CN100366801C - Surface treatment method of environment-friendly chromium-free zirconium-containing electrogalvanizing fingerprint-resistant steel plate - Google Patents
Surface treatment method of environment-friendly chromium-free zirconium-containing electrogalvanizing fingerprint-resistant steel plate Download PDFInfo
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- CN100366801C CN100366801C CNB2005100941504A CN200510094150A CN100366801C CN 100366801 C CN100366801 C CN 100366801C CN B2005100941504 A CNB2005100941504 A CN B2005100941504A CN 200510094150 A CN200510094150 A CN 200510094150A CN 100366801 C CN100366801 C CN 100366801C
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Abstract
The invention relates to a surface treatment method of an environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint-resistant steel plate, in particular to an electro-galvanizing process method for forming a uniform and fine zinc layer on the surface of a cold-rolled steel plate and an environment-friendly chromium-containing zirconium-resistant fingerprint coating for manufacturing the electro-galvanized fingerprint-resistant steel plate. After the cold-rolled sheet is used as a substrate and is subjected to electro-galvanizing, fingerprint-resistant coating is coated on the surface of the sheet, and the method is characterized in that: firstly, adopting a vertical insoluble anode electrogalvanizing process to produce an electrogalvanized plate, then adopting a fingerprint-resistant water-based coating with zirconium replacing chromium to coat the surface of the electrogalvanized plate, and carrying out low-temperature baking curing treatment below 125 ℃ to form an organic composite resin film on the surface of the electrogalvanized plate. The quality of the electro-galvanized layer is stable and reliable, and the organic composite resin film on the surface of the plate does not cause pollution to the environment.
Description
Technical field:
The present invention relates to a kind of surface treatment method of environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet.Be specifically related to a kind of galvanizing technique method at surface of cold-rolled steel plate formation uniform and smooth zinc layer, and the environment-friendly chromium-free zirconium-containing fingerprint-resistant coating that is used to make electro-galvanized fingerprint resistant steel sheet.
Background technology:
Anti-finger print steel plate be with the cold-reduced sheet be substrate behind electro-galvanizing, on the plate face, apply the high value added product of the thick organic composite resin membrane of 1～3 μ m again.The anti-finger print steel plate product is because to have outward appearance beautiful, higher erosion resistance, good anti-finger printing, good electrical conductivity, anti-blackening, resistance to marring, higher chemical stability; The film of anti-fingerprint the and basal body binding force are strong, matrix metal are had characteristics such as better protecting effect, have been widely used in panel, side plate, inner panel and component on medium-to-high grade product of household electrical appliances and automobile industry with on the plate.As the shell of refrigerator, washing machine, compressor of air conditioner, CD player, VCD, DVD, sound equipment, radio-cassette player etc., inner part, base plate, back plate etc.
Electro-galvanizing production can be divided into alkalescence and two kinds of acidity according to the electrolytic solution difference of using, and basic process is to adopt Na
2ZnO
3Be ionogen; Basic process is owing to the electrolytic solution instability, and current density is low, and uneven coating is even, and surface gloss is poor, so be not suitable for high-speed and continuous electro-galvanizing production line.Be of little use the part electro-galvanizing that only is used for fixing at present.Acid process is to adopt ZnSO
4, ZnCl
2The electroplate liquid that acid process adopts has zinc sulfate, zinc chloride, zinc cyanide etc.But because zinc chloride is volatile, the cost height: and zinc cyanide toxicity is very big, so the zinc sulfate use is comparatively extensive.
And can be divided into solubility and insoluble two kinds according to plating tank anodic character, plating is that the part that will be plated is as negative electrode; If then is soluble anode to be deposited metallographic phase metal together as anode; If then is insoluble anode with other insoluble material as anode.But all be to be placed in the salts solution that contains metallizing to some extent, under the direct current effect, obtain the process of metal plating with certain performance.
Can be divided into two kinds of horizontal and radials according to the difference of plating tank structure.Wherein the radial coating bath is with only plating use at single face.Anode in the horizontal coating bath is horizontally disposed, and the band steel runs on up and down between two anodes during plating, the injection direction of plating bath and band steel traffic direction opposite (single face injection), the difficult discharge of the bubble that produces in the production; The easy sagging scratch anode of operating band steel causes short circuit simultaneously, and scratch anodic thing also often takes place.The material that anode uses is Pb-5Sn, and solution is subjected to this pollution also more serious, have in solution to add additive and drive away lead ion, and the muddiness of solution becomes thus, suspended substance deposits in pipeline and coating bath, hinders the proper motion of liquid, and is unfavorable to electroplating.Be in operation, electroplate liquid contacts with the strip, and makes metal ion in the plating bath at the conductive rollers surface deposition, and conductive rollers surface quality variation directly influences the quality of belt steel surface, causes conductive rollers impression and roller spot.Even more serious is, the damage of Pb-5Sn alloy anode and corrosion, make the Pb ion in the electroplate liquid rise very fast, can cause the bonding force of zinc coating bad, for the fatal especially weakness of the product of anti-the fingerprint, because the Pb ion is to cause the black one of the main reasons of cashing elephant occurring on the fingerprint-proof plate surface.
The performance that electro-galvanized layer can improve material surface comprises: surface property such as outward appearance (smooth, gloss, color), wear resistance, solidity to corrosion, hardness, light, electricity, magnetic and heat, but with finger or palm when touching surface of steel plate or steel plate when working in corrosive medium, surface of steel plate causes easily and produces corrosion and diminish attractive in appearance.The case material of electronic products such as CD player, VCD, DVD, sound equipment, radio-cassette player uses steel plate galvanized usually, and when the electronic component of assembling on the casing, the surface that operator's hand touches casing is easy to generate the fingerprint attachment issue.In order to prevent that fingerprint from adhering to, improve solidity to corrosion, anti-finger printing and improve the ground connection property of casing, the production method of having invented a kind of anti-finger print steel plate.
At present, the production method of electro-galvanized fingerprint resistant steel sheet is that the electro-galvanizing substrate is carried out the organic film that Passivation Treatment applies one deck 1～3 μ m then earlier, and used chemical processing agent is respectively the passivator and the water-soluble organic coating of chromate.(the flat 1-176090 of JP) is contained according to patent documentation; contain sexavalent chrome in its surface passivated membrane, it plays the effect of filling up, but film is when being subjected to slight damage; thereby exposed sexavalent chrome makes this locate the effect that passivation has again lost further protection, and its anti-finger printing and anti-blackening are relatively poor.Proposed a kind of surface treatment method that is used to prevent the steel plate blackening of plating Zn-Al alloy in special fair 1-53353 number, this method adopts the treatment solution that contains chromic acid and/or chromic salt and water soluble resin and/or emulsion resin.But effect is very dissatisfied.A kind of method that is used to prevent the surface stain of fusion zinc-containing metal-plated steel strip is being disclosed for the fair 3-49982 of spy number, this method is that usefulness contains the Co ion and/or Ni ionic treatment solution is handled so that on the surface of these metals attached to this steel plate, and then handle this surface of steel plate, thereby prevent its black change with chromic salt.Yet this method will comprise at least that the plating that uses Ni and/or Co is handled and with 2 operations of chromate treating, even will include the operation of being washed again after the plating processing with Ni and/or Co, at this moment comprises 3 operations altogether.Therefore, as adopt this method, it is difficult using original surface processing equipment.In addition, the most important is to have sufficient data to prove that sexavalent chrome is a harmful element, is prohibited in exported product by countries such as European Union, must be replaced by other element.
European patent application EP 156437A1 disclosed a kind of " method of water-based paint, metallizing substrate and the metal substrate that obtains ", be to use a kind of binding agent+at least 2 kinds of lubricants, wherein at least a for containing the inorganics of zinc powder, the steel plate that this method obtains can improve electroconductibility, but when welding, produce zinc fog, harmful, and influence life-span of weld.In addition, European patent application EP 780452A2 discloses a kind of " water-based paint ", and it directly adopts epoxy modified acrylic resin is membrane-forming agent, but being container, uses this coating, and be to adopt the back coating, inapplicable for the electro-galvanizing coil of strip that needs precoated layer to handle.
Summary of the invention:
The objective of the invention is to overcome above-mentioned deficiency, the surface treatment method of the environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet that provide that a kind of electro-galvanized layer steady quality is reliable, the organic composite resin membrane of plate face can not pollute to environment.
The object of the present invention is achieved like this: a kind of surface treatment method of environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet, be to be that substrate is behind electro-galvanizing with the cold-reduced sheet, apply fingerprint-resistant coating on the plate face, it is characterized in that: at first adopt rectilinear insoluble anode galvanizing technique method to produce electrolytic galvanized sheet, adopt a kind of fingerprint-resisting water borne coating that the electrolytic galvanized sheet surface is applied then with zirconium to substitute chromium, low-temperature bake solidification treatment below 125 ℃ forms organic composite resin membrane on the galvanized sheet surface.
The surface treatment method of environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet of the present invention, described rectilinear insoluble anode galvanizing technique method is: the anode in the coating bath is vertically arranged, the band steel also is vertical, turn to by sinking roll strip 180 degree in groove, be provided with two antianodes in the groove, conductive rollers is not dipped in the plating bath outside groove.The gas that produces when vertical channel is electroplated is discharged easily, and band steel operating ratio is more steady.
The surface treatment method of environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet of the present invention, described anode adopts anode box, and the anode box inner side-wall is installed positive plate, and positive plate adopts the insoluble IrO of plating on the Ti substrate
2Anode is not full of plating bath in the coating bath, have plating bath overflow outlet on anode box upper inner wall, and plating bath is flowed out by the outlet of anode box top, has the plating bath inlet in the bottom of anode box, and electroplate liquid is squeezed into anode box by variable frequency pump through anode box bottom plating bath inlet.Anode adopts the insoluble IrO of plating on the Ti substrate
2Anode, the Pb ion content in the plating bath is lower, can not cause black change and other disadvantageous effect of product, since the source of having stopped Pb, SrCO
3Also need not add, plating bath comparatively cleans, for the exploitation of high current density zincincation is laid a good foundation.Being with steel in addition is vertical in coating bath, and band steel scratch anodic chance also greatly alleviates, and the anodic spacing can narrow down to 18mm, has reduced bath voltage (8-12 volt) widely, and power consumption also reduces thereupon.
For plating bath can steadily be flowed out equably in overflow, be horizontally set with two-layer netted dividing plate in the anode box, the aperture of lower floor's web plate is little, and the aperture on upper strata is big.Through the effect of two-layer dividing plate, it is more steady that the plating bath liquid level in the anode box becomes, and this is convenient to the control of plating bath width.
In order to control the width that plating bath flows down, the outlet of plating bath is set as V-shape.When the band steel has wide narrowing down, the faster rotational speed of variable frequency pump, the liquid level in the anode box is just raised, and makes to increase from the effusive width of V-shape overflow port.Otherwise be same principle, variable frequency pump slows down.The speed of variable frequency pump is the width automatic setting of computer according to the band steel.The width of plating bath is consistent with the limit portion that is with steel all the time.
When flowing between anode and band steel owing to liquid for elimination, liquid near outlet can produce contraction, thereby make band steel limit portion the time can produce the phenomenon of holiday phenomenon or strip edge portion zinc layer attenuate by the anode Lower Half, offer the fluid infusion hole on the positive plate, strengthen the flow of bottom plating bath, guarantee the degree of filling of plating bath, also eliminated the plating bath shrinkage phenomenon.
The conductive rollers bottom all is immersed in the cleaning trays, and scavenging solution is to contain vitriolic solution, is used to dissolve the coated metal that the conductive rollers surface is glued.In order to remove the metal foul that the conductive rollers surface is glued, each conductive rollers has been equipped with a cover strigil, and is cleaned with jet apparatus, and the particle that scrapes is washed from the conductive rollers surface, prevents that particle is pressed into coating surface and produces defectives such as roll marks.Thus, the life-span of conductive rollers is also prolonged.
Described fingerprint-resisting water borne coating with zirconium to substitute chromium is made up of the raw material of following weight part:
Acrylic resin 50～75%
Silicon-dioxide 4～15%
Silane glue crosslinking agent 9～25%
Zirconium ion 0.5～1.5%
The weight sum of each component is 100%.
The effect of main ingredient:
Acrylic resin: 50～75 (weight percents) are main resin, film forming host, and＜50%, film is thin, and solidity to corrosion descends;＞75%, thickness, electrical equipment electroconductibility descends.
Silicon-dioxide: 4～15, mean particle size≤20nm, anticorrodent.＜4%, the solidity to corrosion of product descends significantly, salt-fog test＜28 hour;＞15%, the plasticity of product descends.
Silane glue connects agent (solidifying agent): 9～25 guarantee to solidify in the coating short period of time.＜9%, products solidifying is slow, and steel plate glues hand.＞25%, paint solidification is too fast, and thickness is wayward, consumes big.This solidifying agent plays cementation in film, be about to inorganic and organic materials and combine at short notice.
Polytetrafluoroethylene (PTFE): 8～22, lubricant can effectively improve the self lubricity of steel plate, makes product punching performance in the course of processing good, avoids the damage of film.＜8%, the lubricant effect of product is undesirable;＞22%, the easy breakdown of emulsion of product.
Polyethylene wax: the anti scuffing agent, 2～10,＜2%, the antifraying property of product is general; The easy breakdown of emulsion of＞10% product.
Polyvalent metal ion zirconium: improve solidity to corrosion and framework density.
Use zirconium to substitute chromium, when preparing, store in a warehouse, transporting and using, can not pollute, and have excellent self lubricity environment.
Description of drawings:
Fig. 1 is a rectilinear plating tank synoptic diagram of the present invention.
Fig. 2 is an anode box structural representation of the present invention.
Fig. 3 is an anode plate structure synoptic diagram of the present invention.
Embodiment:
The present invention relates to a kind of surface treatment method of environment-friendly chromium-free zirconium-containing electro-galvanized fingerprint resistant steel sheet, be with the cold-reduced sheet be substrate behind electro-galvanizing, on the plate face, apply organic composite resin membrane again.It is concrete
Embodiment is as follows:
Embodiment 1:
Step 1, get the raw materials ready
1, substrate: cold-reduced sheet
2, plating bath: zinc sulfate
3, coating is formed: get acrylic resin 750kg, silicon-dioxide 40kg, silane glue connects agent 90kg, tetrafluoroethylene 80kg, metal zirconium ion 5kg and polyethylene wax 35kg and places in the agitator, mix to make the chromium-free zirconium-containing fingerprint-resistant coating.
The coating bath structure is seen Fig. 1, and the present invention adopts 4 identical coating baths altogether, and each coating bath 5 includes two antianode casees 4 altogether, totally 40 fritter coating IrO
2Positive plate.
Be horizontally set with two-layer netted dividing plate in the anode box, the aperture of lower floor's web plate is little, and the aperture of upper strata web plate is big.On positive plate, offer fluid infusion hole 13, as Fig. 3.Conductive rollers 2 bottoms all are immersed in the cleaning trays 3, and scavenging solution is to contain vitriolic solution, and each conductive rollers 2 has been equipped with a cover strigil, and are cleaned with jet apparatus, and the particle that scrapes is washed from the conductive rollers surface.
Wherein: coating bath electroplating current: 15～20KA, voltage: 14～18V, degree of filling: 80%, zinc coating thickness: 20g/m
2
Roller coat chromium-free zirconium-containing fingerprint-resistant coating on the galvanized sheet face, 120 ℃ of baking-curings are made organic composite resin membrane.
Wherein: the coated weight of filming is controlled at 1.0～1.5g/m
2, the content of solid matter in the coating: 20%, coating pH value is controlled between 7.0～9.0.
1, the black change tested: test piece is placed on a temperature is 70 ℃, humidity is 90% interior the placement 24 hours of trier, and the Δ E before and after the determination test on color difference meter requires Δ E＜6 then
2, anti-finger printing: when touching belt steel surface, do not stay fingerprint, Δ E＜3 with clean finger
3, erosion resistance: salt-fog test is after 72 hours, and the surface is passed judgment on 〉=7 grades.
Embodiment 2:
The difference of embodiment 2 and embodiment 1 is that coating forms: get that acrylic resin 500kg, silica 1 00kg, silane glue connect agent 200kg, tetrafluoroethylene 100kg, metal zirconium ion 15kg, polyethylene wax 85kg place in the agitator, mix to make the chromium-free zirconium-containing fingerprint-resistant coating.All the other are with example 1.
Embodiment 3:
The difference of embodiment 3 and embodiment 1 is that coating forms: get that acrylic resin 600kg, silica 1 00kg, silane glue connect agent 90kg, tetrafluoroethylene 100kg, metal zirconium ion 10kg, polyethylene wax 100kg place in the agitator, mix to make the chromium-free zirconium-containing fingerprint-resistant coating.All the other are with example 1.
Claims (6)
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| CNB2005100941504A CN100366801C (en) | 2005-08-30 | 2005-08-30 | Surface treatment method of environment-friendly chromium-free zirconium-containing electrogalvanizing fingerprint-resistant steel plate |
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| CNB2005100941504A CN100366801C (en) | 2005-08-30 | 2005-08-30 | Surface treatment method of environment-friendly chromium-free zirconium-containing electrogalvanizing fingerprint-resistant steel plate |
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| CNA2007101415632A Division CN101186777A (en) | 2005-08-30 | 2005-08-30 | Fingerprint-resisting water borne coating using zirconium to substitute chromium |
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