CN103882416A - Zirconium metal painting pre-treatment agent for scrubbing cold-roll steel sheets - Google Patents
Zirconium metal painting pre-treatment agent for scrubbing cold-roll steel sheets Download PDFInfo
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Abstract
The invention discloses a zirconium metal painting pre-treatment agent for scrubbing cold-roll steel sheets. Ionic liquid and one of nanometer titania, nanometer zirconia or nanometer zirconium fluoride are added to the pre-treatment agent, so that the oxidized corrosion rate of and the damage caused by ultraviolet radiation of the metal surface can be relieved by the pre-treatment agent. The metal pre-treatment agent is convenient to use, free of environmental pollution, green and environment-friendly, and a plurality of steps are simplified into one step.
Description
Technical field
The present invention relates to coated metal field, particularly a kind of without phosphorus scouring zirconium coated metal pretreating reagent.
Background technology
Most conversion coating treating fluid all contains chromic salt or phosphoric acid salt traditionally; although can obtain more satisfied effect; but along with day by day strengthening and the continuous maturation that transforms application of membrane of countries in the world environmental protection consciousness, traditional industrial technology will progressively be replaced by environment-friendly type conversion film technology.
Application is the anti-corrosion method of widespread use in metal finishing; Coating Pretreatment is the requisite preliminary processes of application; its effect is on protected metal works, to set up one can receive on-metallic protective coating; make metal works there is good sticking power to paint film; so that the two is more firmly attached on together, thus the anti-corrosion capability of raising coating.
At present, at paint industry, metal products is the application of sheet material especially, conventionally adopt phosphating process control corrosion of metal, experienced the exploitation of 140 years, phosphorization technology is constantly perfect, after World War II finishes, phosphorization technology is obtained important improvement at aspects such as low temperature, controlling diaphragm weight, high-speed and continuous, is widely used in corrosion protection technology and metal cold deformation processing industry.But there are a lot of problems in this technique, in most Phosphating Solutions that Present Domestic uses, all contain poisonous or with serious pollution composition, as present most widely used phosphatization accelerator---nitrite, itself be exactly a kind of hazardous and noxious substances; In addition the heavy metal ion such as some nickel, chromium containing in Phosphating Solution is the source of pollution that hazardness is larger, and meanwhile, phosphoric acid salt, the tensio-active agent etc. that in parkerizing process, must adopt are also to environment.Therefore, above-mentioned environment-protecting asepsis phosphatization can not really realize nontoxic pollution-free, and refers to respect to the with serious pollution present situation of current phosphatization, relies on modern technique, to significantly reducing its pollution and toxicity, can meet current environmental requirement.Mainly nitrite, heavy metal Ni due to what phosphorization treatment process toxic was large, damage ratio is more serious
2+, Cr
6+, Mn
2+plasma, therefore, the research in this field also mainly concentrates on as in these material searching substitutes.
It is to adopt the non-phosphating process of environment-friendly type to obtain the effect that bonderizing reaches that phosphatization substitutes, and it is abandoned phosphate system completely and adopts brand-new treatment process, and it is the developing direction of Coating Pretreatment.But, non-phosphating process is processed the technological effect reaching and is wanted inferior a lot of compared to phosphating process, as Chinese patent 200710010966.3 and 201010617760.9 all discloses the treatment technology of the cold-rolled steel sheet of phosphatization substitute technology to galvanized sheet, it need to be soaked in pending workpiece in treatment solution, not only need a large amount for the treatment of solutions, and when after treatment solution use for some time, can can not continue due to the variation of its concentration to use, in addition, this method operation inconvenience, for a large amount of irregular workpiece and the larger workpiece of volume, cannot enter actual production line and carry out normal zirconium processing.
Therefore, urgently develop a kind of coated metal pretreating reagent of quick, energy-conserving and environment-protective easy to use.
Summary of the invention
In order to address the above problem, the inventor has carried out research with keen determination, found that: ionic liquid is all made up of ion at normal temperatures to there is stronger dissolving power, regulate zwitterion by design, can adjust the solvability to inorganics, water, organism and polymkeric substance, electric conductivity is strong, can be used as inhibiter, simultaneously, ionic liquid has less surface tension, can be used as tensio-active agent; The powders such as nano titanium oxide, nano zircite and nanometer Zirconium tetrafluoride have the effect of uv-absorbing, can reduce the corrosion of ultraviolet ray to metallic surface; Water-soluble polymer Polythiophene or polypyrrole have good antiseptic property; and the main purpose of zirconium coated metal pre-treatment is and removes the spots such as the greasy dirt of metallic surface; and metallic surface forms protection; therefore the present invention adds the powder such as ionic liquid and nano titanium oxide, nano zircite and nanometer Zirconium tetrafluoride in pretreating reagent; thereby complete the present invention; in addition, in pretreating reagent provided by the invention, do not contain phosphorus or chromium element, environmental protection.
The object of the present invention is to provide following aspect:
First aspect, the invention provides a kind of cold-rolled steel sheet and cleans zirconium coated metal pretreating reagent, it is characterized in that, this metal pretreating reagent, taking himself gross weight as 100%, comprises the component of following weight percent:
Wherein,
Described ionic liquid is the ionic liquid at room temperature that nitrogen-containing heterocycle compound positively charged ion and inorganic/organic anion form, and is selected from: Tetrafluoroboric acid 1-butyl-3-Methylimidazole ionic liquid, bromo 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid N-ethylpyridine ionic liquid or trifluoroacetic acid 1-butyl-3-Methylimidazole ionic liquid;
The D50 particle diameter 10～60nm of described nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride;
The number-average molecular weight of water-soluble polymer Polythiophene or polypyrrole is 8000～100000;
Described pH adjusting agent is selected from citric acid, oxalic acid, sodium carbonate, sodium bicarbonate;
The pH value that described cold-rolled steel sheet is cleaned zirconium coated metal pretreating reagent is 5.2～8.8.
Second aspect, the invention provides above-mentioned cold-rolled steel sheet and clean zirconium coated metal pretreating reagent, it is characterized in that, described tensio-active agent is nonionic surface active agent, be preferably fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, sapn series or tween series, be particularly preferably octyl phenol Soxylat A 25-7-10, sorbester p18 or tween 80.
The third aspect, the invention provides above-mentioned cold-rolled steel sheet and cleans zirconium coated metal pretreating reagent, it is characterized in that, described silicate or metasilicate are water glass.
Fourth aspect, the invention provides above-mentioned cold-rolled steel sheet and cleans zirconium coated metal pretreating reagent, it is characterized in that, described chitosan be N-deacetylation 70%～100%, molecular-weight average is 9.5 × 10
5～1.4 × 10
6chitosan.
The 5th aspect, the invention provides above-mentioned cold-rolled steel sheet and cleans zirconium coated metal pretreating reagent, it is characterized in that,
Described antioxidant is selected from Resorcinol, Resorcinol, pyrocatechol, catechol, 2,6-di-t-butyl-alpha, alpha-dimethyl amido Pyrogentisinic Acid or 4,4-methylene radical (2,6 di t butyl phenol);
Described film coalescence aid is lauryl alcohol ester.
The 6th aspect, the present invention also provides a kind of using method of being cleaned zirconium coated metal pretreating reagent by the cold-rolled steel sheet described in above-mentioned the first to five aspect, it is characterized in that, cold-rolled steel sheet is cleaned to zirconium coated metal pretreating reagent spreading implement and evenly coat pending workpiece surface.
Described metal pretreating reagent is the cold-rolled steel sheet described in claim and cleans zirconium coated metal pretreating reagent herein.
Clean zirconium coated metal pretreating reagent and using method thereof according to cold-rolled steel sheet provided by the invention, there is following beneficial effect:
(1) cold-rolled steel sheet provided by the invention is cleaned zirconium coated metal pretreating reagent and can be substituted conventional three-in-one, four-in-one scouring Phosphating Solution, the metal product surface such as cold-reduced sheet, galvanized sheet is carried out to pre-treatment, the present invention has more excellent sticking power, energy-conserving and environment-protective performance;
(2) in the time of cold rolled metal workpiece or galvanized workpiece, without being equipped with Special coating pre-processing device and station, only need by clean zirconium coated metal pretreating reagent for rag, brush or roller Direct Uniform coat cold rolled metal workpiece surface or galvanized workpiece is surperficial, the operations such as the degreasing in common zirconium metallization processes, washing, zirconium processing, washing are directly merged into obliterating or brushed step of zirconium liquid, without relevant devices such as special soaking compartment or spray grooves, save space, reduce investment outlay;
(3) cold-rolled steel sheet provided by the invention is cleaned zirconium coated metal pretreating reagent and is not in use produced waste water and waste residue, environmental protection;
(4) to be specially adapted to volume large for scouring zirconium coated metal pretreating reagent provided by the invention, can not enter common zirconium paint line, the surface pretreatment of the slight workpiece of greasy dirt; Or Emergency use cannot normally use for Coating Pretreatment production unit time;
(5) cold-rolled steel sheet provided by the invention is cleaned zirconium coated metal pretreating reagent and is adopted chemically transformed film technique, except treatment process and the advantage such as equipment is simple, easy to operate, less investment benefit, also can avoid etching waste liquor processing, and this cold-rolled steel sheet scouring zirconium coated metal pretreating reagent expection contributes to prevent that ionic environment from polluting.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more clear, clear and definite along with these explanations.
The inventor finds through research, ionic liquid has stronger dissolving power, regulate zwitterion by design, can adjust the solvability to inorganics, water, organism and polymkeric substance, electric conductivity is strong, can be used as inhibiter, simultaneously, ionic liquid has less surface tension, can be used as tensio-active agent; The powders such as nano titanium oxide, nano zircite and nanometer Zirconium tetrafluoride have the effect that uvioresistant absorbs, can reduce the corrosion of ultraviolet ray to metallic surface, therefore the invention provides the metal pretreating reagent (taking the gross weight of metal pretreating reagent as 100%) that comprises following weight percent component:
Wherein, described ionic liquid is the ionic liquid at room temperature that nitrogen-containing heterocycle compound positively charged ion and inorganic/organic anion form, wherein said nitrogen-containing heterocycle compound positively charged ion is alkyl pyridine or 1,3-dialkylimidazolium, wherein alkyl is that chain length is straight chained alkyl, branched-chain alkyl or the cycloalkyl of C2～C8; Described inorganic anion is chlorine aluminate, tetrafluoroborate, hexafluoro-phosphate radical, fluorion, chlorion, bromide anion or iodide ion; Described organic anion is trifluoroacetic acid root or acetate ion, as Tetrafluoroboric acid 1-butyl-3-Methylimidazole ionic liquid, bromo 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid N-ethylpyridine ionic liquid or trifluoroacetic acid 1-butyl-3-Methylimidazole ionic liquid.
Ionic liquid is to be made up of the ion of positively charged and electronegative ion, it is all liquid state between negative 100 degrees Celsius to 200 degrees Celsius, therefore, it is easily dissolved in tensio-active agent, water-soluble polymer Polythiophene or polypyrrole, antioxidant, wetting agent, film coalescence aid, second alcohol and water, easily realize dispersedly, make metal pretreating reagent stable performance homogeneous.Ionic liquid can regulate its solvability to inorganics, water, organism and polymkeric substance by design zwitterion, even its acidity can be adjusted to super acid, thereby the spot of metallic surface is carried out to eccysis, simultaneously, ionic liquid has that larger polarity Modulatory character, viscosity are low, density is large, can form two-phase or heterogeneous system, to a large amount of inorganic and all good dissolving poweies of performance place of organic substance, have the dual-use function of solvent and catalyzer, it is considered to and supercritical CO
2form three large green solvents together with double water-phase; simultaneously; because ionic liquid all exists with ionic condition at normal temperatures; therefore there is larger specific conductivity; therefore the effect that ionic liquid can play inhibition in metallic surface reduces the speed that is corroded of metallic surface, thereby protection metallic surface is intact.In addition, the different organic/inorganic zwitterions that exist in ionic liquid can play Action of Surfactant, thereby increase the uniformity coefficient of metal pretreating reagent in metallic surface coating.
In metal pretreating reagent, when the consumption of ionic liquid is less than 0.2%, ionic liquid consumption is very few, its corrosion inhibition and to increase surface-active effect not obvious; In the time that ionic liquid consumption is greater than 1.7%, its corrosion inhibition in metal pretreatment liquid and increase the not obvious increase of surface-active effect, continues to increase consumption, can roll up production cost, and the waste that brings resource, therefore, it is 0.2～1.7% that the present invention selects the consumption of ionic liquid.
Nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride have stronger uvioresistant activity, and ultraviolet catalytic activity, catalytic decomposition organism under its condition existing at sunlight, be decomposed into micromolecular compound and removed, therefore the present invention adds nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride, and uvioresistant processing is carried out in metallic surface; Meanwhile, the surface of Nano titanium dioxide, zirconium white or Zirconium tetrafluoride powder is in activated state, and the oxygenizement of the active oxygen of its generation has and is similar to the supercoat of sexavalent chrome acid compound as the caused chemical action of oxygenant; In addition, Nano titanium dioxide, nano zircite or nanometer Zirconium tetrafluoride can improve the antirust ability of metallic surface effectively, and strengthen metallic surface frictional coefficient.
When the D50 particle diameter of above-mentioned substance is greater than 60nm, its particle diameter is excessive, disperses inhomogeneously in metal pretreating reagent, and is applied to and easily forms irregular projection behind metallic surface, and reduce the effect of subsequent disposal; In the time that its D50 is less than 10nm, it is easily reunited, difficulties in dispersion, and therefore, selecting D50 particle diameter is 10～60nm.
In the time that the consumption of above-mentioned substance is less than 0.8%, addition is very few, and its uvioresistant effect, oxidation protection effect and rust inhibition are not obvious; In the time that the consumption of above-mentioned substance is greater than 4%; its consumption is excessive; uvioresistant effect, oxidation protection effect and rust inhibition significantly do not increase; and be difficult for other component miscible because of it; and make the homogeneity variation of metal pretreating reagent; therefore, to select the consumption of nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride be 0.8～4% in the present invention.
Water-soluble polymer Polythiophene or polypyrrole have stronger antiseptic power, be added in metal pretreating reagent, can effectively improve the resistance to corrosion of metallic surface, number-average molecular weight is that the preservative property of 8000～100000 water-soluble polymer Polythiophene or polypyrrole are better, in the time that its consumption is less than 0.2%, its preservative effect is not obvious, in the time that its consumption is greater than 2%, its consumption is excessive, not only cause metal pretreating reagent viscosity excessive, be difficult for disperseing, and the not obvious increase of antiseptic property, and cause the waste of raw material, therefore, it is 0.2～2% that the present invention selects the consumption of water soluble molecules Polythiophene or polypyrrole.
Ion in ionic liquid dispersibles around water-soluble polymer Polythiophene or polypyrrole molecule, thereby has increased the erosion resistance of the metal pretreating reagent of water-soluble polymer Polythiophene or polypyrrole.
Ionic liquid, nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride and water-soluble polymer Polythiophene or polypyrrole three synergy; can increase greatly anti-oxidant, uvioresistant and the erosion-resisting ability of metal pretreating reagent; thereby metallic surface is formed to good protection; simultaneously; the corrosion resistance that three mixes rear metal pretreating reagent strengthens, and ensures the functional of coated metal.
Tensio-active agent is selected nonionic surface active agent, avoid itself and ionic liquid to react, thereby ensure that tensio-active agent and ionic liquid can synergys, preferred surfactant is fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, sapn series or tween series, be particularly preferably octyl phenol Soxylat A 25-7-10(OP-10), sorbester p18 or tween 80, tensio-active agent can reduce the surface tension of metal pretreating reagent, make it wetting in metallic surface, emulsification, increase after tensio-active agent, metal pretreating reagent can use at normal temperatures, energy efficient, treatment time is short, only need to soak 1 to 3 minute, and phosphatization immersion will be processed 15 minutes, thereby the present invention uses easy to operate.In the time that dosage of surfactant is less than 0.2%, it is wetting, emulsifying effect is not obvious, and in the time that its consumption is greater than 1%, its consumption is excessive, and the film process time is increased, and therefore, the consumption of option table surface-active agent of the present invention is 0.2～1%.
Silicate or metasilicate are selected water glass, increase binding property and the transparency of metal conditioner, in the time that its consumption is less than 0.5%, its adhesive effect is not obvious, in the time that its consumption is greater than 2%, its viscosity is excessive, reduces metal conditioner in the development rate of metallic surface and the homogeneity of film forming.
Antioxidant is selected from Resorcinol, Resorcinol, pyrocatechol, catechol, 2,6-di-t-butyl-alpha, alpha-dimethyl amido Pyrogentisinic Acid or 4,4-methylene radical (2,6-DI-tert-butylphenol compounds) etc. there is the organic compound of reductibility active group, active group in these compounds can with oxidizing substance generation redox reaction, thereby slow down the oxidized speed of metallic surface, prevent and delay product deterioration by oxidation, as variable color, peculiar smell, oxidative rancidity, this causes that compound has larger solvability in ethanol or water simultaneously.In the time that the consumption of oxidation inhibitor is less than 0.1%, its antioxygenation DeGrain, in the time that its consumption is greater than 0.5%, its antioxygenation effect does not significantly increase, and for cost-saving, it is 0.1～0.5% that the present invention selects the amount ranges of oxidation inhibitor.
It is the wetting agent in metal pretreating reagent that the present invention selects commercially available conventional wetting agent to use, as the organosilicon wetting agent Silok4650 of Guangzhou Si Luoke Chemical Co., Ltd., the non-ionic water wetting agent PM-WET100 of Lanzhou Pu Luomen company, PM-WET101 and polycarboxylate sodium's aqueous wetting agent PM-DISPERSANT5040, the non-ionic water wetting agent GR-500 of Shanghai Ge Running Chemical Industry Science Co., Ltd, Richdol & reg101 of Shang nautical mile specialization work Science and Technology Ltd. non-ionic water wetting agent etc., it can reduce the surface tension of metal pretreating reagent, ensure that metal pretreating reagent can fully launch in metallic surface, make solvent and other component can or penetrate its surface, and metallic surface is wetting.In the time that its consumption is less than 0.2%, its consumption is very few, and lubricant effect is not obvious, and in the time that its consumption is greater than 0.5%, its consumption is excessive, and the surface tension of metal pretreating reagent is too small, and development rate is too fast, wayward, and therefore, it is 0.2～0.5% that the present invention selects its consumption.
Film coalescence aid is lauryl alcohol ester, and it not only can be lowered into film temperature, also can improve film weathering resistance, can scrubbing character, cleanablity, touch-up paint and improve the color developing of coating; Its a small amount of use can realize above-mentioned functions, but in the time that its consumption is less than 0.0001%, its consumption is too low, reduction to film-forming temperature, film weathering resistance, can scrubbing character, the improvement of cleanablity, touch-up paint and the color developing to coating is not obvious; When its consumption is increased to 4% when above, the not obvious increase of its improvement to film properties, therefore, it is 0.01～0.04% that the present invention selects the consumption of film coalescence aid.
PH adjusting agent is selected from citric acid, oxalic acid, sodium carbonate, sodium bicarbonate, for regulating the pH of metal pretreating reagent, makes each component can synergy, and experiment shows, in the time that pH is 5.2～8.8, and the action effect optimum of metal pretreating reagent.
The pH value that described cold-rolled steel sheet is cleaned zirconium coated metal pretreating reagent is 5.2～8.8, the present invention selects the primary solvent as metal pretreating reagent with second alcohol and water, be because its surface can be more much higher than the surface energy of metal plate, can effectively disperse in metallic surface.
The present invention's each component used does not all contain other poisonous element that maybe can cause environmental pollution such as phosphorus or chromium, therefore, and scouring zirconium coated metal pretreating reagent provided by the invention environmental protection.
The present invention also provides the using method of above-mentioned scouring zirconium coated metal pretreating reagent, in the time of cold rolled metal workpiece or galvanized workpiece, do not need special painting pre-processing device and station, only need be by cleaning zirconium coated metal pretreating reagent rag or brush, roller Direct Uniform is coated cold rolled metal workpiece surface or galvanized workpiece surface.Scouring zirconium coated metal pretreating reagent provided by the invention is easy to use, the operations such as the degreasing in common zirconium metallization processes, washing, zirconium processing, washing are directly merged into obliterating or brushed step of zirconium liquid, without relevant devices such as special soaking compartment or spray grooves, save time, space and Financial cost.
Embodiment
It is as follows that the present embodiment agents useful for same is purchased information:
Nano zircite is purchased from Hangzhou Wanjing New Material Co., Ltd., and D50 particle diameter is 45nm;
Nano titanium oxide is purchased from Henan Huarong Environmental Protection Technology Co., Ltd, ZXL-001, median size≤20nm;
PM-WET100 is purchased from Lanzhou Pu Luomen company, non-ionic water wetting agent.
embodiment 1
A kind of zirconium coated metal pretreating reagent of cleaning, taking pretreating reagent gross weight as 100%, comprises the component of following weight percent:
The number-average molecular weight of described water-soluble polymer Polythiophene is 15000.
embodiment 2
The present embodiment is identical with embodiment 1 method therefor, and difference is only that ionic liquid used is bromo 1-butyl-3-Methylimidazole ionic liquid.
embodiment 3
The present embodiment is identical with embodiment 1 method therefor, and difference is only that ionic liquid used is phosphofluoric acid 1-butyl-3-Methylimidazole ionic liquid.
embodiment 4
The present embodiment is identical with embodiment 1 method therefor, and difference is only that ionic liquid used is phosphofluoric acid N-ethylpyridine ionic liquid.
embodiment 5
The present embodiment is identical with embodiment 1 method therefor, and difference is only that ionic liquid used is trifluoroacetic acid 1-butyl-3-Methylimidazole ionic liquid.
embodiment 6
The present embodiment is identical with embodiment 1 method therefor, and difference is only that ionic liquid used is bromo 1-butyl-3-Methylimidazole ionic liquid; The number-average molecular weight of water-soluble polymer Polythiophene is 20000.
embodiment 7
A kind of zirconium coated metal pretreating reagent of cleaning, taking pretreating reagent gross weight as 100%, comprises the component of following weight percent:
Wherein, the number-average molecular weight of described water-soluble polymer polypyrrole is 12000; Regulating above-mentioned composition pH value is 7.0.
embodiment 8
The present embodiment method therefor is identical with embodiment 7, and difference is only that ionic liquid used is bromo 1-butyl-3-Methylimidazole ionic liquid.
embodiment 9
The present embodiment method therefor is identical with embodiment 7, and difference is only that ionic liquid used is phosphofluoric acid 1-butyl-3-Methylimidazole ionic liquid.
embodiment 10
The present embodiment method therefor is identical with embodiment 7, and difference is only that ionic liquid used is phosphofluoric acid N-ethylpyridine ionic liquid.
embodiment 11
The present embodiment method therefor is identical with embodiment 7, and difference is only that ionic liquid used is trifluoroacetic acid 1-butyl-3-Methylimidazole ionic liquid.
embodiment 12
The present embodiment method therefor is identical with embodiment 7, and difference is only that ionic liquid used is bromo 1-butyl-3-Methylimidazole ionic liquid; The number-average molecular weight of water-soluble polymer polypyrrole is 25000.
Comparative example
comparative example 1
This comparative example method therefor is identical with embodiment 1, and difference is only not add ionic liquid.
comparative example 2
This comparative example method therefor is identical with embodiment 1, distinguishes and is only, adding ionic liquid is Tetrabutyl amonium bromide.
comparative example 3
This comparative example method therefor is identical with embodiment 1, and difference is only not add nano zircite.
comparative example 4
This comparative example method therefor is identical with embodiment 1, and difference is only not add water-soluble polymer Polythiophene.
comparative example 5
This comparative example method therefor is identical with embodiment 7, and difference is only not add ionic liquid.
comparative example 6
This comparative example method therefor is identical with embodiment 7, distinguishes and is only, adding ionic liquid is Tetrabutyl amonium bromide.
comparative example 7
This comparative example method therefor is identical with embodiment 7, and difference is only not add nano titanium oxide.
comparative example 8
This comparative example method therefor is identical with embodiment 7, and difference is only not add water-soluble polymer polypyrrole.
Test example
In the present invention in test example the conventional Phosphating Solution of cleaning used purchased from the scouring Phosphating Solution (four-in-one) of great Zheng San river, Jinan company.
(1) clean and spray paint:
6cm × 4cm metal foil test specimen plate (cold-rolled steel sheet or steel plate galvanized) is cleaned with the clean rag that is stained with the pretreating reagent that embodiment 1～12 makes or brushed or roller coat with the brush (or roller) that is stained with the pretreating reagent that embodiment 1～12 makes, after brushing or roller coat, being vertically placed on draughty place dries naturally, the high hydroxyl acrylic polyester of rear spraying to be filmed priming paint (film thickness: 10 μ m), with, acrylic acid top-coat (film thickness: 5 μ are m).
(2) test method
(1) naked mould Kesternich test:
To the metal foil test specimen plate of processing through (), to carry out the antirust time of naked film (25 DEG C, 101KPa, relative humidity 70～75%) and measure, 120 hours corrosion rates are no more than 95% and are designated as O, otherwise be designated as ×.
(2) impact strength test:
To the metal foil test specimen plate of processing through (), test by GB/T1732-93 standard, after test, adopting 4 times of magnifying glasses to observe has flawless and breakage, if do not have obvious crackle and breakage to be designated as O, have obvious crackle and breakage be designated as ×.
(3) adhesion tests (hundred lattice tests):
To the metal foil test specimen plate of processing through (), cut on metal foil test specimen plate by cutting machine, depth of cut is with till reaching metal foil test specimen panel material place, form after the cubic grid of 100 1mm, peel off by cellophane tape, the per-cent that accounts for total meshes number by the film meshes number not coming off is evaluated the sticking power of paint, and per-cent is larger, illustrates that sticking power is larger.
(4) secondary adhesion test (hundred lattice tests):
Metal foil test specimen plate after an adhesion test is flooded after two hours in the water of boiling, carry out the evaluation identical with sticking power.
experimental example 1
The scouring zirconium coated metal pretreating reagent making by embodiment 1～6 and comparative example 1, processes cold-rolled steel sheet (Hangzhou Steel Company Q235 steel plate) by the method for () and processes, then use the method in (two) to test, and result is as shown in table 1:
Table 1: cold-rolled steel sheet (Hangzhou Steel Company Q235 steel plate) is processed
experimental example 2
The scouring zirconium coated metal pretreating reagent making by embodiment 7～12 and comparative example 2, processes electrolytic galvanized sheet (Anshan iron and steel plant, SGCC) by the method for () and processes, then use the method in (two) to test, and result is as shown in table 2:
Table 2: electrolytic galvanized sheet (Anshan iron and steel plant, SGCC) is processed
In conjunction with embodiment and exemplary example, the present invention is had been described in detail above, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that in the situation that not departing from spirit and scope of the invention, can carry out multiple replacement of equal value, modify or improve technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (6)
1. cold-rolled steel sheet is cleaned a zirconium coated metal pretreating reagent, it is characterized in that, this metal pretreating reagent, taking himself gross weight as 100%, comprises the component of following weight percent:
Wherein,
Described ionic liquid is the ionic liquid at room temperature that nitrogen-containing heterocycle compound positively charged ion and inorganic/organic anion form, and is selected from: Tetrafluoroboric acid 1-butyl-3-Methylimidazole ionic liquid, bromo 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid 1-butyl-3-Methylimidazole ionic liquid, phosphofluoric acid N-ethylpyridine ionic liquid or trifluoroacetic acid 1-butyl-3-Methylimidazole ionic liquid;
The D50 particle diameter of described nano titanium oxide, nano zircite or nanometer Zirconium tetrafluoride is 10～60nm;
The number-average molecular weight of water-soluble polymer Polythiophene or polypyrrole is 8000～100000;
Described pH adjusting agent is selected from citric acid, oxalic acid, sodium carbonate, sodium bicarbonate;
The pH value that described cold-rolled steel sheet is cleaned zirconium coated metal pretreating reagent is 5.2～8.8.
2. cold-rolled steel sheet according to claim 1 is cleaned zirconium coated metal pretreating reagent, it is characterized in that, described tensio-active agent is nonionic surface active agent, be preferably fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, sapn series or tween series, be particularly preferably octyl phenol Soxylat A 25-7-10, sorbester p18 or tween 80.
3. cold-rolled steel sheet according to claim 1 is cleaned zirconium coated metal pretreating reagent, it is characterized in that, described silicate or metasilicate are water glass.
4. cold-rolled steel sheet according to claim 1 is cleaned zirconium coated metal pretreating reagent, it is characterized in that, described chitosan be N-deacetylation 70%～100%, molecular-weight average is 9.5 × 10
5～1.4 × 10
6chitosan.
5. cold-rolled steel sheet according to claim 1 is cleaned zirconium coated metal pretreating reagent, it is characterized in that,
Described antioxidant is selected from Resorcinol, Resorcinol, pyrocatechol, catechol, 2,6-di-t-butyl-alpha, alpha-dimethyl amido Pyrogentisinic Acid or 4,4-methylene radical (2,6 di t butyl phenol);
Described film coalescence aid is lauryl alcohol ester.
6. a using method of being cleaned zirconium coated metal pretreating reagent by the cold-rolled steel sheet described in claim 1～5, is characterized in that, cold-rolled steel sheet is cleaned to zirconium coated metal pretreating reagent spreading implement and evenly coat pending workpiece surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117801.6A CN103882416B (en) | 2014-03-26 | 2014-03-26 | Zirconium metal painting pre-treatment agent for scrubbing cold-roll steel sheets |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331981A (en) * | 2015-09-29 | 2016-02-17 | 安徽工业大学 | Composite metal surface treatment agent based on conducting polymer |
| CN107740078A (en) * | 2017-11-01 | 2018-02-27 | 合肥工业大学 | Magnesium lithium alloy ionic liquid chemical conversion solution and the method for forming conductive oxide film |
| CN108266571A (en) * | 2017-12-18 | 2018-07-10 | 合肥亿恒智能科技股份有限公司 | A kind of automobile return pipe supporting rack and preparation method thereof |
| CN111965332A (en) * | 2020-07-31 | 2020-11-20 | 东风本田汽车有限公司 | Method for testing matching performance of zirconium salt pretreatment process and vehicle body steel plate oil product |
| CN112334600A (en) * | 2018-06-28 | 2021-02-05 | 日本帕卡濑精株式会社 | Surface treatment agent for metal material, metal material with surface treatment coating film, and method for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978554A (en) * | 2006-12-14 | 2007-06-13 | 浙江工业大学 | Use and dosage of ioonic liquid as tower filler surface treating agent |
| CN101033363A (en) * | 2007-04-10 | 2007-09-12 | 大连工业大学 | Environment-friendly type galvanizing metal surface treating agent |
| US20080254315A1 (en) * | 2007-01-19 | 2008-10-16 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
| CN102051611A (en) * | 2010-12-31 | 2011-05-11 | 大连工业大学 | Metal surface treating agent |
| CN102787310A (en) * | 2012-08-27 | 2012-11-21 | 大连工业大学 | Metal surface treatment agent |
-
2014
- 2014-03-26 CN CN201410117801.6A patent/CN103882416B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978554A (en) * | 2006-12-14 | 2007-06-13 | 浙江工业大学 | Use and dosage of ioonic liquid as tower filler surface treating agent |
| US20080254315A1 (en) * | 2007-01-19 | 2008-10-16 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
| CN101033363A (en) * | 2007-04-10 | 2007-09-12 | 大连工业大学 | Environment-friendly type galvanizing metal surface treating agent |
| CN102051611A (en) * | 2010-12-31 | 2011-05-11 | 大连工业大学 | Metal surface treating agent |
| CN102787310A (en) * | 2012-08-27 | 2012-11-21 | 大连工业大学 | Metal surface treatment agent |
Non-Patent Citations (3)
| Title |
|---|
| 侯建 等: "聚吡咯在防腐领域中的研究进展", 《2008材料腐蚀与控制学术研讨会论文集》 * |
| 李东光: "《金属表面处理剂配方与制备200例》", 30 November 2012, 化学工业出版社 * |
| 马欢 等: "聚噻吩的电化学合成及其对不锈钢的抗腐蚀研究", 《中国腐蚀与防护学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331981A (en) * | 2015-09-29 | 2016-02-17 | 安徽工业大学 | Composite metal surface treatment agent based on conducting polymer |
| CN107740078A (en) * | 2017-11-01 | 2018-02-27 | 合肥工业大学 | Magnesium lithium alloy ionic liquid chemical conversion solution and the method for forming conductive oxide film |
| CN107740078B (en) * | 2017-11-01 | 2021-01-26 | 合肥工业大学 | Magnesium-lithium alloy ionic liquid chemical conversion solution and method for forming conductive oxide film |
| CN108266571A (en) * | 2017-12-18 | 2018-07-10 | 合肥亿恒智能科技股份有限公司 | A kind of automobile return pipe supporting rack and preparation method thereof |
| CN112334600A (en) * | 2018-06-28 | 2021-02-05 | 日本帕卡濑精株式会社 | Surface treatment agent for metal material, metal material with surface treatment coating film, and method for producing same |
| CN111965332A (en) * | 2020-07-31 | 2020-11-20 | 东风本田汽车有限公司 | Method for testing matching performance of zirconium salt pretreatment process and vehicle body steel plate oil product |
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