-formaldehyde or alkylated melamine-formaldehyde "resins", but it should be noted that the compositions contemplated herein are not always resinous, and they are water-soluble whether monomeric or polymeric.
The preparation of melamine-formaldehyde compo-sitions useful in the method of this in~ention is illustrated by the following examplesO
':
Example 1 : - A mixture of 504 grams (4 moles) of melamine, 1312 ¦ ~ grams of "Methyl Formcel'~(a olution of formaldehyde in a mixture of methanol and water, said solution containing about 55~ formaldehyde) (containing 24 moles of formaldehyde) and 944 grams (29~5 moles) of methanol is heated under reflux for 1-1/2 hours. Acetic acid, 8 mlO, is added and the mixture is refluxed for an additional 3 hours, a further 4 ml, of acetic acid is then added and refluxing is con-- ~ 20 tinued for an additional 1/2 hourO The solution is cooled to room temperature and adjusted by the addition of 10~
alcoholic potassium hydroxide to a pH of 1005. It is thén ~; concentrated by heating at 65C. under vacuum to yield an ." .
` 80~ solution, in a mixture of methanol and water, of the desired melamine-formaldehyde compositionO
Example 2 " ~
Following the procedure of Example 1, a product - is prepared from 126 grams (1 mole) of melamine, 273 grams .;: .~ ... . .
of Methyl Formcel (containing 5 moles of formaldehyde) and 261 grams (8,15 moles) of methanolO
de rnark , Example 3 Following the procedure of Example 1, a product is prepared from 63 grams (0.5 mole) of melamine, 168.5 grams of Methyl Formcel (containing 3 moles of formaldehyde) and 274.6 grams (3.7 moles) of n-butyl alcohol.
Example 4 Following the procedure of Example 1, a product is prepared from 126 grams (1 mole) of melamine, 437 grams of Methyl Formcel (containing 8 moles of formaldehyde) and 187 grams (5.84 moles) of methanol.
Example 5 A commercially available hexamethoxymethylmelamine composition, "Cymel 303" (50 parts by weight), is diluted with 25 parts of water and 25 parts of isopropanol to produce a clear solution.
Example 6 A commercially available methylated melamine-formaldehyde "resin", "Cymel 481", is diluted with a methanol-water (1:4 by weight) mixture to 60% solids. A clear solution 20 is obtained.
The method of this invention may be used for treating ferrous metal, galvanized and aluminum surfaces, with steel and galvanized steel surfaces being preferred. In general, the use of solutions containing very small amounts of the active ingredient is contemplated; preferably the concentration of the melamine-formaldehyde composition in the metal treatment solution is about 0.05-0.75% by weight, ~ more preferably about 0.05-0.5%. The pH of the metal ,~
~ * trade marks 1~78Zi~;7 treatment solution is ordinarily within the acidic range, typically about ~-6 and preferably about ~-5, with the lower pH values being especially preferred for the treat-ment of galvanized metalO The acid used to adjust the pH
may be a mineral acid such as sulfuric, hydrochloric or phosphoric acid, or an organic acid such as acetic acid.
Phosphoric acid is preferredO
The metal treatment solution is applied to the ~ surface of the metal article by any of the usual techniques -~ lO such as brushing, dipping, spraying, roller coating and thelike. Following such application, the mekal surface may be rinsed again with water although omission of this rinse is preferred, and is then dried by conventional means, usually !~ by air-drying at ambient temperature and/or heating to a temperature high enough to remove volatile materials (includ-ing water and alcohol used as solvent). Ternperatures of about 150-200C, are preferred during at least part of the drying operationO It is believed that the melamine-formaldehyde composition on the metal surface cures when dried to form a very thin resin coatingO
In a preferred embodiment of the method of this . - , .
invention, the metal object is initially cleaned and a phos-phate conversion coating is deposited thereonO The phosphate coating may be any of the known types such as iron phosphate, ., .
zinc phosphate, manganese phosphate, calcium- and/or mag-nesium-modified zinc phosphate, etc., and its application is accomplished by any of the methods known to those skilled in the art. Following the phosphating treatment, the metal object is usually rinsed again and is then treated as ~0 described hereinabove.
.. ~ . . .
.
The method of this invention is illustrated by a series of tests in which cold~rolled steel panels are cleaned and treated with the composition described in Example 6, diluted to about 005~ solids (by weight) to provide a coating weight of 20 mg. per square foot. The panels are air-dried at room temperature and finally dried at 176C., after which they are coated with a white alkyd baking enamelO The paint film on each panel is ruptured down to the bare metal by scoring a 6-inch line on the surface of the panel and the scored panel is placed in a cabinet containing a 5~ aqueous sodium chloride solution at 95F. Air is bubbled through the solution to produce a corrosive salt atmosphere which acts on the surface of the test panels, suspended above the level of the salt solutionO
The panels remain in this atmosphere for 168 hours after which they are removed, washed with water and dried with a cloth, A pressure-sensitive tape is then applied to each panel and removed suddenly. This procedure is repeated until no more paint can be removed in this manner. The loss of adhesion caused by corrosion from the scribed line is measured in thirty-seconds of an inch.
When test~d in this way, a panel treated with the composition of Example 6 had a loss of adhesion of 0-2 thirty-seconds of an inch. A control panel, which was merely cleaned and rinsed with water prior to paintingJ
showed complete loss of edhesion.
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS
1. A method of treating ferrous metal objects, galvanized and aluminum objects which comprises contacting the surface of said objects with an aqueous solution comprising about 0.05-0.75%
by weight of at least one melamine-formaldehyde composition, and subsequently drying said object.
by weight of at least one melamine-formaldehyde composition, and subsequently drying said object.
2. A method according to claim 1 wherein the metal object is a steel or galvanized steel object.
3. A method according to claim 1 wherein said solution is an acidic solution comprising polymethylol melamines, lower alkyl ethers thereof, and condensation products of the same.
4. A method according to claim 3 wherein the drying is effected at least partially at a temperature of about 150-200°C.
5. A method according to claim 4 wherein the metal object is a steel object.
6. A method according to claim 3 wherein the metal object is first treated with a phosphate coating solution.
7. A method according to claim 4 wherein the metal object is first treated with a phosphate coating solution.
8. A method according to claim 5 wherein the metal object is first treated with a phosphate coating solution.
9. A method of treating a phosphated ferrous metal, galvanized or aluminum object which comprises contacting the surface of said object with an aqueous solution comprising about 0.05 to 0.75% by weight of at least one melamine-formaldehyde composition, and subsequently drying said object.
10. A method according to claim 9 wherein the metal object is a steel object.
11. A method according to claim 10 wherein the melamine-formaldehyde composition comprises polymethylol-melamines, lower alkyl ethers thereof, and condensation products of the same.
12. A method according to claim 11 wherein the drying is effected at least partially at a temperature of about 150-200°C.
13. A method according to claim 11 wherein the melamine-formaldehyde composition is acidic.
14. A method according to claim 13 wherein the lower alkyl ethers are methyl ethers.
15. A method according to claim 14 wherein the drying is effected at least partially at a temperature of about 150-200°C.
16. A metal object which has been treated according to the method of claim 1.
17. A metal object which has been treated according to the method of claim 4.
18. A metal object which has been treated according to the method of claim 7.
19. A metal object which has been treated according to the method of claim 9.
20. A metal object which has been treated according to the method of claim 13.
21. A metal object which has been treated according to the method of claim 15.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36878373 US3877998A (en) | 1973-06-11 | 1973-06-11 | Treatment of metal surfaces with aqueous solution of melamine-formaldehyde composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078267A true CA1078267A (en) | 1980-05-27 |
Family
ID=23452713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA201,516A Expired CA1078267A (en) | 1973-06-11 | 1974-06-03 | Treatment of metal surfaces with aqueous solution of melamine-formaldehyde composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3877998A (en) |
| CA (1) | CA1078267A (en) |
| DE (1) | DE2427121A1 (en) |
| FR (1) | FR2232581B1 (en) |
| GB (1) | GB1473190A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174980A (en) * | 1974-10-25 | 1979-11-20 | Oxy Metal Industries Corporation | Melamine-formaldehyde and tannin treatment of metal surfaces |
| US4039353A (en) * | 1974-10-25 | 1977-08-02 | Oxy Metal Industries Corporation | Post-treatment of conversion-coated metal surfaces |
| US4053682A (en) * | 1976-06-21 | 1977-10-11 | Monsanto Company | Process for improving the adhesion of hot melts to metal substrates |
| US4114505A (en) * | 1977-01-31 | 1978-09-19 | Loeser William J | Coatings and methods of application |
| JPS6089357A (en) * | 1983-10-22 | 1985-05-20 | 日本ペイント株式会社 | Hydrogen absorbing inhibiting coating steel material and manufacture thereof |
| US5128211A (en) * | 1991-02-28 | 1992-07-07 | Diversey Corporation | Aluminum based phosphate final rinse |
| US5433773A (en) * | 1994-06-02 | 1995-07-18 | Fremont Industries, Inc. | Method and composition for treatment of phosphate coated metal surfaces |
| CA2284342C (en) | 1999-09-29 | 2011-11-01 | Meaney, Daniel J., Jr. | Method, solution and paint for forming a metallic mirror surface or metallic luster |
| US7111950B2 (en) * | 1999-09-29 | 2006-09-26 | American Spray Coatings | Method for forming a metallic mirror surface on a receiving surface |
| US6257732B1 (en) | 1999-09-29 | 2001-07-10 | American Spray Coating | Method for forming a metallic mirror surface and solutions for the same |
| US20060065365A1 (en) | 2004-09-30 | 2006-03-30 | Ferrier Donald R | Melamine-formaldehyde post-dip composition for improving adhesion of metal to polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2383589A (en) * | 1942-03-06 | 1945-08-28 | Bunting | Ferrous metal ice tray |
| DE1269753B (en) * | 1960-09-16 | 1968-06-06 | Metallgesellschaft Ag | Process for the simultaneous phosphating and application of an organic coating on metals |
| US3397077A (en) * | 1963-05-14 | 1968-08-13 | Ernest R Boller | Metal finishing process and composition therefor |
| US3586543A (en) * | 1967-10-20 | 1971-06-22 | Nippon Kokan Kk | Coating treatment of metal surface |
| US3519495A (en) * | 1968-12-31 | 1970-07-07 | Hooker Chemical Corp | Process for coating metal surfaces |
-
1973
- 1973-06-11 US US36878373 patent/US3877998A/en not_active Expired - Lifetime
-
1974
- 1974-06-03 CA CA201,516A patent/CA1078267A/en not_active Expired
- 1974-06-05 DE DE19742427121 patent/DE2427121A1/en not_active Withdrawn
- 1974-06-07 GB GB2539274A patent/GB1473190A/en not_active Expired
- 1974-06-07 FR FR7419707A patent/FR2232581B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US3877998A (en) | 1975-04-15 |
| FR2232581A1 (en) | 1975-01-03 |
| DE2427121A1 (en) | 1975-01-02 |
| FR2232581B1 (en) | 1978-08-11 |
| GB1473190A (en) | 1977-05-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |