CN103805977A - Chromium-free passivation liquid for treating tin-plated steel plate - Google Patents
Chromium-free passivation liquid for treating tin-plated steel plate Download PDFInfo
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- CN103805977A CN103805977A CN201210445665.4A CN201210445665A CN103805977A CN 103805977 A CN103805977 A CN 103805977A CN 201210445665 A CN201210445665 A CN 201210445665A CN 103805977 A CN103805977 A CN 103805977A
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Abstract
The present invention discloses a chromium-free passivation liquid for treating a tin-plated steel plate, wherein the pH value of the chromium-free passivation liquid is 3-4. The chromium-free passivation liquid comprises an inorganic compound containing at least one selected from silicon, titanium and zirconium, a metal compound containing at least one selected from aluminum, vanadium, manganese, cobalt, nickel and molybdenum, a soluble resin, an acid for adjusting the pH value of the passivation liquid to 3-4, and the balance of water and other unavoidable impurities, wherein the contents of silicon, titanium and zirconium are 0.1-20 g/L, the contents of aluminum, vanadium, manganese, cobalt, nickel and molybdenum are 0.1-20 g/L, and the soluble resin content is 0.1-20 g/L. The tin-plated steel plate treated by the chromium-free passivation liquid obtained with the technical scheme has characteristics of excellent corrosion resistance, excellent sulfurization resistance, excellent coating material adhesion and excellent processability.
Description
Technical field
The present invention relates to a kind of composition, relate in particular to a kind of passivating solution.
Background technology
Dry plate is one of important wrapping material, it has certain intensity and plasticity, be easy to shape, there are again good tin-welding, covering with paint property and erosion resistance, and there is a bright outward appearance, it is widely used in light industry, electronics, electrical equipment, and the industry such as instrument, in addition in large quantities for making canned food.Canned food adopts the Lacquered Tin Plate Can packing of electrolytic tinplate (tinplate) conventionally.Because poultry (fowl) meat contains rich in protein and amino acid, in the process of sterilization and storage, tend to generate some atraments at can inwall, even pollute content.Because these atraments are mainly the compounds of sulfur-bearing, be called as sulphur blackening.Its principle is the sulfur-bearing composition in Low acid canned food content, as the decomposes such as Gelucystine, halfcystine, forms the corrosive gases of sulfur-bearing.The metallic iron of can inwall and tin form galvanic couple under moist environment, and electrochemical reaction occurs, the digestion of metallic ion of anode, and now remaining oxygen has played cathodic depolarization, promotes the carrying out of reaction.The ionic bond of sulfonium ion and metallic iron or tin, generates respectively iron sulphide and the tin sulfide of black, and the atrament of generation also contains ironic hydroxide sometimes.
In order to improve the corrosion resisting property of tin plate, prevent tin plate tin layer oxidation jaundice in the time of storage or baking paint, improve the sulfidation-resistance energy of tin plate simultaneously, need to carry out Passivation Treatment to tin plate.The most frequently used is to adopt chromic salt negative electrode Passivation Treatment, and the passive film obtaining is very thin, and corrosion resisting property is fine.But sexavalent chrome toxicity contained in chromic salt is very large, serious environment pollution, be detrimental to health.Therefore,, for protection of the environment, guarantee HUMAN HEALTH, there is at present the much research about high anti-corrosion, environment-friendly chromium-free passivation technology.
For example, open day is on January 16th, 2008, and publication number is CN101104932A, and the Chinese patent literature that name is called " tin plate chromium-free passivation solution " discloses a kind of tin plate chromium-free passivation solution, and this passivating solution contains tertiary sodium phosphate, rose vitriol and water.
Open day is on February 3rd, 2010, and publication number is CN101638804A, name be called " for tin plate not containing chromium passivating liquid and using method thereof " Chinese patent literature a kind of acid metal passivating solution and using method thereof are disclosed.This passivating solution, containing chromium, does not have the inorganic salt that contain rare earth metal cerium (Ce) and lanthanum (La), inorganic salt and the water of ammonium.
Open day is on September 30th, 2009, publication number is CN101545107A, the Chinese patent literature that name is called " surface treatment liquid, surface treatment method and surface treated tin plate " discloses a kind of surface treatment agent for tin plate, wherein contain the phosphorus compound of 1～50g/L, the vanadium compound of 1～20g/L, 1～30g/L is selected from one or more in molybdenum, zirconium, titanium, manganese and tungsten metallization compound, and 1～10g/L has one or more compounds of at least one functional group in hydroxyl, carboxyl, carbonyl or phosphate.
Open day is on May 7th, 2003, publication number CN1416478A, the Chinese patent that name is called " surface treatment tin plate and chemical synthesis treatment liquid " disclose a kind of at tin coating containing the non-chromium passivation treatment fluid on the tin plate of P and Si, this passivating solution phosphoric acid ion, tin ion and silane coupling agent, pH is 1.5～5.5.
Summary of the invention
The object of this invention is to provide a kind of chromium-free passivation liquid for the treatment of tin plate, this passivating solution does not contain chromium, adopts this passivating solution tin plate after treatment to have excellent corrosion resistance nature, anti-curability, coating adhesion property and processing characteristics simultaneously.
Contriver found through experiments, and electrolytic tinplate is after sexavalent chrome passivation, and the passivation layer of chromic salt that its surface forms, preventing that tank skin from playing effective barrier action in producing sulfuration spot.The chrome content of passivation layer is higher, and the performance of anti-sulfuration spot is just stronger.Containing the chromium content of chromium passivating layer and the main factor that affects the anti-sulphur of electrolytic tinplate is substrate surface, is secondly tin coating thickness.Therefore, in chromium-free deactivation, if adopt other compounds to replace sexavalent chrome to carry out passivation, guaranteed often the solidity to corrosion of tin plate, declined but anti-sulphur is produced.Therefore, contriver, through research repeatedly, has invented one and can meet solidity to corrosion and anti-sulphur requirement simultaneously, and also very excellent chromium-free passivation liquid of processing characteristics and coating adhesion property.
According to above-mentioned purpose of the present invention, the present invention proposes a kind of chromium-free passivation liquid for the treatment of tin plate, the pH value of this passivating solution is 3～4, and comprises:
At least mineral compound of one of them that contains silicon, titanium and zirconium, and the content of silicon, titanium and zirconium is 0.1～20g/L, and preferably 0.5～15g/L, is most preferably 1～10g/L;
At least metallic compound of one of them that contains aluminium, vanadium, manganese, cobalt, nickel and molybdenum, and the content of aluminium, vanadium, manganese, cobalt, nickel and molybdenum is preferably 0.5～15g/L of 0.1～20g/L(, is most preferably 1～5g/L);
Water soluble resin, and its content is preferably 0.5～15g/L of 0.1～20g/L(, is most preferably 1～10g/L);
In order to the pH value of passivating solution is adjusted to 3～4 acid.
Surplus is water and other inevitable impurity.
Further, the pH value of chromium-free passivation liquid of the present invention is 3.5.
Further, the acid in chromium-free passivation liquid of the present invention is phosphoric acid.
In the technical program, the mineral compound in chromium-free passivation liquid includes but not limited to: one or more in potassium fluozirconate, ammonium fluozirconate, zirconium sulfate, oxalic acid zirconium potassium, potassium fluotitanate, ammonium titanium fluoride, titanyl sulfate, titanium potassium oxalate(T.P.O.), Sodium Silicofluoride, potassium silicofluoride, ammonium silicofluoride, magnesium silicofluoride.
In the technical program, the metallic compound in chromium-free passivation liquid includes but not limited to: one or more in Tai-Ace S 150, Burow Solution, oxalic acid aluminium, sodium metaaluminate, aluminum phosphate, aluminium dihydrogen phosphate, ammonium meta-vanadate, sodium metavanadate, potassium metavanadate, vanadylic sulfate, oxalic acid vanadyl, phosphate dihydrogen manganese, manganous nitrate, manganous sulfate, manganous carbonate, rose vitriol, cobalt chloride, cobalt oxalate, cobaltous carbonate, single nickel salt, nickelous nitrate, nickel acetate, Sodium orthomolybdate, ammonium paramolybdate.
In the technical program, the water soluble resin in chromium-free passivation liquid is water-soluble cationic resin and/or water-soluble nonionic resin and/or water soluble anion resin.
In the technical program, the water soluble resin of chromium-free passivation liquid includes but not limited to: one or more in cationic acrylate analog copolymer, positively charged ion Styrene-Acrylate Emulsion Polymerization thing, positively charged ion propylene oxide acid copolymer, polyurethane/cationic ester polymer.
The present invention, in the time adopting above-mentioned chromium-free passivation liquid to carry out Passivation Treatment to tin plate, adopts electrolytic passivation method or anode electrolysis passivating method.Wherein electrolytic passivation method is using pending tin plate as negative electrode, and inert material carries out electrolytic passivation as anode; Anode electrolysis passivation is using pending tin plate as anode, and inert material carries out electrolytic passivation as negative electrode.
Wherein, passivation temperature is 10～60 ℃, and preferably 15～50 ℃ is most preferably 20～40 ℃.
Wherein, the density range of Faradaic current is 0.1A～20A/dm
2, preferably 0.5A～10A/dm2, is most preferably 1～5A/dm
2.
Wherein, the scope of passivation time is 0.1～10 second.And the speed of a motor vehicle of considering coil of strip on production line is very fast, generally, in 200m/min left and right, therefore passivation time is conventionally all between 0.5s～2.0s.Therefore preferred passivation time is 0.5s～5s, is most preferably 0.5s～2.0s.
In the time adopting electrolytic passivation method, can adopt DC electrolysis passivation, alternating current electrolysis passivation, pulse electrolysis passivation, double wave pulse electrolytic passivation, pulse electrolysis passivation, direct current to exchange the one in overlapping electrolytic passivation, the overlapping electrolytic passivation of DC pulse.
Embodiment
Below in conjunction with specific embodiments technical solutions according to the invention are introduced further.
Embodiment 1
Ammonium fluozirconate 1.32g, potassium fluotitanate 5.4g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, add water to 1L and dissolve, wherein zirconium content is 0.5g/L, and the content of titanium and cobalt is all 1.0g/L, add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, fully be uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 2
Ammonium fluozirconate 2.65g, potassium fluotitanate 5.4g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, adds water to 1L and dissolves, and wherein zirconium content is 1.0g/L, and the content of titanium and cobalt is all 1.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 3
Ammonium fluozirconate 13.23g, potassium fluotitanate 5.4g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, adds water to 1L and dissolves, and wherein zirconium content is 5.0g/L, and the content of titanium and cobalt is 1.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 4
Ammonium fluozirconate 26.46g, potassium fluotitanate 5.4g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, adds water to 1L and dissolves, and wherein the content of zirconium is 10.0g/L, and the content of titanium and cobalt is 1.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 5
Tetrahydrated zirconium sulfate 19.48g, potassium fluotitanate 5.4g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, is dissolved in water to 1L, and wherein the content of zirconium is 5.0g/L, and the content of titanium and aluminium is 1.0g/L.Add subsequently commercially available water-soluble benzene emulsion resin 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.5.
Embodiment 6
Tetrahydrated zirconium sulfate 19.48g, potassium fluotitanate 27.0g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, is dissolved in water to 1L, and wherein zirconium content is 5.0g/L, and the content of titanium is 5.0g/L, and the content of aluminium is 1.0g/L.Add subsequently commercially available water-soluble benzene emulsion resin 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.5.
Embodiment 7
Tetrahydrated zirconium sulfate 19.48g, potassium fluotitanate 54.0g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, adds water to 1L and dissolves, and wherein zirconium content is 5.0g/L, and the content of titanium is 10.0g/L, and the content of aluminium is 1.0g/L.Add subsequently commercially available water-soluble benzene emulsion resin 5.0g, stir, finally adding phosphoric acid regulator solution pH is 3.5.
Embodiment 8
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 6.69g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, adds water to 1L and dissolves, and wherein zirconium content is 5.0g/L, and the content of silicon and cobalt is all 1.0g/L.Add subsequently commercially available water-soluble benzene emulsion resin 5.0g, stir, finally adding phosphoric acid regulator solution pH is 3.5.
Embodiment 9
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 33.45g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, is dissolved in water to 1L, and wherein zirconium content is 5.0g/L, and the content of silicon is 5.0g/L, and the content of cobalt is 1.0g/L.Add subsequently commercially available water-soluble benzene emulsion resin 5.0g, stir, finally adding phosphoric acid regulator solution pH is 3.5.
Embodiment 10
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 66.90g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4.94g, adds water to 1L and dissolves, and wherein zirconium content is 5.0g/L, and the content of silicon is 10g/L, and the content of cobalt is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 11
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, adds water to 1L and dissolves, and wherein the content of zirconium and silicon is all 5.0g/L, and the content of aluminium is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 12
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 55.58g of 8.8wt%, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and aluminium obtains content 2.5g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 13
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 111.15g of 8.8wt%, adds water to 1L and dissolves, and wherein the content of zirconium and silicon is 5.0g/L, and the content of aluminium is 5.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 14
Tetrahydrated zirconium sulfate 19.48g, titanium potassium oxalate(T.P.O.) 37.0g, ammonium meta-vanadate 2.30g, heating water dissolves to 1L, and wherein the content of zirconium and titanium is 5.0g/L, content of vanadium 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 15
Tetrahydrated zirconium sulfate 19.48g, titanium potassium oxalate(T.P.O.) 37.0g, ammonium meta-vanadate 5.74g, heating water dissolves to 1L, and wherein the content of zirconium and titanium is 5.0g/L, and the content of vanadium is 2.5g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 16
Tetrahydrated zirconium sulfate 19.48g, titanium potassium oxalate(T.P.O.) 37.0g, ammonium meta-vanadate 11.48g, heating water dissolves to 1L, and wherein the content of zirconium and titanium is 5.0g/L, and the content of vanadium is 5.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 17
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, phosphate dihydrogen manganese 7.14g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, the content 1.0g/L of manganese.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 18
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, phosphate dihydrogen manganese 17.86g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, the content 2.5g/L of manganese.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 19
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, phosphate dihydrogen manganese 35.71g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, the content 5.0g/L of manganese.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 20
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, cobalt chloride 2.2g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and the content of cobalt is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 21
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, cobalt chloride 5.5g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and the content of cobalt is 2.5g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 22
Tetrahydrated zirconium sulfate 19.48g, Sodium Silicofluoride 33.47g, cobalt chloride 11.0g, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and the content of cobalt is 5.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 23
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, nickel sulfate hexahydrate 4.48g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of nickel is 1.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.5.
Embodiment 24
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, nickel sulfate hexahydrate 11.19g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of nickel is 2.5g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.5.
Embodiment 25
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, nickel sulfate hexahydrate 22.39g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of nickel is 5.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.5.
Embodiment 26
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, ammonium paramolybdate 1.73g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of molybdenum is 1.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 27
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, ammonium paramolybdate 4.33g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of molybdenum is 2.5g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 28
Ammonium fluozirconate 13.23g, careless potassium titanate 7.40g, ammonium paramolybdate 8.66g, adds water to 1L and dissolves, and wherein the content of zirconium and titanium is 5.0g/L, and the content of molybdenum is 5.0g/L.Add subsequently commercially available water-soluble acrylic resin cation (R.C.) 5.0g, be fully uniformly mixed, finally add the phosphoric acid of 86wt%, regulating final pH is 3.0.
Embodiment 29
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 31.71g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, adds water to 1L and dissolves, and wherein the content of zirconium and silicon is all 5.0g/L, and the content of aluminium is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 1.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 30
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 31.71g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and the content of aluminium is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 5.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Embodiment 31
Tetrahydrated zirconium sulfate 19.48g, ammonium silicofluoride 31.71g, Al
2o
3content, at the phosphate dihydrogen aluminum solution 22.23g of 8.8wt%, adds water to 1L and dissolves, and wherein zirconium and silicone content are all 5.0g/L, and the content of cobalt is 1.0g/L.Add subsequently commercially available water-soluble cationic urethane resin 10.0g, stir, finally adding phosphorus acid for adjusting pH is 3.5.
Table 1 has been listed the interpolation situation of the each metal ion of above-described embodiment 1-31 and water soluble resin intuitively.
Table 1
Using the passivating solution of above-described embodiment 1-31 as electrolytic solution, carry out DC electrolysis passivation using the tin plate without passivation as negative electrode, the tin plate after the passivation that correspondence obtains is still numbered embodiment 1-31, and passivation temperature is 30 ℃, passivation time is 1.0s, and electrolytic current density is 2.0A/dm
2.
In order to verify the implementation result of the technical program, contriver adopts business tin plate through chromating as reference example 1, adopts without the tin plate of any Passivation Treatment and carries out controlled trial as reference example 2 and the technical program.
After passivation, the surface property evaluation method of tin plate is implemented with reference to QB/T2763-2006, and assessment item has: anti-sulphur, resistance to acid, anti-boiling, sticking power, shock resistance, corrosion strength and baking variable color etc., concrete test evaluation method can be referring to GB.Coating used is PPG2004-827/A-3, the heavy 6-7g/m of film
2, coat rear 200 ℃ of bakings 3 times, each 10min.Baking discoloring temperature is 200 ℃, 10min.
1. anti-sulphur test
Testing liquid: the mixing solutions of L-type cysteine hydrochloride (0.5g/L), potassium primary phosphate (3.6g/L), Sodium phosphate dibasic (7.2g/L).Mixing solutions should use in 4h after preparation.
Testing sequence:
1. the square that is 3mm by folding print one-tenth spacing, is immersed in the inert containers that fills testing liquid, seals.Testing liquid should be at 5～7mm apart from the lid inner face of container.
2. test chamber is placed in pressure kettle, is heated to 121 ℃ and keep 60min, natural step-down, cooling after, take out print, clean, dry.Observe film situation.
3. after test, film comes off without obvious sulphur spot, nothing.
Table 2 has been listed the corresponding situation of anti-sulphur rank and sulphur spot.
Table 2
| Anti-sulphur rank | Sulphur spot |
| 1 grade | Without sulphur spot |
| 2 grades | Slight sulphur spot |
| 3 grades | Obviously sulphur spot |
| 4 grades | Serious sulphur spot |
2. resistance to acid test
Testing liquid: acetum (3%), citric acid solution (20g/L).
Testing sequence:
1. by the square of folding print one-tenth spacing 3mm, be immersed in the inert containers that fills testing liquid, seal.Testing liquid should be at 5～7mm apart from the lid inner face of container.
2. test chamber is placed in pressure kettle, is heated to 121 ℃ and keep 30min, natural step-down, cooling after, take out print, clean, dry.Observe film situation.
3. after test, film should be without bubble, without coming off, whitening without variable color, nothing.Film unchanged with ● represent, film occurs that defect is with ■, film occur breaking damaged with ▲ represent.
3. boiling resistance test
1. the square that is 3mm by folding print one-tenth spacing, is dipped in two prints in the inert containers that fills distilled water, and another two prints are placed in the inert containers not adding water.
2. test chamber is placed in pressure kettle, is heated to 121 ℃ and keep 30min, natural step-down, cooling after, take out print.Observe film situation.
3. the product that outer wall applies film after test comes off, whitens without variable color, nothing without bubble, nothing.Film unchanged with ● represent, film occurs that defect is with ■, film occur breaking damaged with ▲ represent.
4. sticking power
Sticking power regulation: category-A product sticking power is not less than 3 grades, and category-B product sticking power is not less than 2 grades, and C series products sticking power is not less than 1 grade.
Determination step:
1., on the scratching instrument that print is 1.5mm in pitch, by the speed of 90～100r/min, marking length is the thread that 60～80mm, diameter are 10mm.Line should be to penetrate film as degree.
2. brush away with writing brush the film of crossing out.The 3M610 adhesive tape that is 25.4mm by width, sticks in thread, by forefinger abdomen translation compression, and reserves 15～20mm adhesive tape as gripping.
3. push down one end of print with finger on the table, by adhesive tape with oblique upper to tearing from film fast.
4. observe the degree that in circle, film is torn of drawing, according to the form below evaluation sticking power.The sticking power of sample should be the arithmetical av of three print measured values.
Table 3 has been listed the come off corresponding situation of area of sticking power rank and film.
Table 3
| Sticking power rank | The film area % that comes off |
| 1 | 0 |
| 2≤ | 10 |
| 3≤ | 25 |
| 4≤ | 50 |
5. corrosion strength test
Testing liquid: the mixing solutions of citric acid (50g/L), SODIUMNITRATE (0.14g/L), xitix (0.5g/L).Testing liquid should use in 4h after preparation.
Testing sequence:
1. the wire of burn-oning at the back side of print, with the back side and the corner of the beeswax coating print of fusing.By in print immersion test solution.Take diameter as 4mm, length is anode as the stainless steel bar of 10mm as negative electrode, print, access 15V direct supply, causes anodic corrosion.After 1h, take out print, clean, be dried.Observe the size and number of etch pit.
2. the evaluation of the corrosion strength of print is evaluated by table 4.
Table 4
6. impact resistance test
Testing liquid: copper-bath (50g/L).
Testing sequence: the tested surface of print is inserted to Apparatus for Impacting at low-temp downwards, highly sweep away from 1m with 1kg weight; Or print is washed into the cover that diameter is 60～90mm.In punching process, should not damage steel substrate.To impact print or cover and immerse in copper-bath, after 30min, take out print, and clean, be dried.Observe and impact the hemisphere face of print or the corrosion condition of cover.
After test, film should be without intensive hot spot.Corrosion-free with ● represent, have partial corrosion point to represent with ■, have a lot of hot spots with ▲ represent.
Table 5 has been listed the Experimental Comparison result of this case embodiment 1～31 and reference example 1～2.
Table 5
| Embodiment and reference example | Anti-sulfuration | Resistance to acid | Anti-boiling | Sticking power | Shock resistance | Corrosion strength | Baking variable color (Δ E) |
| Embodiment 1 | 2 | ● | ● | 1 | ■ | 2 | 0.55 |
| Embodiment 2 | 2 | ● | ● | 1 | ● | 2 | 0.61 |
| Embodiment 3 | 1 | ● | ● | 1 | ● | 1 | 0.38 |
| Embodiment 4 | 1 | ● | ■ | 2 | ● | 1 | 0.26 |
| Embodiment 5 | 2 | ● | ● | 1 | ● | 1 | 0.57 |
| Embodiment 6 | 1 | ● | ● | 1 | ● | 0 | 0.40 |
| Embodiment 7 | 1 | ● | ● | 1 | ● | 0 | 0.41 |
| Embodiment 8 | 2 | ● | ● | 1 | ● | 1 | 0.29 |
| Embodiment 9 | 1 | ■ | ● | 1 | ■ | 0 | 0.36 |
| Embodiment 10 | 1 | ■ | ● | 2 | ■ | 0 | 0.44 |
| Embodiment 11 | 1 | ● | ■ | 1 | ■ | 1 | 0.63 |
| Embodiment 12 | 1 | ● | ● | 1 | ■ | 0 | 0.52 |
| Embodiment 13 | 1 | ■ | ● | 1 | ● | 0 | 0.48 |
| Embodiment 14 | 2 | ● | ● | 1 | ■ | 0 | 0.37 |
| Embodiment 15 | 2 | ● | ● | 1 | ■ | 1 | 0.65 |
| Embodiment 16 | 1 | ● | ● | 1 | ■ | 1 | 0.53 |
| Embodiment 17 | 3 | ● | ■ | 1 | ● | 0 | 0.43 |
| Embodiment 18 | 2 | ● | ■ | 1 | ● | 1 | 0.66 |
| Embodiment 19 | 2 | ■ | ● | 1 | ■ | 1 | 0.72 |
| Embodiment 20 | 2 | ● | ● | 1 | ● | 1 | 0.59 |
| Embodiment 21 | 1 | ■ | ● | 1 | ● | 0 | 0.32 |
| Embodiment 22 | 1 | ● | ● | 1 | ● | 0 | 0.28 |
| Embodiment 23 | 2 | ● | ● | 1 | ● | 1 | 0.33 |
| Embodiment 24 | 1 | ● | ■ | 1 | ■ | 0 | 0.54 |
| Embodiment 25 | 1 | ● | ● | 1 | ■ | 1 | 0.65 |
| Embodiment 26 | 2 | ■ | ● | 1 | ● | 1 | 0.74 |
| Embodiment 27 | 1 | ● | ■ | 1 | ■ | 0 | 0.19 |
| Embodiment 28 | 1 | ● | ● | 1 | ● | 0 | 0.22 |
| Embodiment 29 | 1 | ● | ● | 1 | ■ | 1 | 0.23 |
| Embodiment 30 | 1 | ● | ● | 1 | ● | 0 | 0.51 |
| Embodiment 31 | 1 | ■ | ■ | 1 | ● | 0 | 0.48 |
| Reference example 1 | 2 | ● | ● | 1 | ● | 1 | 0.07 |
| Reference example 2 | 2 | ● | ● | 1 | ■ | 2 | 0.09 |
As seen from Table 5, through the eleetrotinplate low chromium passivating thin plate of processing of the present invention, its anti-sulphur has had and has significantly improved, and all the other are as all suitable with sexavalent chrome passivation result in antiacid, anti-boiling, sticking power, shock resistance and anodic corrosion corrosion strength.
In order further directly to compare the solidity to corrosion of the technical program and sexavalent chrome passivation tin plate, contriver is also with reference to the method for evaluating performance of chromium-free deactivation on galvanized sheet, equally also carry out the corrosion proof test of SST salt fog, test conditions is equal to the standard of galvanized sheet: 5% NaCl concentration, 30 ° of angles, the thermostat temperature of 36 ℃ ± 2 ℃.Because the tin coating of tin plate is very thin, the solidity to corrosion of its substrate, far below galvanized sheet, therefore, is controlled at 16hr by SST test period.
Table 6 has been listed the Experimental Comparison result of this case embodiment 1～31 and reference example 1～2.
Table 6
| Print numbering | Red rust area (%) |
| Embodiment 1 | 60% |
| Embodiment 2 | 50% |
| Embodiment 3 | 30% |
| Embodiment 4 | 30% |
| Embodiment 5 | 40% |
| Embodiment 6 | 30% |
| Embodiment 7 | 20% |
| Embodiment 8 | 70% |
| Embodiment 9 | 60% |
| Embodiment 10 | 65% |
| Embodiment 11 | 50% |
| Embodiment 12 | 40% |
| Embodiment 13 | 30% |
| Embodiment 14 | 60% |
| Embodiment 15 | 70% |
| Embodiment 16 | 60% |
| Embodiment 17 | 70% |
| Embodiment 18 | 60% |
| Embodiment 19 | 60% |
| Embodiment 20 | 60% |
| Embodiment 21 | 50% |
| Embodiment 22 | 50% |
| Embodiment 23 | 65% |
| Embodiment 24 | 60% |
| Embodiment 25 | 60% |
| Embodiment 26 | 60% |
| Embodiment 27 | 50% |
| Embodiment 28 | 40% |
| Embodiment 29 | 65% |
| Embodiment 30 | 55% |
| Embodiment 31 | 50% |
| Reference example 1 | 80% |
| Reference example 2 | 90% |
As can be seen from Table 6, the electrolytic tinplate of conventional chromating is after the 16hr salt-fog test of 5%NaCl solution, red rust area has reached 90%, and adopt the electrolytic tinplate of the technical program processing under same test conditions, its red rust area is between 15%～60%, the solidity to corrosion of the electrolytic tinplate that this explanation was processed through chromium-free passivation liquid of the present invention is very excellent, has surmounted the effect of chromating processing electrolytic tinplate.
Be noted that above enumerate only for specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar variations thereupon.If all distortion that those skilled in the art directly derives or associates from content disclosed by the invention, all should belong to protection scope of the present invention.
Claims (8)
1. for the treatment of a chromium-free passivation liquid for tin plate, it is characterized in that, its pH value is 3～4, and chromium-free passivation liquid comprises:
At least mineral compound of one of them that contains silicon, titanium and zirconium, and the content of silicon, titanium and zirconium is 0.1～20g/L;
At least metallic compound of one of them that contains aluminium, vanadium, manganese, cobalt, nickel and molybdenum, and the content of aluminium, vanadium, manganese, cobalt, nickel and molybdenum is 0.1～20g/L;
Water soluble resin, and its content is 0.1～20g/L;
In order to the pH value of passivating solution is adjusted to 3～4 acid;
Surplus is water and other inevitable impurity.
2. the chromium-free passivation liquid for the treatment of tin plate as claimed in claim 1, it is characterized in that, described mineral compound comprises one or more in potassium fluozirconate, ammonium fluozirconate, zirconyl sulfate, oxalic acid zirconium potassium, potassium fluotitanate, ammonium titanium fluoride, titanyl sulfate, titanium potassium oxalate(T.P.O.), Sodium Silicofluoride, potassium silicofluoride, ammonium silicofluoride, magnesium silicofluoride.
3. the chromium-free passivation liquid for the treatment of tin plate as claimed in claim 2, it is characterized in that, described metallic compound comprises one or more in Tai-Ace S 150, Burow Solution, oxalic acid aluminium, sodium metaaluminate, aluminum phosphate, aluminium dihydrogen phosphate, ammonium meta-vanadate, sodium metavanadate, potassium metavanadate, vanadylic sulfate, oxalic acid vanadyl, phosphate dihydrogen manganese, manganous nitrate, manganous sulfate, manganous carbonate, rose vitriol, cobalt chloride, cobalt oxalate, cobaltous carbonate, single nickel salt, nickelous nitrate, nickel acetate, Sodium orthomolybdate, ammonium paramolybdate.
4. the chromium-free passivation liquid for the treatment of tin plate as claimed in claim 3, is characterized in that, described water soluble resin is water-soluble cationic resin and/or water-soluble nonionic resin and/or water soluble anion resin.
5. the chromium-free passivation liquid for the treatment of tin plate as claimed in claim 4, it is characterized in that, described water soluble resin comprises one or more in cationic acrylate analog copolymer, positively charged ion Styrene-Acrylate Emulsion Polymerization thing, positively charged ion propylene oxide acid copolymer, polyurethane/cationic ester polymer.
6. the chromium-free passivation liquid for the treatment of tin plate as described in any one in claim 1-5, is characterized in that, described acid is phosphoric acid.
7. the chromium-free passivation liquid for the treatment of tin plate as claimed in claim 6, is characterized in that, its pH value is 3.5.
8. the chromium-free passivation liquid for the treatment of tin plate as described in any one in claim 1-5, is characterized in that, its pH value is 3.5.
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Application publication date: 20140521 |