CN1386901A - Metal surface treating agent and method, and surface treatment of metal material - Google Patents
Metal surface treating agent and method, and surface treatment of metal material Download PDFInfo
- Publication number
- CN1386901A CN1386901A CN02118035A CN02118035A CN1386901A CN 1386901 A CN1386901 A CN 1386901A CN 02118035 A CN02118035 A CN 02118035A CN 02118035 A CN02118035 A CN 02118035A CN 1386901 A CN1386901 A CN 1386901A
- Authority
- CN
- China
- Prior art keywords
- compound
- vanadium
- metal
- acid
- metallic
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
To provide a chromium-free metallic surface treating agent used for imparting excellent corrosion resistance and alkali resistance to a metallic material and to provide a metallic surface treating method and a surface treated metallic material using the same. This metallic surface treating agent contains at least one kind of vanadium compound (A) and a metallic compound (B) containing at least one kind of metal selected from the groups consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium. For further improving the physical properties thereof, the prescription of the ratio of pentavalent vanadium ions to the whole vanadium and the incorporation of an organic compound having a specific functional group, an etching agent, a water soluble high polymer or/and a water-based emulsion resin are possible. The metallic surface treating method and the surface treated metallic material use the same treating agent.
Description
Technical field
The present invention is relevant to be the coiled sheet of former material to minor metal, can invest superior solidity to corrosion and alkali resistance on the surface of molding, and for making formation not contain the tunicle of chromium and the metal conditioner of usefulness, metal surface treating method, through giving the surface-treated metallic substance.
Again specifically, the present invention is relevant, and to be formed at time zinc-based metal plated steel sheet, copper coin, aluminum-based metal material be the car body of former material for making, automobile spare part, building materials, household electrical appliances invest superior solidity to corrosion and the alkali-proof tunicle that does not contain chromium and surface treatment agent, the surface treatment method of usefulness with making on moulding goods such as spare part, casting product, the coiled sheet etc., through giving the surface-treated metallic substance.
Background technology
The metallic substance of zinc-based metal plated steel sheet, steel plate, aluminum-based metal material etc. is subjected to ion contained in the oxygen, moisture, moisture in the atmosphere etc. and oxidation, corrosion.As for preventing these corroding method, metal material surface is contacted with the treatment solution that contains chromium of chromic acid chromium hydrochlorate, Plessy's green etc. and make the method that forms the chromic salt tunicle.
Adopt the formed tunicle of these chromate treating, have superior solidity to corrosion, coating tack, but in this treatment solution, contain deleterious valency chromium, numerous and diverse or expend cost during wastewater treatment, in addition, the also valency chromium that contains in the tunicle that forms in processing, so see it by environment face, safe face, this is excluded use.
As for the method that adopts the non-chromate treatment solution that does not contain chromium, in Japanese kokai publication hei 7-278410 communique, disclose metal material surface that the phenol resins based polymer that contains particular configuration and acidic cpd are arranged with polymer composition and surface treatment method, disclose the superior metal conditioner and the treatment processs such as anti-finger printing of the silicon oxygen coupler more than two kinds of the reactive functional group that the particular configuration with not of the same race mutually and mutually reactive is arranged in the Japanese kokai publication hei 8-73775 communique, disclose the metal conditioner and the treatment process of the phenol resins based polymer that the silicon oxygen coupler that contains particular configuration and particular configuration are arranged in the Japanese kokai publication hei 9-241576 communique, disclose in the Japanese kokai publication hei 10-1798 communique Resins, epoxy that contains at least one nitrogen-atoms is arranged, the acrylic ester resin, the metal conditioner of organic polymer such as peace ester resin and specific polybasic anionic, treatment process and processing metallic substance, disclose in the Japanese kokai publication hei 10-60233 communique to have and contain (1) and contain the rust-preventive agent that the bisphenol-A epoxy of particular configuration is a resin (2), the solid shape proportion by subtraction of mixing phenol resin and characteristic resins such as polyester in addition becomes 4: 1～and 1: 4 rust-preventive agent, adopt the treatment process of (1) and (2) and handle metallic substance.
Yet in the metal finishing that does not adopt chromium of these patent gazettes, though there is treatment solution not contain chromic advantage, opposite formed tunicle and chromate treating solidity to corrosion deficiency have the also insufficient shortcoming of anti-finger printing, oilness in addition.
Again in Japanese kokai publication hei 10-1789 communique, among specific polybasic anionic, record vanadic acid, only the vanadic acid of the oxygen acid of the vanadium of pentavalent is that water tolerance, alkali resistance are inferior, so especially with when the metallic substance of cleanings such as alkali through giving processing, have by tunicle and peel off, solidity to corrosion is the improper of extreme reduction.Record again and handle after washing and dry,, have the problem of the waste water such as COD that cause by organism though there is not the problem of chrome waste water.
In addition, as for the invention of using vanadium compound as rust-preventive agent, in Japanese kokai publication hei 1-9229 communique, disclose the phosphate ion source that emits phosphate ion under the environment of the existence of water and oxygen is arranged, emit the rust proof paint of vanadic acid ionic vanadic acid ion source and film formation property resin, in No. 2795710 communique of Japanese Patent, announcement has the vanadic acid ionic vanadic acid ion source of (A) being emitted specific concentrations in making the dispersion liquid that is scattered in water, and the antirust composition that (B) specific compound of the deliquescent organic phosphoric acid etc. of expression specific concentrations cooperates with specific ratios in making the dispersion liquid that is scattered in water.The vanadic acid ion source because of the rust-stabilising pigment that acts as rust proof paint gives interpolation, if when the high-temperature calcination vanadic acid ion source more than 600 ℃, then forms the pigment that median size is counted μ m.The particle of this pigment have to a certain degree thickness (several times of the particle diameter of pigment) though film in can bring into play corrosion protection result, yet fail to bring into play corrosion protection result fully at the film of field of surface treatment (below the number μ m).Left standstill again when the treatment agent, wherein these particles have aggegation and settled improper.
Therefore be that metal conditioner is unavailable forming the non-chromate that can invest the tunicle of superior solidity to corrosion, alkali resistance and anti-finger printing simultaneously under the present situation to metal material surface.
Summary of the invention
The present invention finishes for the problem that solves above-mentioned known technology and bring, and to provide metallic substance is invested superior solidity to corrosion and alkali resistance and the metal conditioner that does not contain chromium, metal surface treating method and the surface-treated metal material of usefulness are purpose.
The inventor serves as the surface treatment agent processing metal material surface of necessary composition to solving the means of aforementioned problems, rely on and adopting with vanadium compound and specific metallic compound, and discovery can have superior solidity to corrosion and alkali-proof tunicle, so that finish the present invention.
That is to say that the present invention is relevant to containing at least a vanadium compound (A), and the metallic compound (B) of at least a metal selected of the colony that is formed by zirconium, titanium, molybdenum, tungsten, manganese and cerium is the metal conditioner of feature.
In aforementioned vanadium compound (A), Oxidation Number is the vanadium ion of pentavalent and the ratio V of full vanadium
5+/ V is in 0～0.6 scope, but the stability of the vanadium compound of treatment agent forms the solidity to corrosion of tunicle and the viewpoint of the raising of alkalescence is also more suitable.
Again in the aforementioned metal surface treatment agent, make again and contain organic compound (C) with at least a functional group that the colony that formed by hydroxyl, carbonyl, carboxyl, 1～3 grade of amido, vinegar amido, phosphate and phosphonate group selects, situation at the vanadium compound that adopts pentavalent, this is reduced into 4 valencys or 3 valencys, and/or is to make the stability of the vanadium compound in the treatment solution of the present invention improve more suitable.
Again, in the aforementioned metal surface treatment agent, make and contain by mineral acid, at least a etching reagent (D) that organic acid and fluorine cpd are selected is for the tack that makes formed tunicle improves more suitable.
Again, in the aforementioned metal surface treatment agent, make again and contain water-soluble polymer or water system latex resin (E), more suitable in order to the solidity to corrosion, anti-finger printing, solvent resistance and the surface lubrication that improve the tunicle that forms.
About after metal material surface is handled with aforesaid any metal conditioner, heat drying to the temperature of previous materials becomes the 50-250 ℃ of surface treatment method for the metallic substance of feature again in the present invention.
The present invention moreover the relevant surface-treated metal material that adopts the aforementioned surfaces treatment process and have tunicle through giving formation.
Embodiment
Making the vanadium compound (A) that contains in metal conditioner of the present invention, is the vanadium compound of 5 valencys, 4 valencys, 3 valencys or divalent, for example Vanadium Pentoxide in FLAKES (V by the Oxidation Number of vanadium
2O
5), metavanadic acid (HVO
3), metavanadic acid amine ammonium, sodium metavanadate, oxygen base vanadium trichloride (VOCL
3) wait vanadium compound, the vanadous oxide (V of Oxidation Number pentavalent
2O
3), vanadium dioxide (VO
2), oxygen base Vanadosulfuric acid (VOSO
4), oxygen base acetyl group vinegar copper acid esters vanadium [V0 (0C (CH
3)=CHCOCH
3)]
2], vanadium acetyl group vinegar copper acid fat [V (OC (CH
3)=CHCOCH
3)]
3], vanadium trichloride (VCl
3), phosphorus vanadium base copper acid { H
15-X[PV
12-xMo
xO
40] nH
2O (6＜X＜12, n＜30) }, Vanadosulfuric acid (VSO
47H
2O), vanadous chloride (VCl
2), the vanadium compound of the Oxidation Number 4～divalent of vanadium oxide (VO) etc. etc. select at least a.
The vanadium compound that this treatment agent contains Oxidation Number 4 valencys following (being generally 4～divalent) is advisable as vanadium compound.That is Oxidation Number is the vanadium ion of pentavalent and the ratio V of full vanadium
5+/ V (in the formula, V
5+And V represents that separately Oxidation Number is vanadium quality and whole vanadium quality of 5 valencys) be preferably in 0～0.6 scope, more be preferably in 0～0.4 scope, more suitable again in 0～0.2 scope, and the most suitable in 0～0.1 scope.
Aforementioned proportion surpasses at 0.6 o'clock, and the stability variation of the vanadium compound in treatment agent, the solidity to corrosion of formed tunicle, alkali resistance can reduce.
As for making the method that in this treatment agent, contains 4～divalent vanadium compound, except that the vanadium compound that adopts aforesaid 4～divalent, can adopt reductive agent that the vanadium compound of 5 valencys is reduced into 4～divalent in advance.Used reductive agent be inorganic system, organic system any one all can, but organic system preferably is preferably especially and adopts aforementioned organic compound (C).
Make and contain at least a metallic compound (B) that the colony that is formed by zirconium, titanium, molybdenum, tungsten, manganese and cerium in the metal conditioner of the present invention is selected, the salt of the oxide compound of aforementioned metal, oxyhydroxide, complex compound, mineral acid or organic acid etc., as for relevant metallic compound (B), for example can enumerate Zircosol ZN (ZrO (NO
3)
2), zirconyl acetate, zirconyl sulfate, zirconyl carbonate amine { (NH
4)
2[Zr (CO
3)
2(OH)
2], zirconium acetate, zirconyl carbonate (TiOSO
4), two acetyl group third the bronze medal { (C of zirconium lactate, diisopropoxy titanium
5H
7O
2)
2Ti[OCH (CH
3)
2]
2, the reactant of lactic acid and alkyl dioxide, platinic acid (H
2MoO
4), ammonium molybdate, Sodium orthomolybdate, molybdophosphate compound (ammonium phosphomolybdate { (NH for example
4)
3[PO
4MO
12O
36] 3H
2O}, molybdophosphate sodium { Na
3[PO
412MO
12O
3] nH
2O}, metatungstic acid { H
6[H
2W
12O
40], ammonium metawolframate { (NH
4)
6[H
2W
12O
40], metatungstic acid sodium, to wolframic acid { H
10[W
12O
46H
10], to ammonium tungstate, to sodium wolframate, cross mangaic acid (HmnO
4), potassium permanganate, sodium permanganate, phosphate dihydrogen manganese [Mn (H
2PO
4)
2], manganous nitrate [Mn (NO
3)
2], manganous sulfate, manganous fluoride, manganous carbonate (MnCO
3), manganese acetate, cerous acetate [Ce (CH
3CO
2)
3], cerous nitrate, Cerium II Chloride etc.
In metal conditioner of the present invention, look in case of necessity, the organic compound that is contained (C) has at least a functional group's that the colony that formed by hydroxyl, carbonyl, carboxyl, 1～3 grade of amido, vinegar amido, phosphate and sulfonic group selects organic compound.
To the organic compound (C) of being correlated with, can enumerate: methyl alcohol, ethanol, Virahol, alcohols such as ethylene glycol, formaldehyde, acetaldehyde, furfural, acetyl group acetone, the acetyl group ethyl acetate, two trimethylammonium acetyl group methane, the carbonyl compound of 3-methylpentane diketone etc., formic acid, acetate, propionic acid, tartrate, xitix, glyconic acid, citric acid, organic acids such as oxysuccinic acid, triethylamine, trolamine, quadrol, compare pyridine, miaow is bitten, than coughing up, woods, unit's hydrogen is than amine compound such as pyridines, Dimethyl formamide, ethanamide, the third vinegar amine, N-methyl-prop vinegar amine, Deng the sulfuric acid amine compound, glycine, Beta Alanine, proline, the amido acids of L-GLUTAMICACID etc., amido three (methylene sulfonic acid), 1-hydroxy ethylene-1,1 '-disulfonic acid, ethylenediamine tetraacetic (methylene sulfonic acid), organic phosphoric acids such as phytic acid, glucose, seminose, monoses such as semi-lactosi, maltose, oligosaccharides classes such as sucrose, starch, natural polysaecharides such as Mierocrystalline cellulose, Weibull, humic acids, lignin sulfonic acid, the aromatics of poly-phenol etc., polyvinyl alcohol, polyoxyethylene glycol, polyacrylic acid, polypropylene vinegar amine, poly-ethyliminum, the synthetic macromolecule of water-soluble nylon etc. etc.
In these organic compound, so that at least a person that selects that a part contains more than 2 is advisable, and contain more than 2 at least a person who selects from hydroxyl, carbonyl, carboxyl, phosphate and sulfonic group as the functional group for better with a part in aforementioned functional group.
The use of these organic compound (C), the situation at the vanadium compound that uses pentavalent is reduced into 4 valencys, 3 valencys or divalent with this, and/or is that the stability of the vanadium compound in the treatment solution of the present invention is improved so more suitable.
Organic compound (C), prior Hybrid Heating vanadium compound (for example at 40～100 ℃ of 5～120 clock) etc., and make and fully carry out reduction reaction, the mixture of stabilization reaction can be matched with in the surface treatment agent, but also can be used as after the surface treatment agent of simple mixing has been coated on the metallic surface, the beginning reduces also possible when heat drying.
In surface treatment agent of the present invention, look in case of necessity, at least a compound of the etching reagent that is contained (D) for selecting by the salt (particularly alkaline metal salt such as ammonium salt or sodium salt, sylvite) and the fluorine cpd of mineral acid, organic acid, mineral acid or organic acid, when being coated with cloth treating agent or the material metal use.As for relevant etching reagent (D), can adopt organic acid such as mineral acid such as phosphoric acid, nitric acid, sulfuric acid or its salt (particularly ammonium salt, sodium salt, sylvite), formic acid, acetate or its salt (particularly ammonium salt, sodium salt, sylvite), hydrofluoric acid, boron to fluoridize hydracid (HBF
4), silicon fluoridizes hydracid (H
2SiF
6), zirconium fluoridizes hydracid (H
2ZrF
6), titanium fluoridizes hydracid (H
2TiF
6), Tin tetrafluoride. (I) (SnF
2), Tin tetrafluoride. (II) (SnF
4), the fluorine cpd of ferrous fluoride.
The use of etching reagent (D) improves because of the tack that can make formed tunicle, so more suitable.As for the amount of each constituent in the treatment agent of the present invention, vanadium compound (A) is to convert in vanadium to be preferably 1～200g/L, is preferably 2～100g/L.Metallic compound (B) converts in metal and is preferably 1～200g/L, is preferably 2～100g/L, and the mass ratio of vanadium compound (A)/metallic compound (B) converts in metal again, is preferably 1/9～9/I, is preferably 2/8～8/2.
Organic compound (C) is 1 o'clock with the vanadium quality of 5 valencys of the Oxidation Number in the vanadium compound, is preferably 0.05～10, is preferably 0.1～5.If when reducing the excessive interpolation of aequum, because of the stability in going back the treatment solution of substance can improve, so more suitable.
Etching reagent (D) is preferably 1～200g/L, is preferably 2～100g/L.
In treatment agent of the present invention, for improving its solidity to corrosion, anti-finger printing, solvent resistance and surface lubrication, can add water-soluble polymer or water system latex resin (E), water-soluble polymers such as polyacrylic acid, polypropylene vinegar amine, tool vinyl alcohol, polyoxyethylene glycol for example, water system latex resins such as the acrylic resin of water-dispersion kenel, urethane resin, Resins, epoxy, vibrin, polyamide resin, polyene resin, ethylene-acrylic acid polymer based resin, polyformaldehyde resin, poly-butyral resin; These can use two or more uses also capable of being combined separately, again, resin in the water system latex resin (E) can be aqueous dispersion, also can be solid shape disperses, the addition of water-soluble polymer or water system latex resin (E), 5～95% quality with complete nonvolatile component are advisable, and better with the 10-90% quality.
In the treatment agent of the present invention, can add the silicon colloidal sol and/or the metal-sols such as alumina sol, TiO 2 sol of water-dispersion kenel, add these materials whereby in order to improve solidity to corrosion, water tolerance, anti-finger printing, at this moment, the amount of being added is advisable with 2～80% quality of complete nonvolatile component, and is better with 5～60% quality again.
At treatment agent of the present invention, can add silicon alkane couplers such as amido silicon alkane, epoxy group(ing) silicon alkane, thiol group silicon alkane, to improve adherence, solidity to corrosion, at this moment, the amount of interpolation is preferably 5～40% quality of whole nonvolatile component, is preferably the 10-30% quality whereby.
Again, in the treatment agent of the present invention, can add polyethylene wax, Poly Propylene Wax, Microcrystalline Wax, carnauba wax, poly-tetrafluoro closes lubricants such as ethene, whereby to give sliding, shaping processability, antisitic defect, at this moment, the amount of adding is preferably 1～40% quality of complete nonvolatile component, more is preferably the 5-30% quality.
And refer to composition remaining behind 110 ℃ of heat drying surface treatment agents in the whole nonvolatile component of the present invention.
Though the employed solvent of surface treatment agent of the present invention is based on water, the improvement of the drying property of tunicle etc. is looked and also do not hindered alcohol, ketone, ethoxy ethanol in case of necessity is the merging use of water-miscible organic solvent.
In addition, do not undermine purport of the present invention or by the scope of film properties in can add interfacial agent, defoamer, all spreader, fungi-proofing mould proof, tinting material etc.
Next illustrates surface treatment method of the present invention.
Do not give special restriction as for step before the present invention, but before carry out this processing, be attached to oil content, dirt, inferior alkaline defatting agent or the acid film fat agent cleaning on the former material or carried out hot water wash, solvent cleaning usually for removal.Its backsight carries out the surface adjustment by acid, alkali etc. in case of necessity, aspect the cleaning on former material surface, sanitising agent is not remained on the former material surface as far as possible being preferably after the cleaning to be washed to.
As for this treatment process, surface treatment agent of the present invention is coated the surface of metallic substance after, if can get final product, then do not give special restriction as for coating process, drying means etc. at 50～250 ℃ of heat dryings.
Usually on former material surface, adopt the rolling method that makes the transfer printing of treatment agent roller coat and give coating, or utilize the method that press dry with running roller after the showering such as sprinkle mode, the raw-material method of dipping in treatment solution, the method for spray cloth treating agent to the former material.The temperature of treatment solution is not given special restriction, but the solvent of this treatment agent system so treatment temp is preferably 0～60 ℃, is preferably 5～40 ℃ based on water.
Drying step not necessarily need heat or with the physical removal of blowing etc. also can, but form property for making by mould, the tack raising, heat drying also can.The temperature of this situation is 50～250 ℃, is preferably 60～220 ℃.
The adhesion amount of formed tunicle is preferably 0.005～1.5 μ m in dry film thickness, suitable 0.01～1.0 μ m, fail to obtain enough solidity to corrosions during less than 0.005 μ m, and on tack between being coated with, if on tunicle, can generate be full of cracks etc. when surpassing 1.5 μ m, the misgivings of the tack reduction of tunicle itself are arranged.
On the formed tunicle of surface treatment agent of the present invention, the organic polymer tunicle is set whereby to making desciccator diaphragm thickness become 0.3～3.0 μ m, except that the solidity to corrosion and alkali resistance that improve the metal to be treated material, can invest anti-finger printing, solvent resistance and surface lubrication.
As for the method that this kind organic polymer tunicle is set, coating with the organic polymer of water-soluble or water dispersible be principal constituent on be coated with treatment agent (Z), the arrival temperature of former material is that the method for 50～250 ℃ of heat dryings is good.Keep supplying the organic polymer of the water-soluble or water dispersible that is coated with treatment agent (Z) use, polymerization addition polymerization unsaturated monomer and CALCIUM ACRYLATE be that resin, polyene cigarette are resin, the epoxy that is got by condensation reaction is a resin, amino acid is that resin, polyester based resin, polyamide are resin, phenol resin etc., aforementioned organic macromolecule glass tansition temperature is preferably 0～120 ℃, is preferably 10～100 ℃.Tunicle shortcoming intensity, hardness during less than 0 ℃, if film-forming properties is inferior when surpassing 120 ℃, tack is inferior.
Be coated with treatment agent on aforementioned, contain wait organic polymer to select thus at least a, other are that the obdurability of tunicle or anti-finger printing are improved, and are advisable so that contain the water dispersible silicon, moreover for oilness is improved, are good to add water system wax.The amount of these compositions is 100 quality timesharing with whole non-volatile contents, is that organic polymer is preferably 50～100 quality branches in non-volatile content, and the water dispersible silicon is preferably 0～40 quality branch, and water system wax is preferably 0～30 quality branch.Can make the linking agent that contains crosslinked organic polymer again.[effect]
Surface treatment agent of the present invention gives to be coated on the former material metal and makes when the heat drying, with the reaction of former material metallic surface, forms fine and close passive state tunicle.
Demonstrate and rely on the superior solidity to corrosion of the formed tunicle of surface treatment agent of the present invention, remove blocking the effect that the oxygen, moisture, the ionic that hide resistance tunicle institute tool see through, can be considered the effect (smoothing of current potential) of corroding the electronics delocalization is caused.With the specific vanadium compound of the present invention (A), the vanadium compound system of pentavalent is to exist with oxygen bonded multivalent anions, because of water tolerance, alkali resistance inferior, so fail to obtain enough performances, but adopt treatment agent at least a in the vanadium compound of the vanadium compound of the vanadium compound contain through giving reductive 4 valencys, 3 valencys and divalent and give the formation tunicle, can be considered water tolerance, alkali resistance improves.Again, used organic compound (C), if when 5 valency vanadium compound reduces, then can be considered simultaneously will be in the aqueous solution vanadium through giving reductive 4 valencys, 3 valencys and at least a valence of divalent the effect of integration salt stabilization be arranged in the aqueous solution.
On tunicle of the present invention if on bestowing based on organic polymer when being coated with tunicle, then owing on be coated with tunicle the effect that multiplies each other that blocks effect solidity to corrosion is further improved.[embodiment]
Next utilizes embodiment and comparative example explanation the present invention, but the present invention's example only only, is not in order to limiting the present inventor, and the appraisal procedure of the disposable plates test portion of pretending for embodiment, comparative example is as follows.1, former material
A: galvanizing steel plate (thickness of slab: 0.8mm)
B: hot-dip galvanized steel sheet (thickness of slab: 0.8mm)
The wrong steel plate galvanized of C:55% (thickness of slab: 0.5mm) 2, treatment solution of the present invention
(1) treatment solution composition
(A) is as follows for the vanadium compound that has used.
A1: ammonium meta-vanadate
A2: five oxidation dioxies
A3: three vanadium oxides
A4: the metallic compound (B) that oxygen base acetyl group vinegar copper acid esters vanadium has used is as follows.
B1: ammonium molybdate
B2: ammonium metawolframate
B3: zirconium carbonate amine
B4: hydrofluotitanic acid
B5: (C) is as follows for the organic compound that manganous carbonate has used.
Bad hematic acid of C1:L-Hangzhoupro
C2:D-glucose
C3: oxalic dialdehyde
C4: citric acid
(D) is as follows for the etching reagent that has used.
D1：HF
D2：H
2ZrF
6
D3：CH
3COOH
D4：H
2SiF
6
D5：(NH4)
2HPO
4
The water-soluble polymer or the water system latex resin (E) that use are as follows.
E1: water system is gathered urethane resin, and (the first industrial pharmacy (share) is made, superflex100)
E2: the many compound resins of water system ethylene-acrylic acid (ethylene/acrylic acid=80/20
*, molecular-weight average about 20,000)
E3: water system Resins, epoxy (rising sun electrochemical industry (share) system adecallenjinEPEA-0434)
E4: water system acrylic resin (butylacrylic acid ester/methacrylic ester/2-hydroxyethyl meth acrylate/vinylformic acid/epihydric alcohol methylpropenoic acid ester/vinylbenzene=50/20/5/8/2/15)
*
(2) equipment of treatment solution
The situation of embodiment 1～7 and comparative example 1～2
Vanadium compound (A), metallic compound (B), etching reagent (D) are given deionized water to mix, heated 1 hour at 50 ℃.The situation of embodiment 8～16 and comparative example 3.After in 5% aqueous solution of organic compound (C), mixing vanadium compound (A), heated 30 minutes, be cooled to room temperature, add metallic compound (B), connect potato etching reagent (D), add deionized water at last and be adjusted to specified concentration at 80～100 ℃.The situation of embodiment 17～21 and comparative example 4
After vanadium compound (A) being mixed into 5% aqueous solution of organic compound (C), with 80～100 ℃ of heating 30 minutes, be placed under the room temperature and cool off, add etching reagent (D) and water-soluble polymer or water system latex resin (E), add deionized water at last again and be adjusted to finite concentration.3, be coated with treatment solution on
It is as follows to be coated with treatment agent (Z) and treatment process on having used.
Z1: (the first industrial Pharmacy stock Co., Ltd makes the water system polyurethane, Supeflex100) divide 100 quality branches in solid shape, (produce chemical limited-liability company daily makes the water system silicon, Snow tex C) with the silicon 20 quality branch that convert, water system wax (Mitsui Chemicals Inc. makes, Chemipearl W900) divides the water system treatment solution of the non-volatile content 10% that is formed by 10 quality branches in solid shape.
Z2: ethene-acrylic acid copolymer compound (ethylene/acrylic acid=80/20, molecular-weight average about 20,000) in the ammonia and the water system polymkeric substance divide the 100 quality branches that convert in solid shape, the water dispersible silicon is in the convert water system treatment solution of the non-volatility composition 20% that formed by 10 quality branches of silicon.4, treatment process
(1) degreasing
After the alkaline defatting agent Parclean364S that makes with Japanese parkerizing limited-liability company (20g/L just throws stoste, 60 ℃ of 10 seconds of spray cloth, spray cloth pressure 50kpa) gives degreasing with former material, spray cloth and washed for 10 seconds.
(2) coating of treatment solution of the present invention and drying
I: be coated with device #3 coating treatment solution with rod, adopt hot air circulation type baking oven and carry out drying for 80 ℃ in the plate temperature.
II: be coated with device #3 coating treatment solution with rod, adopt hot air circulation type baking oven and carry out drying for 120 ℃ in the plate temperature.
(3) be coated with the coating and the drying of treatment solution on
Adopting on treatment solution of the present invention, the formed tunicle of treatment process, be coated with device with rod and be coated on and be coated with treatment solution to the 1 μ m of dry film thickness, at 100 ℃ of heat dryings of plate temperature on aforementioned to one-tenth.5, appraisal procedure
(1) solidity to corrosion
Be as the criterion with JIS-Z-2371 salt spray testing method, carry out brine spray after 72 hours, ask for the white rust generation area after 120 hours and give assessment.
The assessment benchmark: white rust generation area ◎ less than more than 10%, 0 10% less than 30%, Δ more than 30% less than 60%, * more than 60%
(2) alkali resistance
Just throw after stoste becomes 20g/L and adjust 60 ℃ grease-removing agent aqueous solution washing in 30 seconds in the alkaline defatting agent Parclean364S that spray cloth on the disposable plates has been made by Japanese Parkerizing limited-liability company, 80 ℃ of dryings.To the condition of this plate, with Evaluation Method assessment solidity to corrosion with above-mentioned (1) record.
(3) anti-finger printing
To point to press down and be pressed on the disposable plates surface, with the vestige state of visual inspection fingerprint and give assessment.
Assessment benchmark: ◎ do not have fully vestige, zero little vestige, △ have vestige, * have clear and definite vestige remaining
(4) solvent resistance
Be mixed with the three-dimensional body (1cm cube) of alcoholic acid roll of gauze in silicon-oxygen resin system to test face with 50000kpa wiping 10 times back and forth.
Evaluation criteria: the ◎ tunicle is almost unstripped, zero little tunicle peel off △ have the part tunicle peel off, * tunicle comprehensively peels off and can see ground
The treatment solution content and the treatment process of embodiment and comparative example are shown in table 1, table 2 and table 3, and the assessment result of disposable plates is shown in table 4 and table 5.By the formed tunicle of treatment agent of the present invention (embodiment 1～16) that contains specific vanadium compound (A) and specific metallic compound (B), demonstrate superior solidity to corrosion and alkali resistance by table 4 as can be known.In contrast to this, it is inferior aspect solidity to corrosion and alkali resistance not contain the comparative example 1～3 of vanadium compound (A) or metallic compound (B).
As shown in Table 5, in embodiment 17～21, and the tunicle of embodiment 1～11 on, the solidity to corrosion or the alkali resistance that apply the tunicle of resinizing (Z1 or Z2) person (embodiment 22～32) are superior, anti-finger printing, solvent resistance are also superior as can be known again.In contrast to this, it is inferior aspect solidity to corrosion and alkali resistance not contain the comparative example 4～6 of vanadium compound (A) or metallic compound (B).
Table 1
*In metal
| Embodiment and comparative example | Former material | Treatment solution is formed (g/L) | Treatment process | |||
| Vanadium (A) * | ??V 3++V 4+/ complete | Metallic compound (B) * | Etching reagent (D) | |||
| Embodiment 1 | ????a | ????A1(7) ????A3(18) | ????0.72 | ????B1(5) ????B4(10) | ????… | ????I |
| Embodiment 2 | ????a | ????A1(7) ????A3(18) | ????0.72 | ????B1(5) ????B4(10) | ????D2(2) | ????I |
| Embodiment 3 | ????a | ????A4(3) | ????1.0 | ????B4(2) | ????D2(2) | ????I |
| Embodiment 4 | ????b | ????A2(7.2) ????A3(2.8) | ????0.28 | ????B3(10) | ????D1(10) | ????II |
| Embodiment 5 | ????b | ????A1(3) ????A3(1) ????A4(2) | ????0.5 | ????B2(2) ????B5(5) | ????D2(10) | ????II |
| Embodiment 6 | ????c | ????A3(5) ????A4(10) | ????1.0 | ????B4(10) | ????D4(1) | ????I |
| Embodiment 7 | ????a | ????A1(7) | ????0 | ????B1(5) ????B4(10) | ????D1(2) | ????I |
| Comparative example 1 | ????a | ????… | ????… | ????B1(5) ????B4(10) | ????D1(2) | ????I |
| Comparative example 2 | ????b | ????A2(7.2) ????A3(2.8) | ????0.28?? | ????… | ????… | ????II |
Table 2
*In metal
| Embodiment and comparative example | Former material | Treatment solution is formed (g/L) | Treatment process | |||||
| Vanadium (A) * | ??V 5+/ full V | Metallic compound | Organic compound (C) | Etching erosion (D) | Silicon-dioxide | |||
| Embodiment 8 | ????a | ?A1(12) | ????0.2 | ??B1(5) ??B4(5) | ??C1(5) | ??D1(2) | ??--- | ????I |
| Embodiment 9 | ????b | ?A(7.5) | ????0 | ??B2(5) | ??C2(7.5) | ??D3(5) | ??--- | ????II |
| Embodiment 10 | ????a | ?A1(15) | ????0 | ??B3(15) | ??C3(15) | ??D2(5) | ??--- | ????II |
| Embodiment 11 | ????c | ?A1(10) ?A2(20) | ????0.6 | ??B4(6) ??B5(4) | ??C1(1) | ??D4(10) | ??--- | ????I |
| Embodiment 12 | ????a | ?A1(13) | ????0 | ??B3(26) | ??C1(40) | ??D5(20) | ??--- | ????I |
| Embodiment 13 | ????a | ?A2(20) | ????0 | ??B3(20) | ??C1(60) | ??--- | ??--- | ????I |
| Embodiment 14 | ????b | ?A1(25) | ????0 | ??B3(35) | ??C1(50) | ??D5(40) | ??(80) | ????II |
| Embodiment 15 | ????a | ?A1(10) | ????0 | ??B2(30) | ??C4(40) | ??D2(30) | ??(30) | ????I |
| Embodiment 16 | ????c | ?A2(10) | ????0 | ??B1(20) ??B2(20) | ??C4(80) | ??D2(40) | ??--- | ????I |
| Comparative example 3 | ????a | ?A1(12) | ????0.2 | ??… | ??C1(5) | ??D1(2) | ??--- | ????I |
Table 3
| Embodiment and comparative example | Raw material | Treatment solution is formed (g/l) | Treatment process | ||||||
| Vanadium *??(A) | V 5+/ full V | Metallic compound *(B) | Organic compound (C) | Etching reagent (D) | Resin | Silicon-dioxide | |||
| Embodiment 17 | ?a | ?A1(4) | ????0 | ?B3(8) | C1(12) | D5(6) | E1(120) | --- | ????I |
| Embodiment 18 | ?a | ?A2(16) | ????0 | ?B3(16) | C1(48) | --- | E2(120) | --- | ????I |
| Embodiment 19 | ?b | ?A1(8) | ????0 | ?B3(10) | C1(15) | D5(12) | E2(50) | (20) | ????II |
| Embodiment 20 | ?a | ?A1(5) | ????0 | ?B2(15) | C4(20) | D2(15) | E3(130) | (15) | ????I |
| Embodiment 21 | ?c | ?A2(7) | ????0 | ?B1(14) ?B2(14) | C4(56) | D2(28) | E3(60) | --- | ????I |
| Comparative example 4 | ?a | ?A1(4) | ????0 | ?--- | C1(2) | D1(2) | E1(120) | --- | ????I |
Embodiment 22: utilize the processing that is coated with treatment agent Z1 on the tunicle that forms in embodiment 1.
Embodiment 23: utilize the processing that is coated with treatment agent Z1 on embodiment 2 established tunicles.
Embodiment 24: utilize the processing that is coated with treatment agent Z1 on embodiment 3 established tunicles.
Embodiment 25: utilize the processing that is coated with treatment agent Z2 on embodiment 4 established tunicles.
Embodiment 26: utilize the processing that is coated with treatment agent Z1 on embodiment 5 established tunicles.
Embodiment 27: utilize the processing that is coated with treatment agent Z2 on embodiment 6 established tunicles.
Embodiment 28: utilize the processing that is coated with treatment agent Z1 on embodiment 7 established tunicles.
Embodiment 29: utilize the processing that is coated with treatment agent Z2 on embodiment 8 established tunicles.
Embodiment 30: utilize the processing that is coated with treatment agent Z1 on embodiment 9 established tunicles.
Embodiment 31: utilize the processing that is coated with treatment agent Z2 on embodiment 10 established tunicles.
Embodiment 32: utilize the processing that is coated with treatment agent Z2 on embodiment 11 established tunicles.
Comparative example 5: on embodiment 1 established tunicle, utilize the processing that is coated with treatment agent Z1.
Comparative example 6: on embodiment 2 established tunicles, utilize the processing that is coated with treatment agent Z1.
Comparative example 7: on embodiment 3 established tunicles, utilize the processing that is coated with treatment agent Z2.
Table 4
| Embodiment and comparative example | After solidity to corrosion SST48 hour | After alkali resistance SST48 hour |
| Embodiment 1 | ○ | ○ |
| Embodiment 2 | ◎ | ◎ |
| Embodiment 3 | ○ | ○ |
| Embodiment 4 | ◎ | ○ |
| Embodiment 5 | ◎ | ◎ |
| Embodiment 6 | ◎ | ○ |
| Embodiment 7 | ○ | △ |
| Embodiment 8 | ◎ | ◎ |
| Embodiment 9 | ◎ | ◎ |
| Embodiment 10 | ◎ | ◎ |
| Embodiment 11 | ◎ | ◎ |
| Embodiment 12 | ◎ | ◎ |
| Embodiment 13 | ◎ | ◎ |
| Embodiment 14 | ◎ | ◎ |
| Embodiment 15 | ◎ | ◎ |
| Embodiment 16 | ◎ | ◎ |
| Comparative example 1 | △ | × |
| Comparative example 2 | △ | × |
| Comparative example 3 | △ | × |
Table 5
The effect of invention
| Embodiment and comparative example | Behind the solidity to corrosion SST 120 hours | Behind the alkali resistance SST 120 hours | Anti-finger printing | Solvent resistance |
| Embodiment 17 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 18 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 19 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 20 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 21 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 22 | ○～◎ | ○～◎ | ○ | ○ |
| Embodiment 23 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 24 | ◎ | ○ | ○ | ◎ |
| Embodiment 25 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 26 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 27 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 28 | ○ | ○～△ | ◎ | ◎ |
| Embodiment 29 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 30 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 31 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 32 | ◎ | ◎ | ◎ | ◎ |
| Comparative example 4 | △ | × | ◎ | △ |
| Comparative example 5 | △ | × | ○ | △ |
| Comparative example 6 | △ | × | ○ | △ |
| Comparative example 7 | △ | × | ○ | △ |
Treatment agent of the present invention does not contain the chromate-free type of deleterious chromium cpd, being had with known chromic salt tunicle by the formed tunicle of this surface treatment agent has equal or equal above solidity to corrosion, and it is very big to have utility value on surface treatment agent of the present invention, surface treatment method and the surface-treated metal material industry.
Claims (7)
1, a kind of metal conditioner is characterized in that: it contains and contains at least a kind of vanadium compound (A), and the metallic compound (B) of at least a metal selected of the colony that formed by zirconium, titanium, molybdenum, tungsten, manganese and cerium.
2, metal conditioner as claimed in claim 1 is characterized in that: wherein in vanadium compound (A), Oxidation Number is the vanadium ion of pentavalent and the ratio V of full vanadium
5+/ V is in 0～0.6 scope.
3, metal conditioner as claimed in claim 1 or 2 is characterized in that: wherein also contain the organic compound (C) with at least a functional group that the colony that formed by hydroxyl, carbonyl, carboxyl, 1～3 grade of amido, vinegar amido, phosphate and sulfonic group selects.
4, as each metal conditioner of claim 1 to 3, it is characterized in that: wherein also contain at least a etching reagent of selecting by mineral acid, organic acid and fluorine cpd (D).
5, as each metal conditioner of claim 1 to 4, it is characterized in that: wherein also contain water-soluble polymer or water system latex resin.
6, a kind of surface treatment method of metallic substance is characterized in that: after handling metal material surface with each metal conditioner of claim 1 to 4, heat drying to the temperature of previous materials becomes 50～250 ℃.
7, a kind of surface-treated metal material is characterized in that: have the surface treatment method that adopts claim 5 and the tunicle that forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001133946A JP3851106B2 (en) | 2000-05-11 | 2001-05-01 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| JP2001133946 | 2001-05-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1386901A true CN1386901A (en) | 2002-12-25 |
Family
ID=18981718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02118035A Pending CN1386901A (en) | 2001-05-01 | 2002-04-18 | Metal surface treating agent and method, and surface treatment of metal material |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20020084817A (en) |
| CN (1) | CN1386901A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN100339507C (en) * | 2003-06-20 | 2007-09-26 | 联合工艺公司 | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| CN102747352A (en) * | 2012-07-03 | 2012-10-24 | 中国人民解放军国防科学技术大学 | Passivator and passivation for hot galvanized sheet |
| CN102877055A (en) * | 2011-07-15 | 2013-01-16 | 日本帕卡濑精株式会社 | Metal surface treatment agent and metal material obtained through processing with same |
| CN104073138A (en) * | 2014-06-17 | 2014-10-01 | 张家港市橡燊达机械有限公司 | Alloy metal substrate treatment agent |
| CN104145046A (en) * | 2012-03-09 | 2014-11-12 | 日本油漆株式会社 | Chemical conversion agent and chemical conversion coating film |
| US10138559B2 (en) | 2013-04-03 | 2018-11-27 | Nippon Paint Surf Chemicals Co., Ltd. | Chemical conversion agent and metal surface treatment method |
| CN110129855A (en) * | 2019-06-11 | 2019-08-16 | 南通大学 | A kind of surface treatment method of corrosive protection of aluminium alloy |
| TWI678433B (en) * | 2017-09-14 | 2019-12-01 | 日商迪普索股份有限公司 | Trivalent chromium chemical conversion treatment liquid for zinc or zinc alloy base and chemical conversion treatment method using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5827053B2 (en) * | 2011-07-15 | 2015-12-02 | 日本パーカライジング株式会社 | Water-based metal surface treatment agent and metal material treated with the treatment agent |
-
2002
- 2002-04-18 CN CN02118035A patent/CN1386901A/en active Pending
- 2002-05-01 KR KR1020020023997A patent/KR20020084817A/en not_active Application Discontinuation
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339507C (en) * | 2003-06-20 | 2007-09-26 | 联合工艺公司 | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| US7699926B2 (en) | 2004-01-08 | 2010-04-20 | China International Marine Containers (Group) Co., Ltd. | Chrome-free passivating solution |
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN102877055B (en) * | 2011-07-15 | 2016-05-04 | 日本帕卡濑精株式会社 | Metal conditioner and utilize this inorganic agent to process and the metal material that obtains |
| CN102877055A (en) * | 2011-07-15 | 2013-01-16 | 日本帕卡濑精株式会社 | Metal surface treatment agent and metal material obtained through processing with same |
| CN104145046B (en) * | 2012-03-09 | 2018-10-12 | 日涂表面处理化工有限公司 | Chemical conversion treating agent and chemical conversion treatment epithelium |
| CN104145046A (en) * | 2012-03-09 | 2014-11-12 | 日本油漆株式会社 | Chemical conversion agent and chemical conversion coating film |
| US9879345B2 (en) | 2012-03-09 | 2018-01-30 | Nippon Paint Surf Chemicals Co., Ltd. | Chemical conversion agent and chemical conversion coating film |
| CN102747352A (en) * | 2012-07-03 | 2012-10-24 | 中国人民解放军国防科学技术大学 | Passivator and passivation for hot galvanized sheet |
| US10138559B2 (en) | 2013-04-03 | 2018-11-27 | Nippon Paint Surf Chemicals Co., Ltd. | Chemical conversion agent and metal surface treatment method |
| CN104073138A (en) * | 2014-06-17 | 2014-10-01 | 张家港市橡燊达机械有限公司 | Alloy metal substrate treatment agent |
| TWI678433B (en) * | 2017-09-14 | 2019-12-01 | 日商迪普索股份有限公司 | Trivalent chromium chemical conversion treatment liquid for zinc or zinc alloy base and chemical conversion treatment method using the same |
| CN110129855A (en) * | 2019-06-11 | 2019-08-16 | 南通大学 | A kind of surface treatment method of corrosive protection of aluminium alloy |
| CN110129855B (en) * | 2019-06-11 | 2021-04-27 | 南通大学 | Surface treatment method for corrosion prevention of aluminum alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020084817A (en) | 2002-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4167046B2 (en) | Metal surface treatment agent, metal surface treatment method and surface treatment metal material | |
| CN1200137C (en) | Metal surface treatment agent, treating method for metal material and metal material of metal surface treatment | |
| TWI473665B (en) | Surface-treating composition and surface-treated steel sheet | |
| CN1200139C (en) | Method for providing metal surface with protection against corrosion | |
| AU2006260006B2 (en) | Chrome-free composition of low temperature curing for treating a metal surface and a metal sheet using the same | |
| CN1174062C (en) | Chromium free paint composition and painted metal plate | |
| JP5075321B2 (en) | Aqueous treatment agent for metal surface | |
| JP5588058B1 (en) | Chrome-free metal surface treatment agent | |
| JP6118419B2 (en) | Surface treatment agent for metal material, method for producing surface-treated metal material | |
| CN1341160A (en) | Composition for metal surface treatment and surface treated metallic material | |
| US20060014893A1 (en) | Method for coating metal substrates with a radically polymerizable coating agent and coated substrates | |
| CN1163311C (en) | Aluminium hydrophilic processing technology, used primary agent and hydrophilic coating | |
| CN1665958A (en) | Precoat metal plate excellent in press workability and method for production thereof | |
| CN104073100B (en) | A kind of galvanized steel plain sheet low temperature resistance and fingerprint resistance surface conditioning agent and environment-friendly type surface process galvanized steel plain sheet | |
| CN101018888A (en) | Method and composition for forming a non-chrome conversion coating on steel surface | |
| JP2007002330A (en) | Surface treatment agent for zinc or zinc alloy galvanized steel sheet, and surface treated zinc or zinc alloy galvanized steel sheet | |
| CN1210356C (en) | Metal surface treatment agent, method thereof and metal material used with said method | |
| CN1386901A (en) | Metal surface treating agent and method, and surface treatment of metal material | |
| JP4970773B2 (en) | Metal surface treatment agent, metal material surface treatment method and surface treatment metal material | |
| JP4521010B2 (en) | Metal surface treatment agent, metal surface treatment method and surface treatment metal material | |
| JP2012012668A (en) | Composition for forming rust preventive film and method for forming rust preventive film using the same and rust prevention-treated metal | |
| JP2000144444A (en) | Production of surface treated steel sheet excellent in corrosion resistance | |
| JP2005008975A (en) | Metal surface treatment method, surface-treated aluminum based metal and pretreatment method to hydrophilic treatment | |
| JP6564036B2 (en) | Water-based treatment agent, galvanized steel or zinc alloy plated steel, and painted galvanized steel or painted zinc alloy plated steel | |
| TW506996B (en) | Treating agents for metal surface, process of treating metal material and surface treated metal materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |