CA2121486A1 - Treatment for the formation of a corrosion resistant film on metal surfaces - Google Patents
Treatment for the formation of a corrosion resistant film on metal surfacesInfo
- Publication number
- CA2121486A1 CA2121486A1 CA002121486A CA2121486A CA2121486A1 CA 2121486 A1 CA2121486 A1 CA 2121486A1 CA 002121486 A CA002121486 A CA 002121486A CA 2121486 A CA2121486 A CA 2121486A CA 2121486 A1 CA2121486 A1 CA 2121486A1
- Authority
- CA
- Canada
- Prior art keywords
- phosphate
- cationic
- treatment
- metal
- salt
- 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.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- 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
- C23C22/08—Orthophosphates
-
- 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
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2301/00—Inorganic additives or organic salts thereof
- B05D2301/10—Phosphates, phosphoric acid or organic salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
Abstract
A phosphate surface-treatment bath which contains a cationic organic polymeric compound (or salt thereof) that contains at least one cationic nitrogen atom and has a molecular weight of 1,000 to 1,000,000 forms a highly corrosion resistant film on metal surfaces (e.g., iron, zinc, aluminum, etc.) that is also an excellent paint undercoat. The film preferably is one in which the resin composed of the cationic organic compound (or salt thereof) has penetrated into the grain boundaries between phosphate crystals with an accompanying formation of a phosphate crystal/resin composite.
A film formed in accordance with the present invention affords a remarkable improvement in corrosion resistance and paint adherence, compared with the phosphate conversion achieved with the same treatment, except for the omission of the organic polymer containing cationic nitrogen. In addition, even when the primer coating step is omitted, the present invention exhibits a performance approximately equivalent to the application of a primer coating on a conventional phosphate film.
A film formed in accordance with the present invention affords a remarkable improvement in corrosion resistance and paint adherence, compared with the phosphate conversion achieved with the same treatment, except for the omission of the organic polymer containing cationic nitrogen. In addition, even when the primer coating step is omitted, the present invention exhibits a performance approximately equivalent to the application of a primer coating on a conventional phosphate film.
Description
W093~0926~ PCT/US92/OX811 -~` 2121486 ~escri~tion TREATMENT FOR T~E FORMATION OF A CORR08ION RE8I8TAN~ FILM
Technical ~ield The present invention relates to a novel treatment ag-ent that forms a strongly corrosion-resistant film on the surface of metals such as iron, zinc, aluminum, and the 5 like. This film is also an excellent paint undercoat.
ç~ground Art At present, increasingly hiqh levels of corrosion re-si~tance are being required of painted objects such as au-tomobile bodies and construction materials. Metal surfaces have heretofore been treated by phosphate treatments, chro-mate treatments, etc.; however, the prior metal surface treatment agents do not always exhibit a satisfac_ory cor-rosion~resistance and paint adherence.
The art is already familiar with the formation of a , ~ ~
phosphate film on a metal surface as a generally applicable pretreatment method when organic films, e.g., paints, ad-hesives, and the like, are applied on the su~rfaces of met-als such as iron, zinc, aluminum, and the like. The cor-rosion resistance and paint adherence are improved by this addition of a phosphate film on the metal surface prior to the application of the organic coating (typically paint3.
When higher levels of corrosion resistance are required, both a phosphate treatment and a post-treatment (e.~., sealing with chromic acid and the like) or primèr appli-cation are carried out prior to painting. However, these post-treatments (e.g., sealing with chromic acid and the like) contribute only minor benefits. Moreover, while the application of a primer does improve the paintability, this also expands the painting process and thus substantially impairs the workability.
Nevertheless, primer application is currently requi~ed for painted objects such as automobile bodies and construc-SUBSTITUTE SHEET
. ~
W093~0926~ 2 12 i ~ 8 ~ PCT/US92/08811 tion materials. In the case of automobile bodies, a ~-nc phosphate film is formed on the metal surface, which i8 then immersed in aqueous paint for electrodeposit~on coat-ing. This coating operation ls a type of primer coating, s and its purpose is to increase the corrosion resistance of the painted surface and to secure corrosion resistance for the interior surfaces of the automobile body, which can be difficult to finish coat. A primer coating is similarly applied on construction materials prior to finish coating o in order to increase the corrosion resistance.
While improvements in operatinq efficiency and cost reduction in painting operations require a contraction of the process, a satisfactory response to this goal has yet to be developed. Thus, phosphate films alone have a poor s corrosion resistance, while painting alone does not satisfy the requirements for corrosion resistance and paint adher-ence. When higher levels of corrosion resistance are re-;~ quired, both a phosphate film and a primer coating are re-quired. This results in high painting costs and reguires large work areas. The development of a metal surface treatment agent that exhibits a high corrosion resistance and paint adherence is therefore desired. The development of a metal-surface-treatment agent that permits the omis-sion of primer coating is also desired.
25 Disclosure of_the Invention ~roblems to Be_Solved bY the Invention As a means of responding to the above-listed problems, the present invention takes as its object the introduction of a metal-surface-treatment agent that can impart a high 30 corrosion resistance and paint adherence to metals that are suitable for phosphate film treatment, such as iron, zinc, aluminum, and the like (hereinafter briefly denoted simply as "metal"). A further object of the present invention is the introduction of a metal surface treatment agent that 35 permits the omission of primer coating while at the same time retaining the level of corrosion resistance currently available.
wo g3tog26~ 2 1 2 1 ~ ~ 6 PCI`/IJS92/0881 1 `
Summary of the Invention As the result of extenslve research directed at solv-ing the aforementioned problems, it has now been discovered that a high corrosion resistance and palnt adherence are s obtained by film formation from a phosphate treatment bath that contains an organic polymeric compound (or salt there-of) having certain properties. The present invention was developed as a result of this discovery.
That 18, a film that exhibits the highly desirable o properties specified above can be formed by treating the metal surface with a treatment agent for the formation of ;~ a film on metal surfaces, wherein said treatment agent characteristically compri~es a phosphate surface treatment bath ~hich contains a cationic organic polymeric compound s (or salt thereof) that contains at least 1 cationic nitro-gen atom and has a molecular weight of 1,000 to 1,000,000.
The film according to the present invention preferably is a composite film in which the resin composed of the cation-~ ic organic compound (or salt thereof) has penetrated into -~ ~ the grain boundaries between phosphate crystals with an accompanying formation of a phosphate crystal/resin com-posite.
The surface treatment agent according~to the present invention comprises the solution or stable dispersion of a s cationic organic polymeric compound (or salt thereof) i~ a phosphate treatment bath. Said phosphate treatment bath comprises any surface-treatment bath that is capable of forming a phosphate film on the surface of a metal such as iron, zinc, aluminum, etc., either for a single species of 30 metal alone or simultaneously on the surfaces of two or more species of the preceding metals. In general, its es-sential components are zinc ions and phosphate ions, but it may optionally contain nitrate ions, other metal ions (nickel, manganese, calcium, and the like), fluoride, and 3s various types of oxidants. However, the phosphate treat-ment bath is not specifically restricted within the context of the present invention, and the present invention encom-wo g3/0926:~ 2 1 2 1 4 8 6 PCr~lS92/0881 .
passes all known phosphate treatment baths.
The cationic organic polymeric compound should contain at least 1 cationic nitrogen atom and should have a molecu-lar weight of 1,000 to 1,000,000. Although its structure is not restricted in the broadest embodiments of the inven-tion, organic polymers are particularly preferred that have a resin skeleton comprising at least one selection from epoxy resins, urethane resins, polybutadiene resins, acryl-ic resins, and maleic anhydride resins, wherein these o resins contain a cationic nitrogen-containing group.
The salts of the cationic organic polymeric compound encompass its inorganic salts and organic salts. The inor-ganic salts are exemplified by phosphate, nitrate, sulfate, and the like, and the organic salts are exemplified by ace-tate, propionate, glyconate, and the like. A single spe-cies or two or more species of this cationic organic poly-meric compound (or salt thereof) can be employed. Only a weak improvement in corrosion resistance is obtained at molecular weights below 1,000, while it is very difficult to obtain dissolution or stable dispersion in zinc phos-phate baths at molecular weights in excess of 1,000,000.
Noreover, paint additives (such as pigment and the like), other types of resins, activators, and the like may be added on an optional basis.
With respect to the technique for treating the metal surface, the present invention can employ conversion treat-ment ~y spray or immersion as well as electrolytic metho-dologies, and the treatment agent according to the present invention is not limited to a particular treatment method.
Examples The effects of the present invention will be explai-ned in detail in the following using illustrative examples and comparison examples; however, the present invention is not limited to the examples, which describe merely a typical 3s pre-paint phosphate treatment and a typical painting sys-tem. In comparison examples, evaluation and treatment were conducted as in the examples, but with the use of organic ~- 4 :~ SUBSTITUTE SHEET
,~
W093/0926~ 2 1 2 1 ~ ~ e PCT/US92/088t1 polymeric compound outside the scope of t~e present inven-tion and with omission of the cationic organic polymer altogether.
The general conditions for the examples and comparison s examples were as follows:
WorkDieces: Cold-rolled steel sheet; electroplated steel sheet ~zinc coating z 20 g/m2); aluminum sheet (JIS 5052).
Surface treatment agents: The cationic organic polymeric compounds used in the examples and the polymeric compounds ~; lo used in t~e comparison examples are reported in Table 1.
PARBOND~M L3020 (surface-treatment agent for automotive applications from Nihon Parkerizing Company, Limited) was used for the organic`polymer-free phosphate surface treat-, ment bath. This was a typical phosphate surface-treatment `~ 1s bat~.
Treatment sequence:
1) Degreasing: 2 % solution of FINECLEANERTH L4460 (from ~ Nihon Parkerizing Company, Ltd.), 120 second spray at `~ 42 C
Technical ~ield The present invention relates to a novel treatment ag-ent that forms a strongly corrosion-resistant film on the surface of metals such as iron, zinc, aluminum, and the 5 like. This film is also an excellent paint undercoat.
ç~ground Art At present, increasingly hiqh levels of corrosion re-si~tance are being required of painted objects such as au-tomobile bodies and construction materials. Metal surfaces have heretofore been treated by phosphate treatments, chro-mate treatments, etc.; however, the prior metal surface treatment agents do not always exhibit a satisfac_ory cor-rosion~resistance and paint adherence.
The art is already familiar with the formation of a , ~ ~
phosphate film on a metal surface as a generally applicable pretreatment method when organic films, e.g., paints, ad-hesives, and the like, are applied on the su~rfaces of met-als such as iron, zinc, aluminum, and the like. The cor-rosion resistance and paint adherence are improved by this addition of a phosphate film on the metal surface prior to the application of the organic coating (typically paint3.
When higher levels of corrosion resistance are required, both a phosphate treatment and a post-treatment (e.~., sealing with chromic acid and the like) or primèr appli-cation are carried out prior to painting. However, these post-treatments (e.g., sealing with chromic acid and the like) contribute only minor benefits. Moreover, while the application of a primer does improve the paintability, this also expands the painting process and thus substantially impairs the workability.
Nevertheless, primer application is currently requi~ed for painted objects such as automobile bodies and construc-SUBSTITUTE SHEET
. ~
W093~0926~ 2 12 i ~ 8 ~ PCT/US92/08811 tion materials. In the case of automobile bodies, a ~-nc phosphate film is formed on the metal surface, which i8 then immersed in aqueous paint for electrodeposit~on coat-ing. This coating operation ls a type of primer coating, s and its purpose is to increase the corrosion resistance of the painted surface and to secure corrosion resistance for the interior surfaces of the automobile body, which can be difficult to finish coat. A primer coating is similarly applied on construction materials prior to finish coating o in order to increase the corrosion resistance.
While improvements in operatinq efficiency and cost reduction in painting operations require a contraction of the process, a satisfactory response to this goal has yet to be developed. Thus, phosphate films alone have a poor s corrosion resistance, while painting alone does not satisfy the requirements for corrosion resistance and paint adher-ence. When higher levels of corrosion resistance are re-;~ quired, both a phosphate film and a primer coating are re-quired. This results in high painting costs and reguires large work areas. The development of a metal surface treatment agent that exhibits a high corrosion resistance and paint adherence is therefore desired. The development of a metal-surface-treatment agent that permits the omis-sion of primer coating is also desired.
25 Disclosure of_the Invention ~roblems to Be_Solved bY the Invention As a means of responding to the above-listed problems, the present invention takes as its object the introduction of a metal-surface-treatment agent that can impart a high 30 corrosion resistance and paint adherence to metals that are suitable for phosphate film treatment, such as iron, zinc, aluminum, and the like (hereinafter briefly denoted simply as "metal"). A further object of the present invention is the introduction of a metal surface treatment agent that 35 permits the omission of primer coating while at the same time retaining the level of corrosion resistance currently available.
wo g3tog26~ 2 1 2 1 ~ ~ 6 PCI`/IJS92/0881 1 `
Summary of the Invention As the result of extenslve research directed at solv-ing the aforementioned problems, it has now been discovered that a high corrosion resistance and palnt adherence are s obtained by film formation from a phosphate treatment bath that contains an organic polymeric compound (or salt there-of) having certain properties. The present invention was developed as a result of this discovery.
That 18, a film that exhibits the highly desirable o properties specified above can be formed by treating the metal surface with a treatment agent for the formation of ;~ a film on metal surfaces, wherein said treatment agent characteristically compri~es a phosphate surface treatment bath ~hich contains a cationic organic polymeric compound s (or salt thereof) that contains at least 1 cationic nitro-gen atom and has a molecular weight of 1,000 to 1,000,000.
The film according to the present invention preferably is a composite film in which the resin composed of the cation-~ ic organic compound (or salt thereof) has penetrated into -~ ~ the grain boundaries between phosphate crystals with an accompanying formation of a phosphate crystal/resin com-posite.
The surface treatment agent according~to the present invention comprises the solution or stable dispersion of a s cationic organic polymeric compound (or salt thereof) i~ a phosphate treatment bath. Said phosphate treatment bath comprises any surface-treatment bath that is capable of forming a phosphate film on the surface of a metal such as iron, zinc, aluminum, etc., either for a single species of 30 metal alone or simultaneously on the surfaces of two or more species of the preceding metals. In general, its es-sential components are zinc ions and phosphate ions, but it may optionally contain nitrate ions, other metal ions (nickel, manganese, calcium, and the like), fluoride, and 3s various types of oxidants. However, the phosphate treat-ment bath is not specifically restricted within the context of the present invention, and the present invention encom-wo g3/0926:~ 2 1 2 1 4 8 6 PCr~lS92/0881 .
passes all known phosphate treatment baths.
The cationic organic polymeric compound should contain at least 1 cationic nitrogen atom and should have a molecu-lar weight of 1,000 to 1,000,000. Although its structure is not restricted in the broadest embodiments of the inven-tion, organic polymers are particularly preferred that have a resin skeleton comprising at least one selection from epoxy resins, urethane resins, polybutadiene resins, acryl-ic resins, and maleic anhydride resins, wherein these o resins contain a cationic nitrogen-containing group.
The salts of the cationic organic polymeric compound encompass its inorganic salts and organic salts. The inor-ganic salts are exemplified by phosphate, nitrate, sulfate, and the like, and the organic salts are exemplified by ace-tate, propionate, glyconate, and the like. A single spe-cies or two or more species of this cationic organic poly-meric compound (or salt thereof) can be employed. Only a weak improvement in corrosion resistance is obtained at molecular weights below 1,000, while it is very difficult to obtain dissolution or stable dispersion in zinc phos-phate baths at molecular weights in excess of 1,000,000.
Noreover, paint additives (such as pigment and the like), other types of resins, activators, and the like may be added on an optional basis.
With respect to the technique for treating the metal surface, the present invention can employ conversion treat-ment ~y spray or immersion as well as electrolytic metho-dologies, and the treatment agent according to the present invention is not limited to a particular treatment method.
Examples The effects of the present invention will be explai-ned in detail in the following using illustrative examples and comparison examples; however, the present invention is not limited to the examples, which describe merely a typical 3s pre-paint phosphate treatment and a typical painting sys-tem. In comparison examples, evaluation and treatment were conducted as in the examples, but with the use of organic ~- 4 :~ SUBSTITUTE SHEET
,~
W093/0926~ 2 1 2 1 ~ ~ e PCT/US92/088t1 polymeric compound outside the scope of t~e present inven-tion and with omission of the cationic organic polymer altogether.
The general conditions for the examples and comparison s examples were as follows:
WorkDieces: Cold-rolled steel sheet; electroplated steel sheet ~zinc coating z 20 g/m2); aluminum sheet (JIS 5052).
Surface treatment agents: The cationic organic polymeric compounds used in the examples and the polymeric compounds ~; lo used in t~e comparison examples are reported in Table 1.
PARBOND~M L3020 (surface-treatment agent for automotive applications from Nihon Parkerizing Company, Limited) was used for the organic`polymer-free phosphate surface treat-, ment bath. This was a typical phosphate surface-treatment `~ 1s bat~.
Treatment sequence:
1) Degreasing: 2 % solution of FINECLEANERTH L4460 (from ~ Nihon Parkerizing Company, Ltd.), 120 second spray at `~ 42 C
2) Water wash: 30 second spray at room temperature 3) Surface conditioning: 0.1 % solution of PARCOLENETM ZN
(from Ni~on Parkerizing Company, Ltd.), 20 second spray at room temperature ;~ 4) The surface-treatment agents accordi~g to the present - ~ 25 invention and the surface-treatment agents in the c~m-parison examples were both applied under the following conditions: immersion at 42 C for 120 seconds.
5) Water wash: 30 second spray at room temperature 6) Wash with deionized water (conductivity, 0.2 mi-: 30 crosiemens/cm): 20 second spray at room temperature After completion of the six process steps noted above and drying, painting was conducted by the following pro-cesses (the primer step was sometimes omitted, as noted in the tables below):
~;
,, - ~ S
; ~
` :
W093/0926~ 2 1 2 1 ~ 8 6 P~ S92/0881 1 Table 1 Designa- Chemical Nature of the organic Molecular tion of PolYmeric Compound Used Weiaht s Treatment A adduct of HN(CH3)2 with bisphenol A8,800 epoxy resin B copolymer of methyl methacrylate20,000 o and dimethylaminoethyl methacrylate C adduct of H2NCH2N(CH3)2 with maleic2,000 anhydr~de resin a adduct of H2NCH2N~CH3)2 with maleic800 maleic anhydride resin b polyvinyl alcohol 3,000 1) Primer coating: Electrodeposition painting with ELE-CRONTM 9410 from Kansai Paint Kabushiki Kaisha to pro-duce a film thickness = 20 micrometers; baking at 175 .
: 20 C for 30 minutes 2) Intermediate coating: XPX36 from Kansai Paint Kabu-shiki Kaisha; fllm thickness = 30 micrometers; baking at~140 C for 30 minutes 3~) Finish coating: RUGABAKE~M B 531 from Xans~i Paint Ka-bushiki-Kaisha; film t~ickness 40 micrometers; baking at 140 C for 30 minutes.
All the process steps noted above were carried out in the same manner for both the examples and tbe compari~on examplas, except for the chemical nature of the surface-treatment agents used (in step 4).
Performance evaluation:
1) Water-resistant secondary adhesion: The painted sheet was immersed in deionized water at 40 C for 240 hours, and a checkerboard of 100 squares (2 mm x 2 mm) was scribed into the base material using a sharp cut-~; ter. After peeling with cellophane tape, the number of peeled squares was counted. A smaller number of peeled squares indicates a better score.
2) Composite cycle test: A cross was scribed in the o painted sheet throuqh to the base material, using a ~, ~
~ 6 ,, ~
W093/0926~ 2 1 2 1 ~ 8 6 PCT/US92/08811 sharp cutter, and the painted sheet was then subjected to 14 repetitions of the Tl - T2 cycle (see below).
After the test, evaluation was carried out by measur-ing the maximum one side film blister width from the s inscribed cross.
Tl : salt-spray test (JIS Z 2371) : 24 hours T2 : wetting test (50 C, 70 % RH) : 216 hours ~enefits of the Invention Tables 2, 3, and 4 report the paint adherence and cor-~ 10 rosion resistance of the films o~tained by surface treat--~ ; ment, re~pectively, of cold-rolled ~teel ~heet, electrogal-vanized ~teel sheet, and aluminum sheet. These tables also include the results for the comparison examples~
In the case of treatment by a metal-surface-treatment ~s agent for composite film formation in accordance with the pre~ent invention, the results confirm a remarkable im-provement in corrosion resistance and paint adherence over phos p ate treatment. In addition, even with omission of primer~ coating, the present invention exhibits a perform-ance approximately equivalent to the application of a pri-mer coat on phosphate film.
When an organic polymeric compound was used that was not within the scope of the present invention, either æub-stantially no effect was obtained or the performance was in fact degraded.
As discussed hereinbefore, the metal surface treatment agent for composite film formation in accordance with the invention increases the corrosion resistance and paint ad-herence and makes possible the omission of primer coating.
, ~ ~
wo g3/0926~ 2 1 2 1 4 8 ~ PCT/US92/08811 ~ .
Table 2 I
Example Organic Polymer Primer Water Compos-("Ex") Component Coating Resist- ite or Com- Used? ant Cycle parison Secon- Test:
Example dary Blister ("CE") TypeConcen- Adhe- Width Number tration sion: in mm Number Peeled _ ¦Ex 1 A~ 0.1 % yes 0 < 0.5 Ex 2 ~ 0.5 % yes 0 S 0.5 : Ex 3 2.0 ~ yes < o.~
_ I
: . Ex 4 A1.0 % no 0 1.7 , CE 1 na ne yes 0 1.5 .; ~ CE 2 none ~ no 57 4.4 CE 3 a ¦ 1.0 % ~ yes 0 1.4 CE 4 b ¦ 1.0 % yes 37 1.7 ~ . ....
. Table 3 Example Organic Polymer Primer Water Compos-( nEx~l ) Component Coating Resist- ite : or Com- Used? an~ Cycle parison Secon- Test:
: ~ Example . _ dary Blister . ¦ ("CE") Type Concen- Adhe- Width , .Number tration sion: in mm . Number . Peeled ~
Ex s A 0.1 % yes 0 < 0.5 . _ Ex 6 B 0.5 % yes 0 ~ 0.5 .
Ex 7 C 2.0 % yes 0 < 0.5 Ex 8 A 1.0 % no 1.2.
CE 5 nc ne yes 0 1.0 CE 6 none no 36 2.2 CE 7 a 1.0 % yes 0 1.1 CE 8 b 1.0 % yes 17 1.8 :~ 8 ~ ;~ SUBSTITUTE SHEET
W093/0926~ 2 1 2 1 ~ 8 ~6 PCT/~S92/08811 ~, Table 4 . I
- ._ Example Organic Polymer Primer Water Compo~-("Ex") Component Coating Resist- lte or Com- Used? ant Cycle parison Secon- Test:
Example dary Blister ("CE") Type Concen- Adhe- Width Number tration sion: in mm Number Peeled Ex 9 A 0.1 % yes 0 S 0.5 Ex 10 B 0.5 % yes S 0.5 Ex 11 C 2.0 % yes 0 S 0.5 Ex 12 A 1.0 % no 6 0.7 ~: CE 9 none yes 5 0.8 :: ~ CE 10 none no 36 1.5 CE 11 a 1.0 t yes _ 4 0.8 CE 12 b 1.0 % yes 17 1.2 :
,`
'~
~ .
.
::
(from Ni~on Parkerizing Company, Ltd.), 20 second spray at room temperature ;~ 4) The surface-treatment agents accordi~g to the present - ~ 25 invention and the surface-treatment agents in the c~m-parison examples were both applied under the following conditions: immersion at 42 C for 120 seconds.
5) Water wash: 30 second spray at room temperature 6) Wash with deionized water (conductivity, 0.2 mi-: 30 crosiemens/cm): 20 second spray at room temperature After completion of the six process steps noted above and drying, painting was conducted by the following pro-cesses (the primer step was sometimes omitted, as noted in the tables below):
~;
,, - ~ S
; ~
` :
W093/0926~ 2 1 2 1 ~ 8 6 P~ S92/0881 1 Table 1 Designa- Chemical Nature of the organic Molecular tion of PolYmeric Compound Used Weiaht s Treatment A adduct of HN(CH3)2 with bisphenol A8,800 epoxy resin B copolymer of methyl methacrylate20,000 o and dimethylaminoethyl methacrylate C adduct of H2NCH2N(CH3)2 with maleic2,000 anhydr~de resin a adduct of H2NCH2N~CH3)2 with maleic800 maleic anhydride resin b polyvinyl alcohol 3,000 1) Primer coating: Electrodeposition painting with ELE-CRONTM 9410 from Kansai Paint Kabushiki Kaisha to pro-duce a film thickness = 20 micrometers; baking at 175 .
: 20 C for 30 minutes 2) Intermediate coating: XPX36 from Kansai Paint Kabu-shiki Kaisha; fllm thickness = 30 micrometers; baking at~140 C for 30 minutes 3~) Finish coating: RUGABAKE~M B 531 from Xans~i Paint Ka-bushiki-Kaisha; film t~ickness 40 micrometers; baking at 140 C for 30 minutes.
All the process steps noted above were carried out in the same manner for both the examples and tbe compari~on examplas, except for the chemical nature of the surface-treatment agents used (in step 4).
Performance evaluation:
1) Water-resistant secondary adhesion: The painted sheet was immersed in deionized water at 40 C for 240 hours, and a checkerboard of 100 squares (2 mm x 2 mm) was scribed into the base material using a sharp cut-~; ter. After peeling with cellophane tape, the number of peeled squares was counted. A smaller number of peeled squares indicates a better score.
2) Composite cycle test: A cross was scribed in the o painted sheet throuqh to the base material, using a ~, ~
~ 6 ,, ~
W093/0926~ 2 1 2 1 ~ 8 6 PCT/US92/08811 sharp cutter, and the painted sheet was then subjected to 14 repetitions of the Tl - T2 cycle (see below).
After the test, evaluation was carried out by measur-ing the maximum one side film blister width from the s inscribed cross.
Tl : salt-spray test (JIS Z 2371) : 24 hours T2 : wetting test (50 C, 70 % RH) : 216 hours ~enefits of the Invention Tables 2, 3, and 4 report the paint adherence and cor-~ 10 rosion resistance of the films o~tained by surface treat--~ ; ment, re~pectively, of cold-rolled ~teel ~heet, electrogal-vanized ~teel sheet, and aluminum sheet. These tables also include the results for the comparison examples~
In the case of treatment by a metal-surface-treatment ~s agent for composite film formation in accordance with the pre~ent invention, the results confirm a remarkable im-provement in corrosion resistance and paint adherence over phos p ate treatment. In addition, even with omission of primer~ coating, the present invention exhibits a perform-ance approximately equivalent to the application of a pri-mer coat on phosphate film.
When an organic polymeric compound was used that was not within the scope of the present invention, either æub-stantially no effect was obtained or the performance was in fact degraded.
As discussed hereinbefore, the metal surface treatment agent for composite film formation in accordance with the invention increases the corrosion resistance and paint ad-herence and makes possible the omission of primer coating.
, ~ ~
wo g3/0926~ 2 1 2 1 4 8 ~ PCT/US92/08811 ~ .
Table 2 I
Example Organic Polymer Primer Water Compos-("Ex") Component Coating Resist- ite or Com- Used? ant Cycle parison Secon- Test:
Example dary Blister ("CE") TypeConcen- Adhe- Width Number tration sion: in mm Number Peeled _ ¦Ex 1 A~ 0.1 % yes 0 < 0.5 Ex 2 ~ 0.5 % yes 0 S 0.5 : Ex 3 2.0 ~ yes < o.~
_ I
: . Ex 4 A1.0 % no 0 1.7 , CE 1 na ne yes 0 1.5 .; ~ CE 2 none ~ no 57 4.4 CE 3 a ¦ 1.0 % ~ yes 0 1.4 CE 4 b ¦ 1.0 % yes 37 1.7 ~ . ....
. Table 3 Example Organic Polymer Primer Water Compos-( nEx~l ) Component Coating Resist- ite : or Com- Used? an~ Cycle parison Secon- Test:
: ~ Example . _ dary Blister . ¦ ("CE") Type Concen- Adhe- Width , .Number tration sion: in mm . Number . Peeled ~
Ex s A 0.1 % yes 0 < 0.5 . _ Ex 6 B 0.5 % yes 0 ~ 0.5 .
Ex 7 C 2.0 % yes 0 < 0.5 Ex 8 A 1.0 % no 1.2.
CE 5 nc ne yes 0 1.0 CE 6 none no 36 2.2 CE 7 a 1.0 % yes 0 1.1 CE 8 b 1.0 % yes 17 1.8 :~ 8 ~ ;~ SUBSTITUTE SHEET
W093/0926~ 2 1 2 1 ~ 8 ~6 PCT/~S92/08811 ~, Table 4 . I
- ._ Example Organic Polymer Primer Water Compo~-("Ex") Component Coating Resist- lte or Com- Used? ant Cycle parison Secon- Test:
Example dary Blister ("CE") Type Concen- Adhe- Width Number tration sion: in mm Number Peeled Ex 9 A 0.1 % yes 0 S 0.5 Ex 10 B 0.5 % yes S 0.5 Ex 11 C 2.0 % yes 0 S 0.5 Ex 12 A 1.0 % no 6 0.7 ~: CE 9 none yes 5 0.8 :: ~ CE 10 none no 36 1.5 CE 11 a 1.0 t yes _ 4 0.8 CE 12 b 1.0 % yes 17 1.2 :
,`
'~
~ .
.
::
Claims (6)
1. A phosphate conversion coating treatment composition for metal surfaces, characterized in that the treatment composition comprises a cationic organic polymeric compound that contains at least 1 cationic nitrogen atom and has a molecular weight of 1,000 to 1,000,000, or a salt of such a cationic organic polymeric compound.
2. A phosphate conversion coating treatment according to claim 1, wherein the cationic organic polymeric compound is a compound having a resin skeleton comprising at least one selection from epoxy resins, urethane resins, polybutadiene resins, acrylic resins, and maleic anhydride resins.
3. A process for forming a protective coating on a metal by contacting the metal with a phosphate conversion coating solution, characterized in that the phosphate conversion coating solution has a composition according to claim 1 or 2.
4. A process according to claim 3, wherein the metal is iron, zinc, or aluminum.
5. A process according to claim 4, wherein the protective coating formed has a composite structure, in which the res-in containing the cationic organic compound salt thereof penetrates into grain boundaries between phosphate crys-tals.
6. An article of manufacture comprising an outer surface of an organic protective coating, an intermediate film in-cluding phosphate ions underlying the organic protective coating, and a metal underlying the intermediate coating, characterized in that the intermediate coating has a com-posite structure, in which a resin containing a cationic nitrogen containing organic polymer or a salt thereof pene-trates into grain boundaries between phosphate crystals.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPH3-308,227 | 1991-10-29 | ||
| JP03308227A JP3139795B2 (en) | 1991-10-29 | 1991-10-29 | Metal surface treatment agent for composite film formation |
| CN92112560A CN1086269A (en) | 1991-10-29 | 1992-10-29 | Form the treatment process of anti-corrosion film in the metallic surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2121486A1 true CA2121486A1 (en) | 1993-05-13 |
Family
ID=36791816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002121486A Abandoned CA2121486A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0610315A1 (en) |
| JP (1) | JP3139795B2 (en) |
| CN (1) | CN1086269A (en) |
| AU (1) | AU2884192A (en) |
| BR (1) | BR9206685A (en) |
| CA (1) | CA2121486A1 (en) |
| MX (1) | MX9206223A (en) |
| NZ (1) | NZ244928A (en) |
| WO (1) | WO1993009265A1 (en) |
| ZA (1) | ZA928377B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306526A (en) * | 1992-04-02 | 1994-04-26 | Ppg Industries, Inc. | Method of treating nonferrous metal surfaces by means of an acid activating agent and an organophosphate or organophosphonate and substrates treated by such method |
| JP3193798B2 (en) * | 1993-01-13 | 2001-07-30 | 日本パーカライジング株式会社 | Metal surface treatment liquid for forming composite film for cold working of metal and method for forming composite film |
| DE4341602A1 (en) * | 1993-12-07 | 1995-06-08 | Bayer Ag | Use of a polyurethane dispersion as a penetration base and a process for the production of multicoat paint systems |
| JPH101782A (en) * | 1996-06-13 | 1998-01-06 | Nippon Paint Co Ltd | Metallic surface treating agent, treatment and surface treated metallic material |
| JPH1046101A (en) * | 1996-08-01 | 1998-02-17 | Nippon Parkerizing Co Ltd | Coated metallic material prepared by forming undercoat for film lamination on the surface of metallic material and its production |
| JPH10182916A (en) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | Metal surface-treating composition containing acrylic resin and containing n-heterocycle, treatment by using the same and treated metal material |
| DE69719047T2 (en) | 1996-10-21 | 2003-09-04 | Nippon Paint Co Ltd | METHOD FOR TREATING METAL SURFACES FOR FOOD CONTAINERS WITH A COMPOSITION CONTAINING AN ACRYLIC RESIN AND CONTAINERS CONTAINED THEREFORE |
| FR2769325B1 (en) * | 1997-10-08 | 1999-12-03 | Cfpi Ind | ACID BATH FOR ZINC PHOSPHATATION OF METAL SUBSTRATES, CONCENTRATE FOR THE PREPARATION OF THE BATH AND PHOSPHATATION METHOD USING THE SAME |
| US5972433A (en) * | 1997-12-05 | 1999-10-26 | Calgon Corporation | Method for treatment of metal substrates using Mannich-derived polyethers |
| FR2837209B1 (en) * | 2002-03-13 | 2004-06-18 | Rhodia Chimie Sa | USE OF BLOCK COPOLYMERS CARRYING PHOSPHATE AND / OR PHOSPHONATE FUNCTIONS AS ADHESION PROMOTERS OR AS PROTECTIVE AGENTS AGAINST CORROSION OF A METAL SURFACE |
| JP2008057047A (en) * | 2002-06-28 | 2008-03-13 | Jfe Steel Kk | Method for producing surface-treated zinc series metal plated steel sheet |
| JP4989842B2 (en) * | 2002-12-24 | 2012-08-01 | 日本ペイント株式会社 | Pre-painting method |
| US8075708B2 (en) | 2002-12-24 | 2011-12-13 | Nippon Paint Co., Ltd. | Pretreatment method for coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2159511B (en) * | 1984-04-25 | 1988-09-21 | Dearborn Chemicals Ltd | A method of inhibiting corrosion in aqueous systems |
| US4978399A (en) * | 1988-01-04 | 1990-12-18 | Kao Corporation | Metal surface treatment with an aqueous solution |
| DE3906898A1 (en) * | 1989-03-03 | 1990-09-06 | Henkel Kgaa | ZINC-BARIUM PHOSPHATION OF METAL SURFACES |
| JPH04193957A (en) * | 1990-11-28 | 1992-07-14 | Nippon Parkerizing Co Ltd | Chromating solution for substrate for clear coat |
-
1991
- 1991-10-29 JP JP03308227A patent/JP3139795B2/en not_active Expired - Lifetime
-
1992
- 1992-10-22 CA CA002121486A patent/CA2121486A1/en not_active Abandoned
- 1992-10-22 EP EP92922276A patent/EP0610315A1/en not_active Withdrawn
- 1992-10-22 WO PCT/US1992/008811 patent/WO1993009265A1/en not_active Application Discontinuation
- 1992-10-22 AU AU28841/92A patent/AU2884192A/en not_active Abandoned
- 1992-10-22 BR BR9206685A patent/BR9206685A/en active Search and Examination
- 1992-10-28 MX MX9206223A patent/MX9206223A/en unknown
- 1992-10-29 ZA ZA928377A patent/ZA928377B/en unknown
- 1992-10-29 NZ NZ244928A patent/NZ244928A/en unknown
- 1992-10-29 CN CN92112560A patent/CN1086269A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ZA928377B (en) | 1993-05-14 |
| NZ244928A (en) | 1994-10-26 |
| EP0610315A1 (en) | 1994-08-17 |
| JPH05117869A (en) | 1993-05-14 |
| CN1086269A (en) | 1994-05-04 |
| AU2884192A (en) | 1993-06-07 |
| MX9206223A (en) | 1993-11-30 |
| BR9206685A (en) | 1995-10-24 |
| WO1993009265A1 (en) | 1993-05-13 |
| JP3139795B2 (en) | 2001-03-05 |
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