CN1086269A - Form the treatment process of anti-corrosion film in the metallic surface - Google Patents
Form the treatment process of anti-corrosion film in the metallic surface Download PDFInfo
- Publication number
- CN1086269A CN1086269A CN92112560A CN92112560A CN1086269A CN 1086269 A CN1086269 A CN 1086269A CN 92112560 A CN92112560 A CN 92112560A CN 92112560 A CN92112560 A CN 92112560A CN 1086269 A CN1086269 A CN 1086269A
- Authority
- CN
- China
- Prior art keywords
- resin
- salt
- organic polymer
- cationic
- metal
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000005260 corrosion Methods 0.000 title abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229920000620 organic polymer Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 8
- -1 ion organic compound Chemical class 0.000 claims abstract description 8
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 4
- 238000007746 phosphate conversion coating Methods 0.000 claims 4
- 239000011253 protective coating Substances 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229940085991 phosphate ion Drugs 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000000805 composite resin Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000004922 lacquer Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 9
- 239000002987 primer (paints) Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000012756 surface treatment agent Substances 0.000 description 6
- 230000037452 priming Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
One bonderite that contains a kind of cationic organic polymer (or its salt) at metal (as iron, zinc, aluminium, or the like) the high anti-corrosion film of surface formation, this film also is excellent coating substrate lacquer, described cationic organic polymer contains at least one cationic nitrogen-atoms, and molecular weight is 1,000-1,000,000, the resin that this film preferably wherein is made of positively charged ion organic compound (or its salt) infiltrates the crystal boundary of phosphoric acid salt grain, and forms phosphoric acid salt/resin composite body simultaneously.
Description
The present invention relates to a kind of novelty such as iron, zinc, aluminium or the like metallic surface forms the treatment process of strong anti-corrosion film.The coating substrate that this anti-corrosion film also is an excellence.
At present, scribble the object of coating,, need more and more higher solidity to corrosion as car body and building materials.Up to the present, the metallic surface is to adopt phosphoric acid salt, chromate treating.Yet existing metal conditioner does not always show gratifying solidity to corrosion and clagging power.
The prior art that people know is, if with organic membrane, for example, and coating, binding agent, or the like, be coated in metal, for example, iron, zinc on the surface of aluminium or the like, then forms one deck phosphate layer with common applicable pretreatment process on this metallic surface.Using organic coating (being typically coating) before, the method improvement by on the metallic surface, forming one deck phosphate layer solidity to corrosion and clagging power.When requiring higher solidity to corrosion, before applying coating, carry out phosphatizing and aftertreatment (for example, with chromic acid or the like sealing) or use two kinds of processing of priming paint.Yet a less effect is only played in these aftertreatments (for example, with chromic acid or the like sealing).And, although use priming paint to improve the adhesive power of coating, also increased coating processes, therefore in fact damaged operability.
But, use priming paint for the object that scribbles coating for example car body and building materials, still need at present.For car body, form lithoform in the metallic surface, it is immersed in the water soluble paint to form electrodeposited coating then.This coating procedure is a type of primer coating, its objective is the solidity to corrosion on the surface of improving coated coating, and the solidity to corrosion of guaranteeing the car body internal surface, and this car body is difficult to be coated with finishing paint.Before using overlay coating also similarly with the priming paint application in building materials, to improve its solidity to corrosion.
The operating efficiency and the requirement that reduces cost reduce technological process, the exploitation but the gratifying method of this target awaits in applying operation.Therefore, when coating itself does not satisfy requiring of solidity to corrosion and coating adhesive power, only still has relatively poor solidity to corrosion with phosphate layer.When the higher solidity to corrosion of needs, will use phosphate layer and primer coating simultaneously.This has just caused high production cost, and needs bigger work area.Therefore, need exploitation to have the metal conditioner of high anti-corrosion and high coating adhesive power.Simultaneously, also needing to develop can be without the metal conditioner of primer coating.
As solution to the problems described above, the purpose of this invention is to provide a kind of metal conditioner, it can make the metal that is suitable for phosphate layer and handles (for example, iron, zinc, aluminium, or the like slightly be called " metal " down) have high anti-corrosion and a coating adhesive power.Further purpose of the present invention provides a kind of metal conditioner, and it can keep existing solidity to corrosion when having omitted primer coating.
For the result who addresses the above problem the extensive studies of carrying out is, have now found that, bathe film forming with the phosphatizing that contains organic polyhydroxyl compound (or its salt) with some characteristic, can obtain high anti-corrosion and coating adhesive power.The present invention just is being based on this discovery and is developing.
That is to say, anti-corrosion film with above-mentioned higher required character, can form by adopting process metal surfaces, this treatment agent can be in the metallic surface film forming, wherein this treatment agent is characterised in that comprising Bonderisation bathes, it contains this polymkeric substance of cationic organic polymer (or its salt) and contains at least 1 cationic nitrogen atom, and its molecular weight is 1,000-1,000,000 anti-corrosion film of the present invention is composite membrane preferably, and the crystal boundary that the resin that wherein constitutes positively charged ion organic compound (or its salt) has penetrated into phosphoric acid salt crystal grain forms phosphoric acid salt crystal grain/resin composite body simultaneously.
Surface treatment agent of the present invention comprises solution or the stable dispersions of cationic organic polymer in phosphate-treated solution.This phosphatizing is bathed and is comprised that any surface treatment bathes, and it can form the anti-corrosion film of phosphoric acid salt on the surface of metal (as, iron, zinc, aluminium, or the like), both can handle a kind of monomer sample of metal, the surface that also can handle two or more samples of above-mentioned metal simultaneously.Usually, its basal component is zine ion and phosphate anion, but it can contain nitrate ion arbitrarily, other metal ion (nickel, manganese, calcium, or the like), fluorochemical, and various oxygenant.But phosphatizing is bathed and do not make clear and definite qualification in text of the present invention, and the present invention has comprised all known phosphate and handled bath.
Cationic organic polymer must contain at least one cationic nitrogen-atoms, and its molecular weight is 1,000-1,000,000.Though its structure does not limit in the wideest embodiment of the present invention, but, the organic polymer that especially preferably has the resin matrix structure, wherein contain at least a Resins, epoxy that is selected from, urethane resin, polybutadiene, acrylic resin, maleic anhydride resin, wherein, these resins all contain the nitrogen atom group.
The salt of cationic organic polymer comprises its inorganic salt and organic salt, and the example of inorganic salt is as being phosphoric acid salt, nitrate, and vitriol, or the like, the example of organic salt is as being acetate, propionic salt, and gluconate, or the like.Can use the sample of one or both or multiple cationic organic polymer (or its salt).Less than 1,000 o'clock, solidity to corrosion can only obtain less improvement at molecular weight, and surpassed at 1,000,000 o'clock at molecular weight, then was difficult to obtain solution or stable dispersions in the zinc phosphate salt bath.
Further, paint additive (as pigment, or the like), the resin of other kind, activator, or the like also can on the basis of selecting, add.
About the technology of process metal surfaces, the present invention can use transformation processing method, as spraying or dipping, and electrolytic method, all treatment agents among the present invention are not subjected to the restriction of particular treatment method.
Embodiment
Effect of the present invention is carried out detailed explanation by the following examples and comparative example.Yet the present invention is not limited only to embodiment, and present embodiment has only been described typical precoating phosphatizing and typical coating system.In comparative example, with done among the embodiment with embodiment in identical evaluation and processing, but be to use the organic polymer outside the scope of the invention and omitted cationic organic polymer.
The usual conditions of embodiment and comparative example are as follows:
Workpiece: cold-rolled steel sheet; Electroplating steel plate (zinc plated film=20g/m
2); Aluminium sheet (JIS5052).
Surface treatment agent: the polymkeric substance that uses in cationic organic polymer that uses among the embodiment and the comparative example is shown in table 1.PARBOND
TML3020 is used for the surface treatment agent of car body, and Japanese phosphatizing company limited produces, and the Bonderisation that is used to not have organic polymer is bathed.This is that a kind of typical phosphates surface treatment is bathed.
Processing sequence:
1) degrease: 2% FINECLEANER
TML4460(Japan phosphatizing company limited) solution was in 42 ℃ of hydro-peenings 120 seconds.
2) washing: in room temperature hydro-peening 30 seconds.
3) surface conditioning: 0.1% PARCOLENE
TMZN(Japan phosphatizing company limited) solution was in room temperature hydro-peening 20 seconds.
4) surface treatment agent of surface treatment agent of the present invention and comparative example is all used in following condition; Flooded 120 seconds in 42 ℃.
5) washing: in room temperature hydro-peening 30 seconds.
6) washed with de-ionized water (specific conductivity, 0.2 little Siemens/cm) was in room temperature hydro-peening 20 seconds.
After above-mentioned steps is finished,, apply (step of priming is saved sometimes, and institute's following table is described) according to following step drying:
Table 1
The chemical molecular amount of the organic polymer that treatment process adopts
Character
A HN (CH
3)
2With dihydroxyphenyl propane 8,800
The adducts of Resins, epoxy
B methyl methacrylate and methacrylic acid 20,000
The multipolymer of dimethylamino ethyl ester
C H
2NCH
2N(CH
3)
22,000
Adducts with maleic anhydride resin
a H
2NCH
2N(CH
3)
2800
Adducts with maleic anhydride resin
B polyvinyl alcohol 3,000
1) primer coating: galvanic deposit ELECRON
TM9410 (Ken Sai (Kansai) coating Co., Ltd. products) are carried out galvanic deposit coated with producing film thickness=20 micron; Baked 30 minutes in 175 ℃.
2) inter coat: KPX36(agree match (Kansai) coating Co., Ltd. and produces); Thickness=30 micron; Baked 30 minutes in 140 ℃.
3) overlay coating: RUGABAKE
TMB531(agree match coating Co., Ltd. and produces); Thickness=40 micron; Baked 30 minutes in 140 ℃.
The sample of all embodiment and comparative example is all handled in a like fashion by above-mentioned steps, just the chemical property difference (step 4) of the surface treatment agent that adopts.
Performance evaluation:
1) water-fast second adhesive power: the sheet material that has applied impregnated in the deionized water 240 hours in 40 ℃, and sharp icking tool marks 100 squares, and (chessboard of 2mm * 2mm), cut is to base material.After peeling off with glassine paper, calculate the quantity of being stripped from square.The area of being stripped from is more little, shows that performance is good more.
2) compound cycle test: draw a cross and be deep into base material with sharp-pointed cutting knife in the sheet surface that has applied, then with sheet material by T
1→ T
2Circulation (face as follows) re-treatment 14 times.After the test, measure the width that maximum film bubbling is gone up on a surface, come assess performance thus from cross.
T
1: salt-fog test (JIS Z2371): 24 hours
T
2: wetting test (50 ℃, 70%RH): 216 hours
Table 2,3 and 4 have reported by respectively cold-rolled steel sheet, electroplating steel plate and aluminium sheet carry out the adhesive power and the solidity to corrosion of the coating that surface treatment obtains.These tables have also comprised the experimental result of comparative example.
Test-results shows that compare with phosphatizing, solidity to corrosion and clagging power have suitable raising under the situation that adopts the metal conditioner that is used to form composite membrane of the present invention to handle.Therefore, even omitted primer coating, effect of the present invention also is similar to primer coating coating on phosphate layer.
When the organic polymer that uses not within the scope of the invention, perhaps in fact do not tell on, perhaps its performance has in fact descended.
In sum, the metal conditioner that is used to form composite membrane of the present invention has improved solidity to corrosion and clagging power, and can save primer coating.
Table 2
Table 3
Table 4
Claims (6)
1, the phosphate conversion coating treatment compositions that is used for the metallic surface is characterized in that said composition contains a kind of cationic organic polymer, or the salt of this cationic organic polymer, this polymkeric substance contains at least 1 cationic nitrogen-atoms, and molecular weight is 1,000 to 1,000,000.
2, the phosphate conversion coating treatment compositions of claim 1, wherein cationic organic polymer has a kind of resin matrix structure, and it comprises at least a Resins, epoxy that is selected from, urethane resin, polyhutadiene fat, two olefin(e) acid resins, the resin of maleic anhydride resin.
3, a kind of method that forms protective coating in the metallic surface, this method is that metal is contacted with a kind of phosphate conversion coating solution, it is characterized in that containing in this phosphate conversion coating solution the composition of claim 1 or 2.
4, the method for claim 3, wherein metal is an iron, zinc, or aluminium.
5, the method for claim 4, wherein formed protective coating has composite structure, and the resin that wherein contains positively charged ion organic compound or its salt infiltrates in the crystal boundary of phosphoric acid salt crystal grain.
6, a kind of goods; this system device includes machine protective coating outside surface; be positioned at the intermediate coat of the phosphate ion below organic protectiveness film; with the metal that is positioned under the inter coat; it is characterized in that this inter coat has composite structure, the resin that wherein contains organic polymer with cationic nitrogen atom or its salt infiltrates the crystal boundary of phosphoric acid salt crystal grain.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03308227A JP3139795B2 (en) | 1991-10-29 | 1991-10-29 | Metal surface treatment agent for composite film formation |
| AU28841/92A AU2884192A (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| CA002121486A CA2121486A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| PCT/US1992/008811 WO1993009265A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| EP92922276A EP0610315A1 (en) | 1991-10-29 | 1992-10-22 | Treatment for the formation of a corrosion resistant film on metal surfaces |
| BR9206685A BR9206685A (en) | 1991-10-29 | 1992-10-22 | Phosphate conversion coating treatment composition for metal surfaces, process for forming a protective coating on a metal, and manufactured product |
| MX9206223A MX9206223A (en) | 1991-10-29 | 1992-10-28 | TREATMENT FOR THE FORMATION OF A FILM RESISTANT TO CORROSION ON METAL SURFACES. |
| CN92112560A CN1086269A (en) | 1991-10-29 | 1992-10-29 | Form the treatment process of anti-corrosion film in the metallic surface |
| ZA928377A ZA928377B (en) | 1991-10-29 | 1992-10-29 | Treatment for the formation of a corrosion resistant film on metal surfaces. |
| NZ244928A NZ244928A (en) | 1991-10-29 | 1992-10-29 | Phosphate conversion coatings for metal surfaces, containing an organic polymer which has cationic nitrogens; article of manufacture |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
|---|---|
| CN1086269A true CN1086269A (en) | 1994-05-04 |
Family
ID=36791816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112560A Pending CN1086269A (en) | 1991-10-29 | 1992-10-29 | Form the treatment process of anti-corrosion film in the metallic surface |
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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532468C (en) * | 2002-03-13 | 2009-08-26 | 罗狄亚化学公司 | Use of block copolymers bearing phosphate group and/or phosphonate radical functional group as adhesion promoters or as protecting agents against the corrosion of a metallic surface |
Families Citing this family (12)
| 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 | Metal surface treatment agent, treatment method and surface treated metal material |
| JPH1046101A (en) * | 1996-08-01 | 1998-02-17 | Nippon Parkerizing Co Ltd | Coated metal material having a base film for film lamination formed on the surface of metal material, and method for producing the same |
| JPH10182916A (en) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | Acrylic resin-containing metal surface treatment composition containing N heterocycle, treatment method and treated metal material |
| EP0933408B1 (en) | 1996-10-21 | 2003-02-12 | Nippon Paint Co., Ltd. | Metal surface treatment for food can using an acrylic resin containing composition and the so treated can |
| 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 |
| JP2008057047A (en) * | 2002-06-28 | 2008-03-13 | Jfe Steel Kk | Method for producing surface-treated galvanized steel sheet |
| DE60324245D1 (en) | 2002-12-24 | 2008-12-04 | Chemetall Gmbh | Pretreatment process prior to coating |
| JP4989842B2 (en) * | 2002-12-24 | 2012-08-01 | 日本ペイント株式会社 | Pre-painting method |
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 WO PCT/US1992/008811 patent/WO1993009265A1/en not_active Ceased
- 1992-10-22 BR BR9206685A patent/BR9206685A/en active Search and Examination
- 1992-10-22 EP EP92922276A patent/EP0610315A1/en not_active Withdrawn
- 1992-10-22 AU AU28841/92A patent/AU2884192A/en not_active Abandoned
- 1992-10-22 CA CA002121486A patent/CA2121486A1/en not_active Abandoned
- 1992-10-28 MX MX9206223A patent/MX9206223A/en unknown
- 1992-10-29 NZ NZ244928A patent/NZ244928A/en unknown
- 1992-10-29 ZA ZA928377A patent/ZA928377B/en unknown
- 1992-10-29 CN CN92112560A patent/CN1086269A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532468C (en) * | 2002-03-13 | 2009-08-26 | 罗狄亚化学公司 | Use of block copolymers bearing phosphate group and/or phosphonate radical functional group as adhesion promoters or as protecting agents against the corrosion of a metallic surface |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9206223A (en) | 1993-11-30 |
| JPH05117869A (en) | 1993-05-14 |
| ZA928377B (en) | 1993-05-14 |
| AU2884192A (en) | 1993-06-07 |
| EP0610315A1 (en) | 1994-08-17 |
| CA2121486A1 (en) | 1993-05-13 |
| WO1993009265A1 (en) | 1993-05-13 |
| JP3139795B2 (en) | 2001-03-05 |
| BR9206685A (en) | 1995-10-24 |
| NZ244928A (en) | 1994-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2454199C (en) | Chemical conversion coating agent and surface-treated metal | |
| EP1433877B1 (en) | Pretreatment method for coating | |
| CN1200139C (en) | Corrosion protection methods for metal surfaces | |
| KR101315417B1 (en) | Composition for metal surface treatment, metal surface treatment method, and metal material | |
| US3175964A (en) | Surface treatment of metal article by water-soluble (film-forming) material | |
| CN1086269A (en) | Form the treatment process of anti-corrosion film in the metallic surface | |
| RU2632063C2 (en) | Chemical conversion processing agent for surface treatment of metal substrate and method for metal substrate surface treatment with its application | |
| KR890004045B1 (en) | Coating metal substrate with improved corrosion resistance and manufacturing method | |
| EP0624182A1 (en) | Autodeposition coating composition | |
| CN1171824A (en) | Treatment of aluminium or aluminium alloys | |
| US4500610A (en) | Corrosion resistant substrate with metallic undercoat and chromium topcoat | |
| CN1034681C (en) | Method for making manganese-containing zinc phosphate layer on surface of zinc-plated steel | |
| CN1239742C (en) | phosphate-treated zinc-based plated steel sheet | |
| CN1122118C (en) | Method of making iron-electroplated aluminium materials | |
| WO1995027809A1 (en) | Method of pre-treating metal substrates prior to painting | |
| CN111074255A (en) | Metal surface pretreatment agent and preparation method and application thereof | |
| EP0278283B1 (en) | Chromium-containing low-cure coating composition | |
| CN219603688U (en) | Galvanized silane chromium-free passivation coating structure | |
| CN113512722B (en) | Non-phosphorus and non-nitrogen environment-friendly metal surface film treating agent and application thereof | |
| CA2118856A1 (en) | Enhanced corrosion resistant one-step coatings and treated metallic substrates | |
| JP2619626B2 (en) | High corrosion resistant surface treated steel sheet for cationic electrodeposition coating | |
| CA1046980A (en) | Electrocoating metal products | |
| CN1034682C (en) | Chromating method of zinc-based plated steel sheet | |
| JPH0557239A (en) | Aluminum surface treated plate with excellent spot weldability and electrodeposition paintability | |
| CN1465742A (en) | Zinc phosphate treated galvanized steel sheet with good corrosion resistance and color tone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |