CN104805422A - Chromium-free passivating solution used for zinc coating, and application method thereof - Google Patents
Chromium-free passivating solution used for zinc coating, and application method thereof Download PDFInfo
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- CN104805422A CN104805422A CN201510080210.0A CN201510080210A CN104805422A CN 104805422 A CN104805422 A CN 104805422A CN 201510080210 A CN201510080210 A CN 201510080210A CN 104805422 A CN104805422 A CN 104805422A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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Abstract
The invention discloses a chromium-free passivating solution used for zinc coating, and an application method thereof. The chromium-free passivating solution used for zinc coating comprises following raw materials: waterborne alkyd resin, a molybdate, diammonium bis[carbonato-O]dihydroxyzirconate, and the balance water; pH value of the chromium-free passivating solution is adjusted to be 1 to 3 with phosphoric acid; and waterborne alkyd resin is prepared from a waterborne monomer, an unsaturated fatty acid, a polyhydric alcohol, and a polyatomic acid. The chromium-free passivating solution is capable of obtaining passivation coatings with excellent performance on metal surfaces; the performance of the passivation coatings is close to that of chromate passivation coatings, and corrosion resistance of the passivation coatings is even better than that of the chromate passivation coatings, so that chromate can be completely replaced by the chromium-free passivating solution, and environmental-friendly passivation coatings are obtained. The chromium-free passivating solution contains no chromate, so that environment pollution is reduced greatly, and requirements of WEES and ROHS restrictions are satisfied. And in addition, raw material cost is low; and a treatment method is simple and convenient.
Description
Technical field
The invention belongs to the passivation treatment technology field of zinc coating, more specifically, the present invention relates to a kind of zinc coating chromium-free passivation liquid and using method thereof, belong to IPC classification number C23C.
Background technology
As everyone knows, traditional aluminum alloy surface protective process technology mainly chromating, this passivation technology is simple, cost is low, etch resistant properties is good, has self-healing properties.But chromating liquid is containing sexavalent chrome, toxicity is large, and environmental pollution is serious, and plating piece easily produces harm to HUMAN HEALTH in production and removal process.Along with the enforcement of European Union RoHS environmental protection instruction, all electronic and electrical equipments sold on EU market must prohibit the use the heavy metals such as lead, mercury, cadmium, sexavalent chrome, meanwhile domestic corresponding environmental practice is also progressively strict, therefore research and develop economy, environmental protection, the efficient and chromium-free deactivation treatment technology being applicable to large-scale commercial production to replace existing chromating treatment technology, there is very important scientific meaning and practical value.
The chromating mechanism of analysis conventional is not difficult to find, chromating liquid is normally made up of hexavalent chromium compound, trivalent chromium compound, conducting salt, complexing agent etc.In the process that passive film is formed, there is the dissolving of zinc, chromate reduction, and the precipitation of trivalent chromium gel, these reactions define the skeleton of passive film, chromic salt is adsorbed on gel with the form of subsalt and forms surface layer subsequently, so far generates complete sexavalent chrome passivation layer.When passivation layer is because of external force after scratch, in malaria, hexavalent chromium compound is water-soluble and react with the zinc layers exposed, namely again carry out Passivation Treatment, thus make passive film repaired, the said process of chromic salt is known as " self-healing " of sexavalent chrome passivation.Generally, the passivation mechanisms of chromic salt is: trivalent chromium forms the framework material of passive film, and sexavalent chrome produces " self-healing " function of passive film.
In recent years, prospect of the application is had and the good chromium-free passivation liquid of effect mainly zirconium titanium system, molybdate, cerium salt, a trivalent chromium etc.The material of the same contaminate environment such as fluorochemical is there is in zirconium titanium system passivating solution.Molybdenum and chromium of the same clan, and molybdate low toxicity, in the process of substitute chromium hydrochlorate, there is certain advantage, but, at chromate passivation film, because sexavalent chrome has strong oxidizing property, motility, can carry out selfreparing after passive film breaks, people wish that Molybdate Passivation Film also has such character very much, but do not have the strong of hexavalent chromate due to the oxidisability of sexavalence molybdate, therefore, molybdate passivation film does not possess the self-healing properties of chromic salt.
Therefore, the selfreparing problem solving molybdate passivation film is necessary.
Summary of the invention
Based on this, in order to overcome the defect of above-mentioned prior art, the invention provides a kind of zinc coating chromium-free passivation liquid and using method thereof, this chromium-free passivation liquid has self-healing properties like chromate.
In order to realize foregoing invention object, this invention takes following technical scheme:
A kind of zinc coating chromium-free passivation liquid and using method thereof, described chromium-free passivation liquid comprises the raw material of following weight percent:
Aqueous alkide resin 10 ~ 25%
Molybdate 0.5 ~ 3%
Zirconium carbonate amine 0.5 ~ 3%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Wherein, described aqueous alkide resin is prepared by aqueous monomers, unsaturated fatty acids, polyvalent alcohol and polyprotonic acid and obtains.
Wherein in an embodiment, described chromium-free passivation liquid also comprises the trimethylolpropane trimethacrylate accounting for described aqueous alkide resin total mass 12 ~ 25%.
Wherein in an embodiment, described aqueous alkide resin is hyperbranched Synolac, described hyperbranched Synolac obtains for Material synthesis with TriMethylolPropane(TMP), dimethylol propionic acid, linolenic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described hyperbranched Synolac is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.68 × 10
3g/mol, the equal molecular mass M of matter
w=5.4 × 10
3g/mol, heterogeneity index M
w/ M
n=1.15.
Wherein in an embodiment, described aqueous alkide resin is hyperbranched Synolac, described hyperbranched Synolac obtains for Material synthesis with dipentaerythritol, dimethylol propionic acid, eleostearic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described dissaving structure is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.45 × 10
3g/mol, the equal molecular mass M of matter
w=5.2 × 10
3g/mol, heterogeneity index M
w/ M
n=1.17.
Wherein in an embodiment, described aqueous monomers is dimethylol propionic acid.
Wherein in an embodiment, described polyvalent alcohol is glycerine, TriMethylolPropane(TMP), monopentaerythritol or dipentaerythritol.
Wherein in an embodiment, described polyprotonic acid is the mixture of Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE, and described MALEIC ANHYDRIDE accounts for 6 ~ 10% of described polyprotonic acid total mass.
Wherein in an embodiment, described unsaturated fatty acids is linolic acid, linolenic acid or eleostearic acid.
Wherein in an embodiment, described molybdate is Sodium orthomolybdate, potassium molybdate, ammonium molybdate or ammonium phosphomolybdate.
Present invention also offers the above-mentioned using method for zinc coating chromium-free passivation liquid, 25 DEG C ~ 35 DEG C, under pH value is the condition of 1 ~ 3, by the method such as roller coating, dip-coating, chromium-free passivation liquid is coated on galvanized sheet surface, more than 80 DEG C more than temperature-curable 30s.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised more easily can understand present disclosure.Can mention a large amount of term in following specification sheets and claims, these terms are defined as following implication.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context.
" optional " or " optionally " refers to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
In the present invention, described term " aqueous alkide resin " refers to " water-based unsaturated polyol fatty acid acid resin ", namely, in the preparation process of Synolac, the monoprotic acid used is unsaturated fatty acids, and described unsaturated fatty acids is specially linolic acid (linoleate, 12-acid), linolenic acid (elaeostearic acid, 12,15-acid) or eleostearic acid (elaeostearic acid, 11,13-acid), it contains the C=C of two or three.With aqueous monomers, unsaturated fatty acids, polyvalent alcohol and polyprotonic acid for raw material, prepare water-based unsaturated polyol fatty acid acid resin, in atmosphere through structure that a series of cross-linking reaction becomes a kind of height netted, therefore, the passive film of a kind of high-compactness and high-bond can be formed on galvanized sheet surface, greatly improve the Corrosion Protection of galvanized sheet.When unsaturated fatty acids contains more double bonds, its performance is better.Water-based unsaturated polyol fatty acid acid resin concentration lower than 10% time, can not form good skeleton structure, solidity to corrosion is bad, and compares thickness during concentration height, become thickness, cost is high.
In the present invention, in described chromium-free passivation liquid, also comprise the trimethylolpropane trimethacrylate TMPTMA as linking agent, the consumption of described linking agent is 12 ~ 25% of described aqueous alkide resin total mass.There is Diels-Alder and react in the conjugated double bond of TMPTMA and unsaturated polyol fatty acid acid resin, in 2h, titration is complete, and 170 DEG C of reaction 2h, prepare the unsaturated polyol fatty acid acid resin of TMPTMA modification.
In the present invention, described term " aqueous monomers " is trimellitic acid 1,2-anhydride TMA, polyoxyethylene glycol PEG, 5-sodium sulfo isophthalate, dimethylol propionic acid DMPA, maleic anhydride or vinylformic acid, is preferably dimethylol propionic acid DMPA.The water-based group introduced by aqueous monomers, change alkali into through neutralization (conventional neutralizing agent has triethylamine, dimethylethanolamine etc.), provide water-soluble, it directly affects the performance of resin.
In the present invention, described term " polyol " refers to one or more in glycerine, TriMethylolPropane(TMP), monopentaerythritol, dipentaerythritol, ethylene glycol, Diethylene Glycol, propylene glycol, and the present invention is preferably glycerine, TriMethylolPropane(TMP), tetramethylolmethane or dipentaerythritol.
In the present invention, described term " polyprotonic acid " refers to one or more in Tetra hydro Phthalic anhydride, isophthalic anhydride, MALEIC ANHYDRIDE and trimellitic acid 1,2-anhydride, the present invention is preferably the mixture of Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE, and described MALEIC ANHYDRIDE accounts for 6 ~ 10% of described polyprotonic acid total mass.
In the present invention, described term " hyperbranched aqueous Synolac " refers to that the structure of water-based unsaturated polyol fatty acid acid resin is a kind of hyperbranched structure, its be by with polyvalent alcohol and aqueous monomers for Material synthesis hyperbranched resin, then with the hyperbranched resin of synthesis, polyprotonic acid and unsaturated fatty acids for Material synthesis obtains.Hyperbranched is a kind of macromole with 3-D solid structure, many branched structures with similar relative molecular mass and narrow relative molecular mass branch extend towards periphery from core, its imporosity imparts special physical properties and chemical property, as high resolution, low viscosity etc.End group has the easy modification of hyperbranched polymkeric substance of high functionality and is cross-linked in addition, and cross-linking density is large.Hyperbranched Synolac makes its film forming more form compact and stable.
In the present invention, described " hyperbranched aqueous Synolac " has two kinds of preferred structures, and a kind of is the hyperbranched aqueous Synolac obtained for Material synthesis with TriMethylolPropane(TMP), dimethylol propionic acid, linolenic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE; The degree of branching of this dissaving structure is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.68 × 10
3g/mol, the equal molecular mass M of matter
w=5.4 × 10
3g/mol, heterogeneity index M
w/ M
n=1.15.A kind of is the hyperbranched aqueous Synolac obtained for Material synthesis with dipentaerythritol, dimethylol propionic acid, eleostearic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE; The degree of branching of this dissaving structure is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.45 × 10
3g/mol, the equal molecular mass M of matter
w=5.2 × 10
3g/mol, heterogeneity index M
w/ M
n=1.17.
The structural formula of term of the present invention " zirconium carbonate ammonium " is
, it has zirconium hydroxyl, and the activity of zirconium hydroxyl is very high, can form hydrogen bond with hydroxyl, can also react with the terminal hydroxy groups in Synolac simultaneously, is therefore conducive to the crosslinked of passivation layer theca interna inside, has good effect to the solidity to corrosion improving rete.To the compactness improving passive film, bonding force and hardness significantly improve.
In the present invention, described term " molybdate " be Sodium orthomolybdate, one or more in potassium molybdate, ammonium molybdate, ammonium phosphomolybdate.Molybdate is a kind of anode passivation type inhibiter, and it can adsorb in metallic surface, or forms insoluble electrodeposition substance at metallic surface with other materials etc. in corrosion of metal product, medium.
A kind of zinc coating chromium-free passivation liquid provided by the invention, described chromium-free passivation liquid comprises the raw material of following weight percent:
Aqueous alkide resin 10 ~ 25%
Molybdate 0.5 ~ 3%
Zirconium carbonate amine 0.5 ~ 3%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Wherein, described aqueous alkide resin is prepared by aqueous monomers, unsaturated fatty acids, polyvalent alcohol and polyprotonic acid and obtains.
As a kind of preferred implementation of the present invention, described chromium-free passivation liquid also comprises the trimethylolpropane trimethacrylate TMPTMA as linking agent, and the consumption of described linking agent is 12 ~ 25% of described aqueous alkide resin total mass.
As a kind of preferred implementation of the present invention, described aqueous alkide resin is hyperbranched Synolac, it obtains for Material synthesis with TriMethylolPropane(TMP), dimethylol propionic acid, linolenic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described hyperbranched Synolac is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.68 × 10
3g/mol, the equal molecular mass M of matter
w=5.4 × 10
3g/mol, heterogeneity index M
w/ M
n=1.15.
As another kind of preferred implementation of the present invention, described aqueous alkide resin is hyperbranched Synolac, it obtains for Material synthesis with dipentaerythritol, dimethylol propionic acid, eleostearic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described dissaving structure is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.45 × 10
3g/mol, the equal molecular mass M of matter
w=5.2 × 10
3g/mol, heterogeneity index M
w/ M
n=1.17.
As another kind of preferred implementation of the present invention, described aqueous monomers is trimellitic acid 1,2-anhydride TMA, polyoxyethylene glycol PEG, 5-sodium sulfo isophthalate, dimethylol propionic acid DMPA, maleic anhydride or vinylformic acid, is preferably dimethylol propionic acid DMPA.
As another kind of preferred implementation of the present invention, described polyvalent alcohol is one or more in glycerine, TriMethylolPropane(TMP), monopentaerythritol, dipentaerythritol, ethylene glycol, Diethylene Glycol, propylene glycol.Be preferably glycerine, TriMethylolPropane(TMP), monopentaerythritol or dipentaerythritol.
As another kind of preferred implementation of the present invention, described polyprotonic acid is one or more in Tetra hydro Phthalic anhydride, isophthalic anhydride, MALEIC ANHYDRIDE and trimellitic acid 1,2-anhydride.
As another kind of preferred implementation of the present invention, described polyprotonic acid is the mixture of Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE, and described MALEIC ANHYDRIDE accounts for 6 ~ 10% of described polyprotonic acid total mass.
As another kind of preferred implementation of the present invention, described unsaturated fatty acids is linolic acid, linolenic acid or eleostearic acid.
As another kind of preferred implementation of the present invention, described molybdate is Sodium orthomolybdate, potassium molybdate, ammonium molybdate or ammonium phosphomolybdate.
Present invention also offers the using method of the above-mentioned chromium-free passivation liquid for zinc coating, 25 DEG C ~ 35 DEG C, under pH value is the condition of 1 ~ 3, by the method such as roller coating, dip-coating, chromium-free passivation liquid is coated on galvanized sheet surface, more than 80 DEG C more than temperature-curable 30s.
Water-based unsaturated polyol fatty acid acid resin in the present invention, especially hyperbranched Synolac form framework material as main membrane-forming agent and obstruct rete plays a role; part molybdate and zirconium carbonate amine participate in reaction in film process; the composite protection film of very fine and close excellent corrosion resistance is formed with organic film former acting in conjunction; remaining molybdate and zirconium carbonate amine are wrapped in organic membrane; when organic membrane occurs damaged; remaining molybdate and zirconium carbonate amine produce secondary passivity effect by the liquid film of breakage humidity, produce similar chromic " self-healing " function.The present invention containing the chromium of any valence state, is not a kind of chromium-free passivation liquid of environmental protection, and technique is simple, meets demand of industrial production.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
The present invention is described in detail referring to several example.
embodiment
1
A kind of zinc coating chromium-free passivation liquid and using method thereof, described chromium-free passivation liquid comprises the raw material of following weight percent:
Aqueous alkide resin 25%
Sodium orthomolybdate 1%
Zirconium carbonate amine 1%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Described aqueous alkide resin is prepared by following steps: be equipped with agitator, thermometer, oily-water seperating equipment 500ml four-hole boiling flask in once add linolic acid 1.073mol, glycerine 1.016mol, dimethylbenzene (account for formula total mass 5 ~ 10%), Tetra hydro Phthalic anhydride 1mol and catalyzer LiOH (linoleic 0.02%), pass into CO
2, stir, be warming up to 160 DEG C, in 1 ~ 3h, be progressively warming up to 220 ~ 230 DEG C again in 40 ~ 50min, keep esterification, to acid number 10 below mgKOH/g, it is reaction end that viscosity (Gardner-Holdt bubble tube) reaches 10s, obtains transparent products; Be cooled to 150 DEG C, add dimethylol propionic acid DMPA 1.32mol, be warming up to 220 ~ 230 DEG C gradually again, esterification is 55 ~ 65mgKOH/g to acid number, is cooled to 60 DEG C, adds siccative (2-ethylhexoate, linoleic 0.02%) 15min is disperseed, then add in triethylamine and propyl carbinol and 15min, then add high speed dispersion 30min after solubility promoter PM latting drown, obtain aqueous alkide resin.Detect through infrared spectra and show that synthesis obtains described aqueous alkide resin.
The preparation method of the chromium-free passivation liquid for zinc coating of the present invention is: prepare aqueous alkide resin, and by aqueous alkide resin, Sodium orthomolybdate, the mixing of zirconium carbonate amine, regulate pH1 ~ 3 with phosphoric acid, add water constant volume, to obtain final product.
The using method of the chromium-free passivation liquid for zinc coating of the present embodiment is: under 25 DEG C ~ 35 DEG C conditions, by the method such as roller coating, dip-coating, chromium-free passivation liquid is coated on galvanized sheet surface, more than 80 DEG C more than temperature-curable 30s.
embodiment
2
A kind of zinc coating chromium-free passivation liquid, described chromium-free passivation liquid comprises the raw material of following weight percent:
TMPTMA modified water-based alkyd resin 20%
Potassium molybdate 3%
Zirconium carbonate amine 2%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Described TMPTMA modified water-based alkyd resin is prepared by following steps: the aqueous alkide resin preparing acid number 55 ~ 65mgKOH/g according to the method that embodiment 1 is identical, past wherein titration adds the TMPTMA of 20% of Synolac quality, control titration time is 2h, then reacts 2h in 170 DEG C and get final product.Detect through infrared spectra and show that synthesis obtains described TMPTMA modified water-based alkyd resin.
Preparation method and using method are with embodiment 1.
embodiment
3
A kind of zinc coating chromium-free passivation liquid, described chromium-free passivation liquid comprises the raw material of following weight percent:
Hyperbranched Synolac 23%
Sodium orthomolybdate 0.5%
Zirconium carbonate amine 2.5%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Described hyperbranched Synolac is prepared by following preparation method: reflux condensing tube is being housed, agitator, water trap, thermometer, TriMethylolPropane(TMP) 1.732mol and dimethylbenzene (accounting for 5 ~ 10% of formula total mass) is added in the four-hole boiling flask of logical nitrogen protection, be heated to backflow and carry out processed, then add dimethylol propionic acid 1.58mol and a small amount of catalyzer altogether in batches, react 6 ~ 7h at reflux, distillate when no longer including water in water trap, raise temperature of reaction to 150 ~ 165 DEG C gradually, vacuumize reaction 1 ~ 2h further, remove remaining dimethylbenzene, obtain faint yellow hyperbranched resin, system acid number is lower than 20mgKOH/g.Hyperbranched resin, linolenic acid 1.85mol, Tetra hydro Phthalic anhydride 1mol, MALEIC ANHYDRIDE 0.08mol, a small amount of tosic acid and appropriate dimethylbenzene is added in the four-hole boiling flask that reflux condensing tube, agitator, water trap, thermometer, logical nitrogen protection are housed; be heated to backflow; reaction distillates when no longer including water in water trap; reaction terminating, stops heating.Poured out by product, cooling, obtains hyperbranched Synolac.Characterize the hyperbranched Synolac of synthesis, the degree of branching of described hyperbranched Synolac is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.68 × 10
3g/mol, the equal molecular mass M of matter
w=5.4 × 10
3g/mol, heterogeneity index M
w/ M
n=1.15.
The preparation method of zinc coating chromium-free passivation liquid and using method are with embodiment 1.
embodiment
4
Zinc coating chromium-free passivation liquid, described chromium-free passivation liquid comprises the raw material of following weight percent:
Hyperbranched Synolac 25%
Ammonium molybdate 1%
Zirconium carbonate amine 1%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Described hyperbranched Synolac is prepared by following preparation method: reflux condensing tube is being housed, agitator, water trap, thermometer, dipentaerythritol 1.732mol and dimethylbenzene (accounting for 5 ~ 10% of formula total mass) is added in the four-hole boiling flask of logical nitrogen protection, be heated to backflow and carry out processed, then add dimethylol propionic acid 1.58mol and a small amount of catalyzer altogether in batches, react 6 ~ 7h at reflux, distillate when no longer including water in water trap, raise temperature of reaction to 150 ~ 165 DEG C gradually, vacuumize reaction 1 ~ 2h further, remove remaining dimethylbenzene, obtain faint yellow hyperbranched resin, system acid number is lower than 20mgKOH/g.Hyperbranched resin, eleostearic acid 1.85mol, Tetra hydro Phthalic anhydride 1mol, MALEIC ANHYDRIDE 0.08mol, a small amount of tosic acid and appropriate dimethylbenzene is added in the four-hole boiling flask that reflux condensing tube, agitator, water trap, thermometer, logical nitrogen protection are housed; be heated to backflow; reaction distillates when no longer including water in water trap; reaction terminating, stops heating.Poured out by product, cooling, obtains hyperbranched Synolac.Characterize the hyperbranched Synolac of synthesis, the degree of branching of described hyperbranched Synolac is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.45 × 10
3g/mol, the equal molecular mass M of matter
w=5.2 × 10
3g/mol, heterogeneity index M
w/ M
n=1.17.
The preparation method of zinc coating chromium-free passivation liquid and using method are with embodiment 1.
embodiment
5
Zinc coating chromium-free passivation liquid in this embodiment, except the polyprotonic acid used in hyperbranched Synolac preparation process is Tetra hydro Phthalic anhydride, do not have outside MALEIC ANHYDRIDE, other compositions are all identical with embodiment 1, and preparation method and using method are also identical with embodiment 3.
Evaluate the erosion resistance of the galvanized sheet handled by chromium-free passivation liquid by the embodiment of the present invention 1 ~ 5, mainly realized by neutral salt spray test and electrochemistry ancillary test, in order to embody " self-healing " performance of the embodiment of the present invention 1 ~ 5 chromium-free passivation liquid, with conventional chromating liquid as a comparison.Evaluation result is obtained by following experiment content:
(1) neutral salt spray test
Adopt spraying continuously according to GB GB/T 10125-1997, take out in the different time periods, and with the light brush specimen surface of banister brush, rinse with clear water after taking-up, observe the area occurring " white rust ", calculate the area of " white rust " with cross-hatching.
(2) adhesion test
The sticking power evaluating the galvanized sheet protective membrane after chromium-free passivation liquid process of the present invention is undertaken by cross cut test.Draw lattice experiment with reference to GB GB/T 9286-1998, utilize QFH Checker marking knife after lattice are drawn on passive film surface, with the light brush specimen surface of banister brush, use Scotch600 scotch tape, wide 19mm × the 32.9mm of adhesive tape, to draw after lattice part seals 5 minutes, and in 1 ~ 2s, adhesive tape be pulled out, observe the area that comes off finding edge-smoothing place, cut place.
(3) corrosion resistant test after dehydrogenation
To the galvanized sheet adopted after chromium-free passivation liquid process under 210 DEG C of conditions, dehydrogenation, after 2 hours, with the light brush specimen surface of banister brush, is rinsed with clear water after taking-up, is observed the area occurring " white rust ", calculate the area of " white rust " with cross-hatching.
Evaluation test the results are shown in Table shown in 1.
The erosion resistance of the galvanized sheet after table 1 Passivation Treatment
As can be known from Table 1, galvanized sheet 96h neutral salt spray test after the chromium-free passivation liquid Passivation Treatment of embodiment 1 ~ 5 occur the area of white rust be less than the process of chromating liquid after galvanized sheet, and under 210 DEG C of conditions, dehydrogenation is after 2 hours, galvanized sheet after the chromium-free passivation liquid Passivation Treatment of embodiment 1 ~ 5 occurs that the area change of white rust is little, and the galvanized sheet after chromating liquid Passivation Treatment occurs that the area of white rust increases greatly.
Experimental result shows, adopt passivating solution of the present invention can obtain the excellent passive film of adhesion property in metallic surface, the performance of this passive film is suitable with the passivation effect of chromic salt, the solidity to corrosion of the chromate passivation film even exceeded, therefore can substitute chromium hydrochlorate completely, realize environment-friendly type passive film.The present invention relative to prior art, its advantage and significant benefit as follows: passivating solution of the present invention, due to not containing chromic salt, not only significantly reduces environmental pollution, and meets the requirement of WEES and ROHS instruction.Meanwhile, the low in raw material price that passivating solution of the present invention adopts, treatment process is simple.
Aforesaid example is only illustrative, for explaining some features of feature of the present invention.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. a zinc coating chromium-free passivation liquid, is characterized in that, described chromium-free passivation liquid comprises the raw material of following weight percent:
Aqueous alkide resin 10 ~ 25%
Molybdate 0.5 ~ 3%
Zirconium carbonate amine 0.5 ~ 3%
Surplus is water
Phosphorus acid for adjusting pH to 1 ~ 3
Wherein, described aqueous alkide resin is prepared by aqueous monomers, unsaturated fatty acids, polyvalent alcohol and polyprotonic acid and obtains.
2. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described chromium-free passivation liquid also comprises the trimethylolpropane trimethacrylate accounting for described aqueous alkide resin total mass 12 ~ 25%.
3. zinc coating chromium-free passivation liquid according to claim 1, it is characterized in that, described aqueous alkide resin is hyperbranched Synolac, described hyperbranched Synolac obtains for Material synthesis with TriMethylolPropane(TMP), dimethylol propionic acid, linolenic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described hyperbranched Synolac is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.68 × 10
3g/mol, the equal molecular mass M of matter
w=5.4 × 10
3g/mol, heterogeneity index M
w/ M
n=1.15.
4. zinc coating chromium-free passivation liquid according to claim 1, it is characterized in that, described aqueous alkide resin is hyperbranched Synolac, described hyperbranched Synolac obtains for Material synthesis with dipentaerythritol, dimethylol propionic acid, eleostearic acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the degree of branching of described dissaving structure is 0.5 ~ 0.6, the equal molecular mass M of number
n=4.45 × 10
3g/mol, the equal molecular mass M of matter
w=5.2 × 10
3g/mol, heterogeneity index M
w/ M
n=1.17.
5. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described aqueous monomers is dimethylol propionic acid.
6. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described polyvalent alcohol is glycerine, TriMethylolPropane(TMP), monopentaerythritol or dipentaerythritol.
7. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described polyprotonic acid is the mixture of Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE, and described MALEIC ANHYDRIDE accounts for 6 ~ 10% of described polyprotonic acid total mass.
8. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described unsaturated fatty acids is linolic acid, linolenic acid or eleostearic acid.
9. zinc coating chromium-free passivation liquid according to claim 1, is characterized in that, described molybdate is Sodium orthomolybdate, potassium molybdate, ammonium molybdate or ammonium phosphomolybdate.
10. the zinc coating chromium-free passivation liquid described in any one of claim 1 ~ 9, it is characterized in that, described using method is: 25 DEG C ~ 35 DEG C, under pH value is the condition of 1 ~ 3, by the method such as roller coating, dip-coating, chromium-free passivation liquid is coated on galvanized sheet surface, more than 80 DEG C more than temperature-curable 30s.
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| CN107419253A (en) * | 2017-07-04 | 2017-12-01 | 安徽腾龙泵阀制造有限公司 | A kind of surface chromium-free composite passivation solution of galvanized steel plain sheet part for pump |
| CN115029740A (en) * | 2022-06-30 | 2022-09-09 | 江阴市羽项汽车饰件有限公司 | Protective film electroplating solution and electrolysis process |
| CN115505913A (en) * | 2022-11-03 | 2022-12-23 | 广州市钫立新材料科技有限公司 | Steel passivator and passivating method |
| CN115537793A (en) * | 2022-09-30 | 2022-12-30 | 安徽舜邦精细化工有限公司 | Chromium-free passivation sealing treatment method for galvanized steel sheet |
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| CN102586768A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Zinc layer surface passivating treatment liquid |
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| CN102586768A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Zinc layer surface passivating treatment liquid |
| CN102168265A (en) * | 2011-03-25 | 2011-08-31 | 东北大学 | Chromium-free composite passivator and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107419253A (en) * | 2017-07-04 | 2017-12-01 | 安徽腾龙泵阀制造有限公司 | A kind of surface chromium-free composite passivation solution of galvanized steel plain sheet part for pump |
| CN115029740A (en) * | 2022-06-30 | 2022-09-09 | 江阴市羽项汽车饰件有限公司 | Protective film electroplating solution and electrolysis process |
| CN115029740B (en) * | 2022-06-30 | 2023-11-21 | 江阴市羽项汽车饰件有限公司 | Protective film electroplating solution and electrolysis process |
| CN115537793A (en) * | 2022-09-30 | 2022-12-30 | 安徽舜邦精细化工有限公司 | Chromium-free passivation sealing treatment method for galvanized steel sheet |
| CN115505913A (en) * | 2022-11-03 | 2022-12-23 | 广州市钫立新材料科技有限公司 | Steel passivator and passivating method |
| CN115505913B (en) * | 2022-11-03 | 2023-11-14 | 广州市钫立新材料科技有限公司 | Steel passivating agent and passivating method |
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| CN104805422B (en) | 2017-05-03 |
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