CN1093891C - Aqueous zinc phosphate chemical conversion treatment liquid and process - Google Patents
Aqueous zinc phosphate chemical conversion treatment liquid and process Download PDFInfo
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- CN1093891C CN1093891C CN95120534A CN95120534A CN1093891C CN 1093891 C CN1093891 C CN 1093891C CN 95120534 A CN95120534 A CN 95120534A CN 95120534 A CN95120534 A CN 95120534A CN 1093891 C CN1093891 C CN 1093891C
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/16—Orthophosphates containing zinc cations containing also peroxy-compounds
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Abstract
A zinc phosphate conversion coating composition which is accelerated only with nitrogen free organic peroxides is low-polluting and able to form uniform, fine, and dense conversion coatings that exhibit an excellent paint adherence when thin and excellent lubricity/lubricant carrier quality when thick.
Description
The present invention relates to a kind of aqueous zinc phosphate chemical conversion treatment solution that is used for metallic substance, for example steel or galvanized steel, and the method for metallic substance is handled in the zinc phosphate chemical conversion, more specifically say, the present invention relates to a kind of aqueous zinc phosphate chemical conversion treatment solution and be used for the method for metallic substance, it can be formed uniformly and comprise the fine and close zinc phosphate chemical conversion layer of very thin chemical conversion crystalline, and its advantage is to make chemical conversion layer show the enhanced bounding force to paint or lacquer.
As everyone knows, when metallic substance will apply enamelled coating or carry out plastic working, as pre-treatment, usually metallic substance being carried out the zinc phosphate chemical conversion handles, so that it is bonding to increase the solidity to corrosion and the lacquer of metallic substance after japanning, and the lubricating quality that improves metal material surface during plastic working.
The chemical conversion solution that is used for zinc phosphate chemical conversion processing is mainly a kind of acidic aqueous solution that contains zine ion, phosphate anion and oxygenant.Oxygenant for example generally includes: nitrite, oxymuriate, hydrogen peroxide, organic nitro-compound and hydroxylamine compound.These oxygenants have the effect that promotes the chemical conversion reaction, therefore are called as chemical conversion promotor.Sometimes, Chang Gui chemical conversion treatment solution contains nitrate radical (salt).The contained nitrate of chemical conversion treatment solution does not have oxidisability, and is therefore different with chemical conversion promotor.
The effect of chemical conversion promotor is in chemical conversion is handled in the zinc phosphate chemical conversion treatment solution, will become ferric ion by the oxidation of divalent iron ion that dissolves in treatment solution in the ferrous metal material.For example, if handle ferruginous metallic substance continuously with chemical conversion treatment solution, thereby ferrous ion enrichment in chemical conversion treatment solution has hindered the chemical conversion reaction.Therefore, chemical conversion promotor prevents that the effect of the enrichment of ferrous ion in chemical conversion treatment solution from being very important.
But it is to be solved that the chemical conversion promotor of every kind of routine all has variety of issue to have.For example, the shortcoming that is widely used as most the nitrite of chemical conversion promotor is, nitrite is unstable in acidic solution, even when not carrying out the chemical conversion processing, for example at lay up period, they also can natural decomposition also consume, and therefore will replenish the nitrite that is equivalent to consumption, to keep the constant of nitrite concentration.
In addition, know that also a part of nitrite can be converted into NO when oxidizing reaction or natural decomposition reaction
xGas, the NO that obtains
xGaseous diffusion also produces pollution in atmosphere.
When oxymuriate is used as chemical conversion promotor, can produce as the hydrolysis products chlorion, chlorion is enrichment in chemical conversion treatment solution.If contain chlorion,, also can seriously reduce the solidity to corrosion of the metallic substance after the processing even amount seldom at the residual chemical conversion treatment solution of handling of metal material surface.In addition, oxymuriate uses with another kind of chemical conversion promotor usually, for example nitrite.But if oxymuriate uses separately, then it can obviously reduce the speed of response of the chemical conversion treatment solution that obtains.
When using hydrogen peroxide as chemical conversion promotor, it is poor stability in chemical conversion treatment solution, and the oxygen that therefore is easy to be dissolved in the treatment solution decomposes.In addition, hydrogen peroxide is suitable for practical concentration range in chemical conversion treatment solution very narrow, therefore is difficult to its concentration is controlled at suitable scope.If the concentration of hydrogen peroxide that is dissolved in the treatment solution is too high, the result understands the powdery chemical conversion layer of the paired metal material surface poor adhesion of unfavorable terrain.
When organic compounds containing nitrogen such as organic nitro-compound, for example during as chemical conversion promotor, have following shortcoming as nitro guanine or nitrobenzene sodium sulfonate.When using the nitro guanine, because its solubleness in water is very low, therefore it can not be added in the chemical conversion treatment solution as strong solution, and because the nitro guanine to the oxidation of divalent iron ion poor activity, it is difficult to control the concentration of ferrous ion in the chemical conversion treatment solution.In addition, when m-nitrobenzene sodium sulfonate is used as chemical conversion promotor,, therefore it need be used with the strong chemical conversion promotor of another kind because this component has poor chemical conversion character when using separately.In addition, in order to control compound concentration, need carry out large-scale concentration determination experiment, for example chromatography of ions.In addition, if organic nitro-compound or the enrichment in chemical conversion treatment solution of its degradation production, the waste liquid COD value of being handled discharging by chemical conversion increases, and physical environment is had disadvantageous effect.
When organic compounds containing nitrogen, when for example hydroxylamine compound is used as chemical conversion promotor, this compound must join in the chemical conversion treatment solution with 1000ppm or higher high density, and this makes that chemical conversion promoter consumption amount is excessive, also is uneconomic.
Norio Sato is at " Boshoku Gijutsu ", Vol.Reported among 15 No.5 (1996) chromic acid and permanganate result of study as the chemical conversion promotor of zinc phosphate chemical conversion treatment solution.In this report, point out, when these compounds respectively with 5 mmoles/liter and 10 mmoles/liter concentration when using, can not form chemical conversion layer.
Nearly all above-mentioned conventional chemical inversion accelerating agent all comprises nitrogenous compound.Be difficult to from the waste water of chemical conversion processing discharging, remove nitrogenous compound with the chemical wastewater treatment process.These compounds must just can be removed by microbiological treatment.Yet, promptly use microbiological treatment also to be difficult to the nitrogenous compound of high density is removed.But, when concentration is low, also can not remove nitrogenous compound fully by microbiological treatment.Recently, strict more to the restriction of nitrogenous compound discharging, because the discharging of nitrogenous compound is to cause one of reason of river, lake and marsh eutrophication.Therefore, the zinc phosphate chemical conversion treatment solution that does not contain nitrogenous compound that needs development of new.
When the conventional chemical inversion accelerating agent is used for forming as the thin, fine and close of the bottom of enamelled coating and uniformly during chemical conversion layer, need before handling, chemical conversion handle the surface of metallic substance with surface treatment agent in the short period of time.But the treatment solution of surface treatment agent requires complicated control, particular processing device and the additional large space of placing treatment unit.
Therefore, people press for a kind of new chemical conversion promotor of exploitation, and it does not need surface treatment just can form satisfied chemical conversion layer at metal material surface.
Now, zinc phosphate chemical conversion processing and oxymuriate are handled and be widely used as the painted bottom layer treatment, and be bonding with the erosion resistance and the lacquer that strengthen various metallic substance after japanning.
When metallic substance is when comprising the matrix material of iron or multiple metal, the reaction that oxymuriate is handled is very difficult.Therefore, to this matrix material, mainly use the zinc phosphate chemical conversion to handle.
Usually, the crystalline size of the coated crystal that handle to be obtained by the zinc phosphate chemical conversion changes with the processing condition.Comprise that the big coating of coarse crystal and thickness is suitable for plastic working and antirust.When applying paint again on the chemical conversion layer, thick coated crystal can cause gained enamelled coating and chemical conversion layer bonding relatively poor.Therefore, when the zinc phosphate chemical conversion layer was used as the bottom of enamelled coating, requiring chemical conversion layer was a kind of thin layer that is made of even and fine and close coated crystal.
Known thin zinc phosphate chemical conversion layer can be prepared by two kinds of methods.In a kind of method, in coating-precipitin reaction process, interrupt contacting between chemical conversion treatment solution and the metal material surface, with stopped reaction.When making in this way, the precipitation of chemical conversion layer is incomplete, so metal material surface is applied fully.Therefore, in the water rinse step and drying step after chemical conversion is handled, the uncoated part of metal material surface is got rusty, and further makes the anti-corrosion corruption of painted surface of metallic substance dissatisfied.
In another approach, coated crystal is by refinement.According to this method, coating-precipitin reaction can be finished to form thin coating, and therefore the chemical conversion layer that obtains can cover the surface of metallic substance fully.Thereby it is bonding that the chemical conversion coating surface that obtains goes out gratifying lacquer, and the painted metals material has satisfied erosion resistance.
The zinc phosphate chemical conversion is handled and is carried out with dipping method or spraying method usually.The shortcoming of pickling process is to obtain thin coated crystal, and if treatment temp be lower than 55 ℃, chemical conversion handle to need the long time.In addition, although spraying method makes thin than pickling process of the coated crystal that obtains, not good with the japanning performance of the chemical conversion layer of spraying method formation.In addition, in order to finish the chemical conversion reaction in the gratifying short period of time, treatment temp should be 55 ℃ or higher.
Usually, be 50 ℃ or lower in order to form thin coated crystal and to make treatment temp, should before handling, chemical conversion handle metal material surface with the surface treatment agent that contains the colloidal state titanium compound in the short period of time.Surface treatment can the activated metal material the surface, therefore at dipping with spray and can reduce treatment temp in two kinds of methods effectively and shorten the treatment time.In addition, surface-treated surface also forms the chemical conversion layer that comprises thin coated crystal easily, and it has satisfied japanning performance.
As mentioned above, when zinc phosphate chemical conversion processing conduct is used metallic surface painted bottom layer treatment, before handling, chemical conversion with the surface treatment agent that contains the colloidal state titanium compound metallic surface is handled in the short period of time usually.The titanium compound colloid grain that is dispersed in the surface treatment liquid was reunited in the short period of time after the preparation treatment solution, so the surface treatment effect of treatment solution reduces in time.In order to improve the stability of titanium compound colloidal dispersion, Japanese patent examination bulletin No.62-9190 proposes a kind of surface treatment method, has wherein controlled the Mg/P of surface treatment liquid
2O
7The ratio.In addition, the open No.63-18084 of Japanese unexamined patent publication No. discloses a kind of surface treatment method, and wherein surface treatment liquid contains a kind of organism as titanium compound colloidal stablizer.Yet these normal rule method effects in practice far away and unsatisfactory need to remove continuously waste liquid in practice and replenish fresh liquid.The preparation of surface treatment liquid and control are troubles, and will spend the labour, and the consumption of reagent is also very big, so ordinary method is uneconomic.In addition, surface treatment also has other shortcoming, needs surface-treated equipment, need carry out maintenance of equipment, and equipment also needs additional space.
Therefore, people press for a kind of all methods of the chemical conversion layer of even densification that forms of exploitation on metallic substance, this coating can be used as the bottom of coating, and this method does not need to carry out surface treatment with titanium-containing compound colloidal treatment solution, thereby does not have above-mentioned characteristics.
As mentioned above, the zinc phosphate chemical conversion is handled the bottoming that is widely used as various metal charges and handled, and is bonding to strengthen erosion resistance and the lacquer of metallic substance after japanning.Even for comprising that for example iron and one or more other metals are in the composite material of material, this chemical conversion is handled and is also used effectively.
The method that forms the zinc phosphate chemical conversion layer on metallic substance generally includes following steps:
(1) uses the alkali oil removing;
(2) water flushing;
(3) chemical conversion is handled;
(4) water flushing; With
(5) dehydration and dry.
These steps are carried out with said sequence.If chemical conversion layer is as the painted bottom, fine and close chemical conversion crystal layer is handled step (3) before in chemical conversion in order to form evenly, as pre-treatment, with the treatment solution that contains the colloidal state titanium compound metal material surface is carried out surface treatment.
Carry out the surface treatment metal material surface crossed of activation treatment effectively with the treatment solution that contains the colloidal titanium compound, make the sedimentary chemical conversion crystal refinement that obtains and increase the speed that forms chemical conversion layer.Under 60 ℃ or lower relatively low treatment temp, the speed increase that chemical conversion layer forms shows to such an extent that more do not add significantly.
The matter of utmost importance of above-mentioned conventional surface treatment method be number of steps many and required in steps total time very long.Because this problem makes the treatment facility that needs become space big and that requirement is bigger.Above-mentioned conventional surface treatment method comprises five or six steps.In ordinary method, each alkali deoiling step and water rinse step are divided into usually again and severally carry out step by step, to strengthen cleaning performance.Therefore, total step and several step by step very big, and also the total expenses of treatment facility also increases.In addition because in steps and total time step by step elongated, the productive rate of this method reduces.
Second problem of ordinary method is that the item number that will control is too many.For example, in the alkali deoiling step, must control the basicity (total alkalinity and free basicity) of degreasing fluid.In addition, handle in the step, must control the acidity (total acidity and free acidity) of treatment solution in chemical conversion.When the item number of control increased, it is big that the load of operation becomes.In addition, owing in each step, need to consume reagent, so process cost increases.In addition, because surface treatment agent comprises colloidal state titanium compound dispersion as main ingredient, surface treatment liquid stability in time is often unsatisfactory, therefore control surface treatment solution suitably, and discharge periodically and replenish.
For solving above-mentioned two problems, considered to use oil removing and the chemical conversion treatment solution that contains oil removing tensio-active agent and zinc phosphate chemical conversion treating agent, in a step, carry out alkali oil removing and chemical conversion and handle.Yet, in a step, to carry out oil removing and chemical conversion simultaneously and handle, the oil removing partial continuous that chemical conversion is reflected at metal material surface takes place, and therefore the quality and the outward appearance of the chemical transformation coating that obtains are inhomogeneous.
If in chemical conversion processing process, add surface treatment agent to chemical conversion treatment solution, the tensio-active agent that adds with expectation plays the surface-treated effect, because unstable under acidic condition as the colloidal state titanium compound of surface treatment agent main ingredient, so the colloidal state titanium compound can not be realized the surface treatment effect of expecting.That is to say,, not only can not form the microlite of chemical conversion layer, and because the low precipitation speed of coated crystal makes the ununiformity of chemical conversion layer outward appearance increase even add surface treatment agent in the chemical conversion treatment solution.
Therefore, people's an urgent demand can be shortened treatment process, reduces cost of equipment and reagent expense, simplifies the CONTROL PROCESS of treatment solution.Yet the technology barrier that reaches these requirements is very big, does not therefore also fully satisfy these requirements.
An object of the present invention is to provide a kind of aqueous zinc phosphate chemical conversion treatment solution that is used for metallic substance, it can comprise the zinc phosphate chemical conversion layer of all even densifications of thin coated crystal in the metal material surface precipitation, also provides a kind of zinc phosphate chemical conversion to handle the method for metallic substance.
Another object of the present invention provides a kind of aqueous zinc phosphate chemical conversion treatment solution that is used for metallic substance, even carry out surface treatment without surface treatment liquid, it also can metal material surface form can strengthen lacquer bonding thereby can be used as the painted bottom comprising thin coated crystal evenly and fine and close zinc phosphate chemical conversion layer also provides a kind of zinc phosphate chemical conversion to handle the method for metallic substance.
By the phosphoric acid zinc impregnation conversion treating solution of metallic substance and the method that metallic substance is handled in zinc phosphate chemical conversion of the present invention of being used for of the present invention, can realize above-mentioned purpose.
The aqueous zinc phosphate chemical conversion treatment solution that is used for metallic substance of the present invention comprises zine ion and phosphate anion as main ingredient, also comprises the chemical conversion promotor of the 50-1500ppm that contains at least a organo-peroxide.
The method that metallic substance is handled in zinc phosphate chemical conversion of the present invention comprises: make to comprise zine ion and phosphate anion as main ingredient, also comprise that the aqueous treatment of the chemical conversion promotor that contains at least a organo-peroxide contacts with the surface of metallic substance, with at the surface of metallic substance formation zinc phosphate chemical conversion layer.
The present inventor has studied the chemical conversion reaction that how to promote at metal material surface zinc phosphate chemical conversion treatment solution.The inventor has studied the ratio of zinc ion concentration and phosphorus acid ion concentration, not as the influence of zinc phosphate chemical conversion reaction on the various oxygenants of chemical conversion promotor and etchant such as fluorochemicals or the ion pair metallic substance.As a result, confirm various inorganic oxidizer, for example peroxyboric acid radical ion, iodate ion and persulfate ion, and etchant does not have satisfied chemical conversion to promote character.In addition, the result that organic oxidizing agent is studied confirms that if add a kind of organo-peroxide that dissolves in the moisture chemical conversion treatment solution in treatment solution, the chemical conversion reaction obtains promoting, and the zinc phosphate chemical conversion coating that obtains is even and fine and close.
In addition, also find when organic superoxide is used as chemical conversion promotor, not need another kind of conventional chemical inversion accelerating agent or nitrate radical compound are used with organo-peroxide.Therefore, chemical conversion treatment solution can not contain nitrogenous compound or ion.In addition, also find to use organo-peroxide,, also can on metal material surface, form evenly and fine and close zinc phosphate chemical conversion layer even save surface treatment as chemical conversion promotor.In addition, also find to limit the zinc concentration of treatment temp and treatment solution, also can on the metallic surface, form satisfied zinc phosphate chemical conversion layer.The present invention is based on above discovery and be accomplished.
Zinc phosphate chemical conversion treatment solution of the present invention and method are superior, and be free from environmental pollution basically by the waste liquid of technology discharging of the present invention because treatment solution does not have nitrogenous compound and ion basically, and reached the requirement of environmental legislation.Usually, if treatment solution nitrogenous compound and ionic total content (in nitrogen) are limited in the level of 0-200ppm, the harm of contaminate environment is just very little.
Aqueous zinc phosphate chemical conversion treatment solution of the present invention comprises zine ion and phosphate anion as main ingredient, also comprises the chemical conversion promotor that contains at least a organo-peroxide.
As mentioned above, in chemical conversion treatment solution of the present invention, exist nitrogenous compound and ionic total content (in nitrogen) to be limited in the 0-200ppm level, preferably in the 0-100ppm level, more preferably 0-50ppm, the level of preferred 0-20ppm again.
In addition, in chemical conversion treatment solution of the present invention, the content of zine ion changes along with the application of the chemical conversion layer that obtains.Preferably, the content of zine ion in chemical conversion treatment solution is in 0.5-15 grams per liter scope.For example, when chemical conversion treatment solution was used for forming the painted bottom on metallic substance, the common weight of gained coating was 0.5-10.0g/m
2In order to form the chemical conversion layer of above-mentioned weight, chemical conversion treatment solution contains zinc ion concentration and is preferably the 0.5-5.0 grams per liter.
If the content of zine ion is lower than 0.5 grams per liter, the zinc phosphate chemical conversion layer fraction of coverage that obtains on metal material surface may reduce, the chemical conversion laminar surface also may be unsatisfied with the lacquer of enamelled coating is bonding on the metallic substance, and the erosion resistance of the japanning metallic substance that obtains also may be unsatisfied with.In addition, if zinc ion content surpasses 5.0 grams per liters, owing to form thick coated crystal, the bottom that obtains may reduce the lacquer of enamelled coating is bonding.
If chemical conversion treatment solution is used for coating and treats that the metallic substance of plastic working, the zinc ion concentration of treatment solution preferably should be heavily is 5.0-15.0g/m to form
2Chemical conversion layer, and can follow plastic deformation of metal material.In this case, the content of zine ion in chemical conversion treatment solution is preferably in 5.0-15.0 grams per liter scope.In this case, if zinc ion content is lower than 5.0 grams per liters, will be difficult to form 5.0-15.0g/m
2Chemical conversion layer.In addition, if the content of zine ion is higher than 15.0 grams per liters, the weight that obtains chemical conversion layer reaches capacity, and this is uneconomic.
Can produce zine ion by the acid constituents that zinc hydroxide or zinc oxide are dissolved in the chemical conversion treatment solution, or by with water-soluble zinc salt, be dissolved in chemical conversion treatment solution and produce as zinc phosphate or zinc sulfate.
In chemical conversion treatment solution of the present invention, phosphate anion preferably exists with the content of 5.0-30.0 grams per liter.If phosphate anion content is lower than 5.0 grams per liters, just be difficult to form satisfied chemical conversion layer.In addition, if phosphate anion content surpasses the 30g/ liter, the effect of phosphate radical is saturated, and this also is uneconomic.
Can be by in treatment solution, adding phosphoric acid or phosphate aqueous solution, perhaps the phosphoric acid salt with sodium, potassium, magnesium or zinc is dissolved in the treatment solution, thereby produces phosphate anion in chemical conversion treatment solution.
The zinc phosphate chemical conversion treatment solution is an acidic aqueous solution, and its pH value is preferably 2.0-4.0, more preferably 2.5-3.5.In this pH value scope, phosphoric acid (H
3PO
4) and phosphate anion (H
2PO
4 -) exist with following equilibrium relationship (I):
Therefore, in the present invention, phosphate anion comprises phosphoric acid and phosphoric acid hydrogen radical ion.
Chemical conversion treatment solution of the present invention comprises that the chemical conversion that contains by at least a organo-peroxide promotes sharp.The then preferred water soluble of organo-peroxide and oxide structure was arranged or cross those of carboxyl structure.Can be used for organo-peroxide of the present invention and comprise aromatics superoxide, cyclic aliphatic superoxide, aliphatic peroxide, preferably contain the aliphatic peroxide that at least one has the alkyl of 1-7 C atom.Some contain the aromatics superoxide of chain alkyl and organo-peroxide and show not satisfied water-solublely, thereby promote that the effect of chemical conversion is not obvious.
The organo-peroxide that can be used as chemical conversion promotor is preferably selected from: ethyl hydroperoxide, different third pure excessively, uncle-Ding crosses alcohol, uncle-oneself is pure excessively, diethyl superoxide, two-tert-butyl peroxide, acetylacetone peroxide, cumene hydroperoxide and t-butylperoxy toxilic acid, these compounds contain one and cross oxide structure, and peracetic acid, single peroxide phthalic acid and mistake succsinic acid, they contain a perhydroxyl radical structure.
If the solvability of organo-peroxide in chemical conversion treatment solution is low, can as the trimethyl carbinol and Virahol, promote the dissolving of low-solubility compound by in treatment solution, adding a spot of water-soluble organic solvent.
As mentioned above, chemical conversion treatment solution of the present invention contains 50-1500ppm, the chemical conversion promotor of preferred 80-200ppm.The chemical conversion promoter action is insufficient if the content of chemical conversion promotor is lower than 50ppm.If the content of promotor is higher than 1500ppm, then chemical conversion promoter action is an over-drastic, and this is disadvantageous economically.
The effect of chemical conversion treatment solution of the present invention is to make effectively sedimentary zinc phosphate crystal to become thinner, thereby the chemical conversion treatment solution of the application of the invention, be not used to make that zinc phosphate chemical conversion layer crystal attenuates, commonly used surface treatment even do not adopt, still can form uniform, fine and close zinc phosphate chemical conversion layer at metal material surface.And, because needn't joining in the chemical conversion treatment solution of the present invention, nitric acid, nitronic acid (nitron acid) and organic nitro-compound react with the promotion chemical conversion, chemical conversion treatment solution of the present invention needn't contain any nitrogenous compound and ion.Like this, handling the waste water that discharges the step from the chemical conversion of technology of the present invention just needn't be through being used to remove nitrogenous compound and the special wastewater treatment step of ionic.Nature is not got rid of nitrogenous compound is joined in the chemical conversion treatment solution of the present invention.But nitrogenous compound and ionic content preferably are limited to 0-200ppm in chemical conversion treatment solution of the present invention, and in nitrogen, this mentions in front.
Chemical conversion treatment solution of the present invention preferably contains other metal ion except that zine ion.When chemical conversion layer was used as the bottom of enamelled coating, the ion of interpolation was as the etchant or the lacquer adhesion promotor of even etch metal material surface.
Other metal ion except that zine ion comprises nickel ion, mn ion, cobalt ion, iron ion, magnesium ion and calcium ion.Can be dissolved in by oxide compound, oxyhydroxide, carbonate, vitriol and form other metal ion in the chemical conversion treatment solution other metal.
The content of other metal ion in chemical conversion treatment solution of the present invention is 100-300ppm, preferred 200-2000ppm.
When iron or steel being handled, dissolve ferric ion and be enriched in the treatment solution with the content of 10-50ppm from metallic substance with chemical conversion treatment solution of the present invention.The amount of this cumulative trivalent ion is to the effect and the not influence of technology of the present invention of treatment solution.Therefore, before chemical conversion was handled, ferric ion can be added into or be included in the treatment solution in above-mentioned content range.
Chemical conversion treatment solution of the present invention preferably contains an etchant, and this etchant comprises fluorine-containing ion, such as fluoride ion or fluorochemical-complexing ion such as silicofluoride ion, Zirconium tetrafluoride ion.Water-soluble metal (sodium, potassium, the magnesium) salt of fluorochemicals platform hydrofluoric acid, silicofluoric acid, fluorine zirconic acid, hydrofluotitanic acid or above-mentioned acid can be dissolved in the chemical conversion treatment solution, thereby form fluoride ion.
Method of the present invention comprises the step that aqueous zinc phosphate chemical conversion treatment solution is contacted with metal material surface.If the surface of metallic substance is cleaned, the phosphoric acid zinc impregnation conversion treating solution in the inventive method can be directly used in the metallic substance of cleaning.Yet, if the surface of metallic substance is by thin metallic particles, dust or grease contamination, then before chemical conversion is handled, use a kind of aqueous alkaline degreasing fluid, a kind of moisture cleaning emulsion, or a kind of cleaning solvent carries out clean so that pollution substance is removed from the metallic surface to metal material surface.When with a kind of when containing aqueous cleaning, preferred water washes processing to remove the scavenging solution that remains on the metallic surface to metal material surface.
Usually before chemical conversion was handled, metal material surface washed with a kind of alkaline degreaser oil removing and water.In addition, after chemical conversion is handled, the chemical conversion layer water of gained flushing and then dry.The step of each oil removing and flushing can a plurality ofly be carried out step by step.If the chemical conversion layer that forms is as the bottom of enamelled coating, then last cleaning step preferably carries out with deionized water.
In addition, if the chemical conversion layer that forms as the bottom of the enamelled coating on the metallic surface, then metal material surface preferably in the short period of time, carries out surface treatment with a kind of surface treatment agent that contains the colloidal titanium compound before chemical conversion is handled.Yet, can save surface treatment in the methods of the invention.
Surface that the chemical conversion of water flushing metallic substance was handled, and drying randomly varnish with lacquer then.
When being used for the plastic working of metallic substance, preferably after oil removing and water rinse step, metal material surface is carried out pickling so that de-scaling is carried out on the surface by forming chemical conversion layer with chemical conversion treatment solution of the present invention.
When chemical conversion layer will stand plastic working, coatingsurface was preferably with lubricator as the oilness of soap with the enhancing chemical conversion layer.
In metallic substance being carried out the inventive method that the zinc phosphate chemical conversion handles, chemical conversion is handled usually by for example a kind of dipping method, and spraying method or it is used in combination carries out.Handle when being formed for the bottom of enamelled coating when carrying out chemical conversion, handle preferably in room temperature-60 and ℃ carried out 0.5-5 minute.When the chemical conversion processing was used for the metallic substance of pending plastic working, preferred process temperature was 50 ℃-90 ℃, and the treatment time is 1-15 minute.Under above-mentioned treatment condition, can obtain the ideal chemical conversion layer.
Aqueous zinc phosphate chemical conversion treatment solution of the present invention and method have following function and effect.
In zinc phosphate chemical conversion of the present invention was handled, chemical conversion layer-precipitin reaction following steps were carried out.
1. processed a part of metallic substance is dissolved in the chemical conversion treatment solution.
2. owing to the dissolving of metal, the hydrogen ion in chemical conversion treatment solution is reduced, and the pH value of metal material surface increases.
3. because the increase of metal material surface pH value, thereby the zine ion in the chemical conversion treatment solution and phosphate anion are deposited in formation coating on the metal material surface with zinc phosphate crystalline form.
Usually, 1. and 2., when acidic aqueous solution contacts with metal material surface, form local element at metal in material surface in above-mentioned steps, the dissolving of metal occurs in the anode of local element, and hydrogen ion is reduced at the negative electrode of local element.Promptly anodic reaction and cathodic reaction are carried out simultaneously in the subregion of adjacent metal material surface.This phenomenon is called local polarisation.Zinc phosphate chemical conversion layer crystalline precipitation occurs in pH value at the 3. local zone that increases of above-mentioned stage, i.e. cathode zone.Therefore, can obtain very undersized coated crystal by the distribution density that increases positive column and cathodic area.Before the present invention, known when using the common chemical conversion treating solution, the raising of the distribution density of local polarisation only can be achieved by just using a kind of colloidal titanium compound treatment solution that metal material surface is carried out surface treatment before chemical conversion is handled.
In the present invention, when the chemical conversion promotor that comprises at least a organo-peroxide is added into chemical conversion treatment solution, the above-mentioned stage 2. in, the reduction reaction of organo-peroxide replaces hydrionic reduction reaction and preferential the generation, and because etch reaction efficiently takes place at metal material surface in the polarizing effect of metal material surface.In addition, the oxidation effect of organo-peroxide causes the metal material surface unevenness to reduce and improved the distribution density in anode and cathodic area.Thereby make and not adopt formation chemical conversion layer uniform, fine and close, that contain thin coated crystal under the surface-treated situation commonly used.The increase effect of polarization distribution density has benefited from organo-peroxide.By with inorganic oxidizer commonly used,, can not obtain this effect as nitrite and oxymuriate.
When metallic substance is the ferrous metal material, in the dissolved theory of evolution conversion treating solution of a part of iron in the metallic substance and the iron ion of gained be enriched in the treatment solution with the form of ferrous ion.Ferrous ion hinders the chemical conversion reaction.Therefore oxidation of divalent iron ion must be become ferric ion to avoid the blanketing of ferrous ion.When ferrous ion is dissolved in oxygen in the chemical conversion treatment solution gradually during oxidation,, can on metallic substance, form the excellent in chemical conversion coating by a kind of oxygenant being added in the chemical conversion treatment solution with the promotes oxidn reaction.The ferric ion and the reaction of the phosphate anion in the treatment solution that obtain by oxidation form the phosphoric acid iron (F that will remove from treatment solution
ePO
4XH
2O) mud.
In the zinc phosphate chemical conversion treatment solution, the oxidation of ferrous ion is carried out in the following manner with organo-peroxide.Promptly when organic superoxide is organic hydroperoxide, since ferrous ion and organically the hydroperoxide electron transferring between molecules and by organic hydroperoxide formation alkoxy free group (RO) (as reaction formula II, and the alkoxy free group of gained becomes ferric ion by reaction IV with oxidation of divalent iron ion:
And when organic superoxide was the over-churning compound, organic over-churning adduct molecule resolved into acyl group free radical (R ' CO) and alkoxy free group (RO) by reaction III, and these free radicals become ferric ion with (V) with oxidation of divalent iron ion by reacting (IV):
Organo-peroxide also helps to form local element at metal material surface when metallic substance is partially soluble in treatment solution, and promotes the precipitation of thin coated crystal.These effects and effect are owing to organo-peroxide and do not depend on the metal types of metallic substance.
In chemical conversion treatment solution of the present invention, organo-peroxide reagent (chemical conversion promotor) is used as oxygenant, and is enriched in the treatment solution by the degradation production that organo-peroxide obtains.For example the decomposition of the hydroperoxide decomposition that obtains pure and mild peroxy esters obtains alcohol and carboxylic acid.The percarboxylic acids decomposition obtains carboxylic acid in addition.The enrichment of degradation production does not influence the effect of method of the present invention and treatment solution.Correspondingly, even the organo-peroxide degradation production is involved or join in the treatment solution of the present invention before chemical conversion is handled, there is not detrimentally affect yet.
In the methods of the invention, metallic substance is not limit type, shape and size.
That is, the inventive method can be used for all types of iron materials and steel, as steel plate, plating zinc-containing metal steel plate, and all types of aluminium-containing metal materials, as aluminum and aluminum alloy materials such as aluminium one magnesium alloy materials and aluminium one aluminosilicate alloy material.
Aqueous zinc phosphate chemical conversion treatment solution of the present invention also further preferably contains a kind of tensio-active agent that metal material surface cleans that is used for.
The tensio-active agent that is included in this chemical conversion treatment solution can make metal material surface carry out surface cleaning and covering zinc phosphate chemical conversion layer simultaneously.In this case, the surface of metallic substance can be contaminated mistake.As long as can being contained the chemical conversion treatment solution of tensio-active agent, removes pollution substance, then without limits pollution substance.Pollution substance comprises oil or fatty substance, as grease, slushing oil, press oil, and can be polluted by dust, fine metal particle and other material.To the amount of pollution substance without limits.
Being used for surface cleaning promoting agent of the present invention contains and is selected from a kind of of nonionic surface active agent, cats product, anion surfactant, amphoterics at least.Yet, among the present invention preferably without the mixture of cats product and anion surfactant, because this mixture stable bad in chemical conversion treatment solution.
Be used for ionic surfactant pack of the present invention and draw together the non-ionic surfactant compound that contains the polyglycol base, as poly suboxygen alkyl alkyl phenyl ether, Voranol EP 2001, polyoxyethylene-fatty acid ester, polyethenoxy sorbitan-fatty acid ester, polyoxyethylene-polyoxypropylene block polymer; The non-ionic surfactant compound that contains the poly-hydroxy alcohol radical is as anhydro sorbitol-fatty acid ester; The non-ionic surfactant compound of amide-containing is as lipid acid-alkylolamide.
Be used for cats product of the present invention and comprise the cation surface activating compound that contains amine salt group, as senior alkyl amine salt and polyoxyethylene-senior alkylamines; The cation surface activating compound that contains quaternary ammonium group is as alkyl-leptodactyline.
Be used for the amophoteric surface active compound that amphoterics of the present invention comprises the amino acid type, as the alkyl aminopropionic acid methyl esters; And betaine (betaine) type amophoteric surface active compound, as the alkyl dimethyl betaine.
Generally speaking, the solvability of cats product in chemical conversion treatment solution is low under acidic conditions, thereby is difficult to real showing sometimes and is used for the present invention.Yet the anion surfactant of some type has satisfied solvability in treatment solution under acidic conditions, and as the oxyethane addition reaction, senior alkyl ether sulfuric acid monoester salt can be used among the present invention.
Zinc phosphate chemical conversion treatment solution of the present invention preferably contains the surface cleaning tensio-active agent that 0.5-5g/ rises content.The type of used tensio-active agent and content should be decided according to pollution substance to be removed (oil or lipid substrate) type and amount.
When chemical conversion treatment solution contained tensio-active agent, surface cleaning processing can be handled with chemical conversion effectively and carry out simultaneously.Therefore when method be when carrying out continuously, the oil or the fatty substance that are removed are enriched in the treatment solution inevitably.The oil of enrichment or fatty substance are not always handled harmless to chemical conversion.Therefore, the total amount of the oil ﹠ fat material of enrichment preferably is limited to 10g/ liter or lower, and this depends on the type of oil or fatty substance and the type and the content of tensio-active agent with changing.
After carrying out the chemical conversion processing with the chemical conversion treatment solution that contains tensio-active agent, the chemical conversion layer water of gained washes, and residual water is removed from the chemical conversion laminar surface.The step of water flushing can be carried out in step by step with one step or a plurality of with deionized water.Last water flushing is preferably carried out with deionized water step by step.
Use lacquer to apply when the chemical conversion laminar surface of metallic substance by for example electro-plating method, then removing the step (drying step) of anhydrating has not just needed.There is no particular limitation to the exsiccant temperature and time, and drying step can carry out under room temperature or heating.
When with the chemical conversion treatment solution that contains tensio-active agent of the present invention metal material surface being handled, the reaction that oil or fatty substance, dust and/or metallic particles were removed and formed simultaneously chemical conversion layer fully obtains promoting by chemical conversion promotor (organo-peroxide).
Therefore, metal material surface is cleaned simultaneously and has formed even, the fine and close zinc phosphate chemical conversion layer that contains thin coated crystal on the metal material surface that cleans.
Embodiment
The present invention is further made an explanation by following examples, and these embodiment just represent and do not limit the scope of the invention.
Embodiment 1-8 and comparing embodiment 1-4.
In embodiment and comparing embodiment, adopt following metallic substance.
1. thickness is the cold-rolled steel sheet (SPCC-SD) of 0.8mm.Be called " SPC steel plate " below this steel plate.
2. with 20g/m
2Zinc the SPC steel plate is electroplated the steel plate galvanized that makes.Be called " zinc-plated SPC steel plate " below this steel plate.
SPC steel plate and zinc-plated SPC steel plate are cut into the size of 70 * 150mm.
In embodiment and comparing embodiment, on metal material surface, form chemical conversion layer with bottom as enamelled coating by following steps.
1. surface cleaning step
Alkaline degreaser (trade mark: Fine Cleaner L 4460 is made by Nihon ParkerizingCo.)
Component A:20g/ liter
Component B:12g/ liter
Temperature: 43 ℃
Time: 120 seconds
Treatment process: dipping
2. water rinse step: (using water,tap)
Temperature: room temperature
Time: 30 seconds
Treatment process: spray
3. surface treatment step
Contain colloidal state titanium compound surface treatment agent (trade mark: Prepalene ZN, produce) by NihonParkering Co.:
The 1g/ liter is in water
Temperature: room temperature
Time: 30 seconds
Treatment process: spray
4. step is handled in the zinc phosphate chemical conversion
Temperature: 43 ℃
Time: 120 seconds
Treatment process: dipping
Other treatment condition will be pointed out in the back.
5. use the water rinse step of water,tap
Temperature: room temperature
Time: 30 seconds
Treatment process: spray
6. with specific conductivity the deionized water rinsing step of the deionized water of 0.2 μ s/cm
Temperature: room temperature
Time: 20 seconds
Treatment process: spray
7. remove and anhydrate and drying step
Temperature: blow with 110 ℃ of hot blasts
Time: 180 seconds
Embodiment 5 and 7 and comparing embodiment 3 in, 3. above-mentioned surface treatment step is saved, therefore, the surface cleaning step 1. with the water rinse step 2. after, directly the metal material surface of the flushing of cleaning surfaces is carried out the zinc phosphate chemical conversion and handles.
In each of embodiment 1-8 and comparing embodiment 1-4, the free acidity of zinc phosphate chemical conversion treatment solution is transferred to the value of stipulating below by adding aqueous sodium hydroxide solution.By sucking-off 10ml zinc phosphate chemical conversion treatment solution, make indicator with the bromophenol orchid, with the 0.1N NaOH aqueous solution treatment solution that takes out is carried out neutralization titration, the ml vol of the NaOH aqueous solution that mensuration is consumed when making the indicator color from the xanthochromia orchid, thereby the free acidity of definite treatment solution.
In addition, by using fluoride ion electrode to be determined at the concentration of fluorion in the chemical conversion treatment solution.
In addition, the weight of chemical conversion layer is determined by following method.
Measure the weight (W1 is in g) of the metallic substance of band chemical conversion layer.By the metallic substance that has applied being handled to remove chemical conversion layer with removing treatment solution following removing under the treatment condition:
Under the situation of SPC steel plate,
Remove the coating treatment solution: 5% chromic acid aqueous solution;
Remove treatment condition:
Temperature: 75 ℃
Time: 15 minutes
Treatment process: dipping
Under the situation of zinc-plated SPC steel plate,
Remove treatment solution: 28% ammonia soln of the ammonium dichromate of 2% (weight) and 49% (weight), in the purified water of 49% (weight)
Remove treatment condition:
Temperature: room temperature
Time: 15 minutes
Treatment process: dipping
Measure the weight of the metallic substance of decoating (W2 is in g)
(W3 is with gm to press the weight of following formula (VI) calculational chemistry conversion coating
2Meter)
Heavy W3 (the g/m of coating
2)=(W1-W2)/0.021 (VI)
The outward appearance of chemical conversion layer is observed by bore hole or scanning electronic microscope (SEM) observation is assessed, and measures the form and the size of coated crystal by scanning electronic microscope.
In embodiment 1, preparation is by having the following chemical conversion treatment solution of forming 1..
1. chemical conversion treatment solution is formed
Phosphate anion 15g/ liter
Zine ion 1.3g/ liter
Nickel ion 1.0g/ liter
Mn ion 0.5g/ liter
Fluorion 100ppm
Uncle's fourth is crossed pure 450ppm.
Phosphate anion is derived from 75% phosphate aqueous solution, and zine ion is obtained by dissolved oxygen zinc, and nickel ion source is from nickelous carbonate, and mn ion is derived from manganous carbonate, and fluorion is from 55% hydrofluoric acid aqueous solution, and uncle's fourth is crossed alcohol as chemical conversion promotor.
The free acidity of chemical conversion treatment solution transfers to 0.9 point
3. the SPC steel plate is advanced surface treatment by surface treatment step, then in above-mentioned chemical conversion treatment solution, flooding 120 seconds under 43 ℃ the treatment temp.The chemical conversion layer of gained has 1.2g/m
2Weight.Coated crystal is flaky, and mean size is 6 μ m.This chemical conversion layer is linen and even compact.
In embodiment 2, as the zinc-plated SPC steel plate of 1 couple of embodiment implement same surface cleaning step 1., 3. 2. the water rinse step reach surface treatment step, then as using the chemical conversion treatment solution identical with embodiment 1 that surface-treated steel plate is handled under the condition among the embodiment 1.And the steel plate that chemical conversion applies implemented aftertreatment as embodiment 1.
The chemical conversion layer weight of gained is 2.8g/m
2, coated crystal is flaky and mean size is 4 μ m.Coating is canescence and even compact.
In embodiment 3, the SPC steel plate is implemented the identical operation with embodiment 1, uncle's fourth that different is uses content of alcohol excessively is that the free acidity of 80ppm and chemical conversion treatment solution transfers to 0.6 point.
It is 0.9g/m that coating wt is handled in the chemical conversion that obtains
2, coated crystal is flaky and mean size is 8 μ m.Coating is grey black and even compact.
In embodiment 4, the SPC steel plate is implemented the identical operation with embodiment 1, thus different is chemical conversion treatment solution uncle fourth excessively the content of alcohol be 1200ppm and free acidity be adjusted to 0.9 point to regulate nitrogen content to 500ppm by adding 65.5% aqueous nitric acid.
The chemical transformation coating wt of gained is 1.1g/m
2And coated crystal is a sheet, and the crystal mean size is 7 μ m.Chemical conversion layer is grey black and even compact.
In embodiment 5, the SPC steel plate is implemented the identical operation with embodiment 1, different is to save surface treatment step 3., with the content of 400ppm add uncle oneself to cross alcohol pure excessively to replace uncle's fourth, and free acidity transfers to 0.9 point.
The chemical transformation coating wt of gained is 1.0g/m
2And coated crystal is a sheet, and the crystal mean size is 6 μ m.Coating is grey black and even compact.
In embodiment 6, the SPC steel plate is implemented the identical program with embodiment 1, different is to adopt the peracetic acid of 100ppm content pure excessively to replace uncle's fourth, and free acidity transfers to 0.6 point.
The chemical conversion layer weight of gained is 1.3g/m
2And coated crystal is a sheet, and the crystal mean size is 10 μ m.Coating is grey black and even compact.
In embodiment 7, the SPC steel plate is adopted the identical step with embodiment 1, different is to save surface treatment step 3., and it is 500ppm that uncle's fourth is crossed pure content, and free acidity is adjusted to 0.6 point.
It is 1.1g/m that coating wt is handled in the chemical conversion of gained
2, coated crystal is that sheet and mean size are 10 μ m.Coating is grey black and even compact.
In embodiment 8, preparation by the following chemical conversion treatment solution of forming 2.
2. chemical conversion treatment solution is formed
Phosphate anion 15g/ liter
Zine ion 1.3g/ liter
Nickel ion 1.0g/ liter
Mn ion 0.5g/ liter
Fluorion 100ppm
Uncle's fourth is crossed pure 450ppm
Nitrate ion 7.2g/ liter (be equivalent to 1.4g/ and rise nitrogen content)
Phosphate anion is derived from 75% phosphate aqueous solution, and zine ion is obtained by dissolved oxygen zinc, and nickel ion source is from nickelous nitrate, and mn ion is derived from manganous carbonate, and fluorion is from 55% hydrofluoric acid aqueous solution, and nitrate ion is from SODIUMNITRATE and nickelous nitrate.Tert-butyl peroxy alcohol is as chemical conversion promotor.
The free acidity of chemical conversion treatment solution transfers to 0.9 point.
3. the SPC steel plate of surface cleaning being crossed by surface treatment step that washed with water carries out surface treatment, then under 43 ℃ the treatment temp in above-mentioned chemical conversion treatment solution dipping 120 seconds.The chemical conversion layer weight of gained is 1.1g/m
2Coated crystal is that particulate state and mean size are 5 μ m.Coating is grey black and even compact.
Relatively implementing in 1, the SPC steel plate is adopted the operation be same as embodiment 1, it is 5ppm that uncle's fourth that different is is crossed determining alcohol.The coating amount of gained is 0.5g/m
2And produce yellow rust at the chemical conversion laminar surface.
In comparing embodiment 2, implement to be same as the operation of embodiment 1, different is to replace the SPC steel plate with zinc-plated SPC steel plate, it is 5ppm that uncle's fourth is crossed determining alcohol.
The chemical conversion layer weight of gained is 0.9g/m
2, the coated crystal mean size is 15 μ m, chemical conversion layer sparsely forms at surface of steel plate.
In comparing embodiment 3, the SPC steel plate is adopted as the step of embodiment 8, different is to have saved surface treatment step 3., and uncle's fourth is crossed and purely replaced by the nitrite ion of 150ppm.
The chemical conversion layer amount of gained is 0.1g/m
2, promptly on the pending surface of SPC steel plate, almost do not have the chemical conversion cuticula to form, and produced yellow rust.
In comparing embodiment 4, the SPC steel plate has been adopted the operation that is same as embodiment 1, different is to replace uncle's fourth to cross alcohol and add sodium chlorate so that the chemical conversion treatment solution that obtains contains the chloranion that 1.5g/ rises.
The chemical conversion layer amount of gained is 0.9g/m
2, coated crystal be prism-shaped and mean size be 15 μ m.Formed sparse chemical conversion layer and produced yellow rust at pending SPC surface of steel plate.
Test result sees Table 1
Table 1
Remarks (
* 1) a ... uncle's fourth is crossed pure d ... nitrite ion
| Embodiment number | Metallic substance | Surface treatment step | Chemical conversion treatment solution | Chemical conversion layer | |||||||||
| Phosphate anion content (g/l) | Zinc ion content (g/l) | Nitrogen content (ppm) | Chemical conversion promotor | Free acidity (point) | Weight (g/m 2) | Apparent | The coated crystal form | Average crystalline size (μ m) | |||||
| Type (*1) | Content (ppm) | ||||||||||||
| Embodiment | 1 | SPC | Adopt | 15 | 1.3 | 0 | a | 450 | 0.9 | 1.2 | Greyish black | Sheet | 6 |
| 2 | Zinc-plated SPC | Adopt | 15 | 1.3 | 0 | a | 450 | 0.9 | 2.8 | Greyish white | Sheet | 4 | |
| 3 | SPC | Adopt | 15 | 1.3 | 0 | a | 80 | 0.6 | 0.9 | Greyish black | Sheet | 8 | |
| 4 | SPC | Adopt | 15 | 1.3 | 500 | a | 1200 | 0.9 | 1.1 | Greyish black | Sheet | 7 | |
| 5 | SPC | No | 15 | 1.3 | 0 | b | 400 | 0.9 | 1.0 | Greyish black | Sheet | 6 | |
| 6 | SPC | Adopt | 15 | 1.3 | 0 | c | 100 | 0.6 | 1.3 | Greyish black | Sheet | 10 | |
| 7 | SPC | No | 15 | 1.3 | 0 | a | 500 | 0.6 | 1.1 | Greyish black | Sheet | 10 | |
| 8 | SPC | Adopt | 15 | 1.3 | 1400 | a | 450 | 0.9 | 1.1 | Greyish black | Particle | 5 | |
| Comparing embodiment | 1 | SPC | Adopt | 15 | 1.3 | 0 | a | 5 | 0.9 | 0.5 | Yellow rust | Prismatic | |
| 2 | The SPC of plating Zn | Adopt | 15 | 1.3 | 0 | a | 5 | 0.9 | 0.9 | Sparse | Prismatic | 15 | |
| 3 | SPC | No | 15 | 1.3 | 1400 | d | 150 | 0.9 | 0.1 | Yellow rust | Particle | 80 | |
| 4 | SPC | Adopt | 15 | 1.3 | 0 | e | 1500 | 0.9 | 0.9 | Sparse | Prismatic | 5 | |
B ... oneself crosses pure e uncle ... chloranion
C ... peracetic acid
Table 1 has clearly illustrated that in embodiment 1-8 wherein the organo-peroxide content of Ying Yonging is 50-1500ppm, can form satisfied chemical conversion layer on cold-rolled steel sheet and cold rolling, steel plate galvanized.In addition, also confirm the special chemical conversion treatment solution of the application of the invention, even saved the chemical conversion cuticula that surface treatment also can form even compact at metal material surface.
In comparing embodiment 1 and 2,, obtain the effect of insufficient promotion chemical conversion, thereby the chemical conversion layer that obtains has bad coverage on metal material surface because the content of organo-peroxide is less than 50ppm.
In comparing embodiment 3 and 4, replace organo-peroxide of the present invention and adopted other oxygenant.In comparing embodiment 3, saved surface treatment, and replaced organo-peroxide and adopted a kind of nitrite, there is not chemical conversion coating to form basically.In comparing embodiment 4, replace organo-peroxide and adopted oxymuriate, proved conclusively the chemical conversion speed of reaction and reduced greatly.
Embodiment 9-15
In these embodiments, adopted following metallic substance.
1. cold-rolled steel sheet (SPCC-SD), thickness is 0.8mm.
2. thickness is 0.8mm, plates with 30g/m on each surface of steel plate
2The electrogalvanizing steel plate of zinc layer.
3. thickness is the galvanized alloy steel plate of 0.8mm, and each surface of steel plate is coated with 45g/m
2The zinc layer.
4. thickness is the aluminium-magnesium alloy plate (A5052) of 1.0mm.
Steel plate is cut into the fritter that is of a size of 70 * 150mm.Steel plate 2g/m
2Clean and the slushing oil coating.
Among 9 to 15 each embodiment, use the method identical with embodiment 1 to handle metallic substance, different is, the omission surface treatment step, and 3., 4. or 5. replace chemical conversion treatment solution 1. with the chemical conversion treatment solution of following composition.
Chemical conversion treatment solution 3.
Phosphate anion 15g/l
(deriving from 75% phosphate aqueous solution)
Zine ion 1.3g/l
(producing) by dissolved zinc oxide
Nickel ion 0.5g/l
(deriving from nickelous carbonate)
Fluorochemical component 1.0g/l
(deriving from Sodium Silicofluoride)
Chemical conversion promotor is as described below
2-butyl alcohol 30g/l
Free acidity: 0.6 point
Chemical conversion treatment solution 4.
Phosphate anion 13g/l
(deriving from 75% phosphate aqueous solution)
Zine ion 1.1g/l
(obtaining) by dissolved oxygen zinc
Cobalt ion 0.4g/l
(deriving from cobaltous dihydroxycarbonate)
Fluorochemical component 0.4g/l
(deriving from hydrofluoric acid sodium)
Chemical conversion promotor is as described below
Free acidity 0.4 point
Chemical conversion treatment solution 5.
Phosphate anion 17g/l
(deriving from 75% phosphate aqueous solution)
Zine ion 1.5g/l
(by the preparation of dissolved oxygen zinc)
Chemical conversion promotor is as described below
Free acidity: 0.7 point
With aqueous sodium hydroxide solution with chemical conversion treatment solution 3., 4. and 5. each free acidity transfer to above-mentioned value.
Measure free acidity, the weight of chemical conversion layer, the situation of coated crystal and size with above-mentioned same way as.
The following standard evaluation of the fineness of coated crystal.
Cold-rolled steel sheet 1.
Be lower than 35 μ m: satisfied
35 μ m or higher: dissatisfied
Steel plate galvanized 2.
Be lower than 25 μ m: satisfied
25 μ m or higher: dissatisfied
The galvanized alloy steel plate 3.
Be lower than 30 μ m: satisfied
30 μ m or higher: dissatisfied
Aluminium-magnesium alloy plate 4.
Be lower than 30 μ m:: satisfied
30 μ m or higher: dissatisfied
The following standard evaluation of the coverage of chemical conversion layer on the metal material surface.
Metal material surface is applied fully: satisfied
Metal material surface is partly applied: dissatisfied
(trade mark: Elecron 2000, Kansai Paint Co. makes) carries out the galvanic deposit coating to the metal sheet that chemical conversion applies with the cationic electrodeposition lacquer, and forming thickness is the enamelled coating of 20 μ m.
Electro-deposition coating metal sheet test specimen is carried out following coating performance test.
(1) corrosion resistance test of japanning test specimen
The galvanic deposit coated surface of cross cut test specimen impregnated in 50 ℃ of following 5%NaCl heated in water solution 240 hours, takes out from NaCl solution then.After water flushing test specimen and the drying, self adhesive tape adheres to test specimen square section peripheral part, peels off and removes the bubble that forms around the test specimen square section.Measure a side maximum width of bubble.The following standard evaluation of solidity to corrosion of japanning test specimen.
One side maximum width of bubble
Be lower than 7mm: excellence
7mm or higher, but be lower than 10mm: satisfied
10mm or higher: dissatisfied
(2) water-repellancy and the secondary stripping test of japanning test specimen
Under 40 ℃, the electro-deposition coating test specimen flooded in purifying waste water 240 hours, took out from water then.The painted surface of cross cut test specimen.With the Erichsen test machine 3mm is pulled out at middle part, test specimen square section, test specimen is carried out self adhesive tape-stripping test.Measure and calculate the percentage ratio of peeling off of enamelled coating.
With following standard evaluation test result.
Enamelled coating is peeled off (%)
Be lower than 10%: excellence
10% or higher but be lower than 20%: satisfied
20% or higher: dissatisfied
Among the embodiment 9, it is pure excessively that 3. chemical conversion treatment solution contains uncle's 200ppm fourth.Under 45 ℃, 3. the SPC plate impregnated in this treatment solution.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 10,3. chemical conversion treatment solution contains 80ppm two-tert-butyl peroxide.Under 45 ℃, zinc-plated SPC plate impregnated in this treatment solution 3. in.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 11, it is pure excessively that 4. chemical conversion treatment solution contains uncle's 500ppm fourth.Under 40 ℃, 4. the SPC plate is carried out spray treatment with this treatment solution.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 12,4. chemical conversion treatment solution contains the 1100ppm acetylacetone peroxide.Under 40 ℃, zinc-plated SPC plate impregnated in this treatment solution 4. in.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 13,3. chemical conversion treatment solution contains the 500ppm ditertiary butyl peroxide.Under 43 ℃, the SPC plate impregnated in this treatment solution 3. in.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 14, it is pure excessively that 5. chemical conversion treatment solution contains uncle's 500ppm fourth.5. 33 ℃ carried out spray treatment to the alloy steel plate galvanized with this treatment solution.
Treatment condition are shown in table 2, and test result is shown in table 3.
Among the embodiment 15,3. chemical conversion treatment solution contains the 150ppm ditertiary butyl peroxide.Under 43 ℃, aluminium-magnesium alloy plate is carried out spray treatment with this treatment solution.
Treatment condition are shown in table 2, and test result is shown in table 3.
Table 2
Remarks (
*)
2-SPC: cold-rolled steel sheet EG: cold-rolling galvanization steel plate
| Embodiment number | Metallic substance ( *) 2 | Chemical conversion treatment solution | Chemical conversion is handled | ||||||||
| Phosphate anion content (g/l) | Zinc ion content (g/l) | Other metal ion | Organo-peroxide | Fluorochemical (g/l) | Free acidity (point) | Temperature (℃) | Treatment process | ||||
| Type | Content (g/l) | Type ( *) 3 | Content (ppm) | ||||||||
| Embodiment 9 | SPC | 15 | 1.3 | Ni | 0.5 | a | 200 | 1.0 | 0.6 | 45 | Dipping |
| 10 | EG | 15 | 1.3 | Ni | 0.5 | f | 80 | 1.0 | 0.6 | 45 | Dipping |
| 11 | SPC | 13 | 1.1 | Co | 0.4 | a | 500 | 0.4 | 0.4 | 40 | Spraying |
| 12 | EG | 13 | 1.1 | Co | 0.4 | g | 1100 | 0.4 | 0.4 | 40 | Dipping |
| 13 | SPC | 15 | 1.3 | Ni | 0.5 | f | 500 | 1.0 | 0.6 | 43 | Dipping |
| 14 | GA | 17 | 1.5 | - | - | a | 500 | - | 0.7 | 33 | Spraying |
| 15 | AL | 15 | 1.3 | Ni | 0.5 | f | 150 | 1.0 | 0.6 | 43 | Spraying |
GA: galvanized alloy steel plate AL:Al-Mg alloy sheets
(
*)
3-a: uncle's fourth is crossed pure f: ditertiary butyl peroxide
G: acetylacetone peroxide
Table 3
| Embodiment number | Chemical conversion layer | The japanning metallic substance | |||
| Coating wt (g/m 2) | The coated crystal fineness | The metal material surface coverage | Solidity to corrosion | The secondary bonding water tolerance | |
| Embodiment 9 | 0.9 | Satisfied | Satisfied | Excellent | Excellent |
| 10 | 3.5 | Satisfied | ″ | ″ | ″ |
| 11 | 1.2 | ″ | ″ | ″ | ″ |
| 12 | 3.2 | ″ | ″ | ″ | ″ |
| 13 | 1.3 | ″ | ″ | ″ | ″ |
| 14 | 4.3 | ″ | ″ | Satisfied | ″ |
| 15 | 2.5 | ″ | ″ | Satisfied | ″ |
Comparative Examples 5 to 9
In 5 to 9 each Comparative Examples, carry out operation and the test identical, following difference is just arranged with embodiment 9.
In the Comparative Examples 5,3. chemical conversion treatment solution contains the 200ppm nitrite ion.Under 43 ℃, the SPC plate impregnated in the chemical conversion solution that obtains.
Treatment condition are shown in table 4, and test result is shown in table 5.
In the Comparative Examples 6, chemical conversion treatment solution saves chemical conversion promotor in 3..Under 43 ℃, the SPC plate impregnated in the chemical conversion treatment solution that obtains.
Treatment condition are shown in table 4, and test result is shown in table 5.
In the Comparative Examples 7,4. chemical conversion treatment solution contains the 2000ppm chloranion.Under 40 ℃, zinc-plated SPC plate impregnated in the chemical conversion treatment solution that obtains.
Treatment condition are shown in table 4, and test result is shown in table 5.
In the Comparative Examples 8,5. chemical conversion treatment solution omits chemical conversion promotor.
With 33 ℃ of treatment solutions that heat down of gained the galvanized alloy plate is carried out spray treatment.
Treatment condition are shown in table 4, and test result is shown in table 5.
In the Comparative Examples 9, the 3. middle omission chemical conversion of chemical conversion treatment solution promotor.With 43 ℃ of treatment solutions that heat down of gained aluminium-magnesium alloy plate is carried out spray treatment.
Treatment condition are shown in table 4, and test result is shown in table 5.
Table 4
Annotate: (
*)
4D: nitrite ion
| Comparative Examples number | Metallic substance | Chemical conversion treatment solution | Chemical conversion is handled | ||||||||
| Phosphate anion content (g/l) | Zinc ion content (g/l) | Other metal ion | Oxygenant | Fluorochemical (g/l) | Free acidity (point) | Temperature (℃) | Treatment process | ||||
| Type | Content (g/l) | Type ( *) 4 | Content (ppm) | ||||||||
| Comparative Examples 5 | SPC | 15 | 1.3 | Ni | 0.5 | d | 200 | 1.0 | 0.6 | 43 | Dipping |
| 6 | SPC | 15 | 1.3 | Ni | 0.5 | - | - | 1.0 | 0.6 | 43 | Dipping |
| 7 | EG | 13 | 1.1 | Co | 0.4 | e | 2000 | 0.4 | 0.4 | 40 | Dipping |
| 8 | GA | 17 | 1.5 | - | - | - | - | - | 0.7 | 33 | Spraying |
| 9 | AL | 15 | 1.3 | Ni | 0.5 | - | - | 1.0 | 0.6 | 43 | Spraying |
E: chloranion
Table 5
| Comparative Examples number | Chemical conversion layer | The japanning metallic substance | |||
| Coating wt | The coated crystal fineness | The metal material surface coverage | Solidity to corrosion | The secondary bonding water-based | |
| Comparative Examples 5 | 4.0 | Dissatisfied | Dissatisfied | Satisfied | Dissatisfied |
| 6 | 0.5 | ″ | ″ | Dissatisfied | Satisfied |
| 7 | 5.2 | ″ | Satisfied | Satisfied | Dissatisfied |
| 8 | 7.3 | ″ | ″ | Dissatisfied | ″ |
| 9 | 1.5 | ″ | Dissatisfied | ″ | Satisfied |
As table 2 to the 5 clear expressions, among the embodiment 9 to 15, because chemical conversion treatment solution contains the organo-peroxide as chemical conversion promotor, gained zinc phosphate chemical conversion layer is thin, even and fine and close, demonstrate good japanning performance (solidity to corrosion that the japanning metallic substance is good and good lacquer bounding force).
In the Comparative Examples 6,8 and 9 of saving chemical conversion promotor, chemical conversion sluggish and coated crystal localized precipitation, thereby metal material surface is by the chemical conversion layer topical application.
Be used as in the Comparative Examples 7 of oxygenant at the Comparative Examples 5 and the oxymuriate of nitrite as oxygenant, the gained chemical conversion layer is not fine and close, thereby the coating performance that shows is unsatisfactory.
Embodiment 16 to 22 and Comparative Examples 10 to 14
In embodiment 16 to 22 and Comparative Examples 10 to 14, use with embodiment 9 in identical cold-rolled steel sheet (SPC plate), with embodiment 10 in steel plate, the thickness of identical electro-galvanizing be 2.8mm, each surface is coated with 45g/m
2The galvanized alloy steel plate of zinc layer with embodiment 15 in identical aluminium-magnesium alloy plate.Scribbling the amount of being coated with on these plates is 2g/m
2Cleaning and slushing oil (trade mark: NOX-RUST 550, Parker Kosan Co. make).
In each embodiment and Comparative Examples, handle metallic substance with following treatment step.
(1) step is handled in cleaning under the following condition and chemical conversion.
(2) rinse step of use tap water
Temperature: room temperature
Time: 30 seconds
Treatment process: spray
(3) using specific conductivity is the treatment step of the deionized water of 0.2 μ s/cm
Temperature: room temperature
Time: 20 seconds
Treatment process: spray
(4) use dewatering and drying step of warm air air blast
Temperature: 110 ℃
Time: 180 seconds
In each embodiment and the Comparative Examples, the free acidity of regulating cleaning and chemical conversion treatment solution with aqueous sodium hydroxide solution (except that specifying) is to following value.With with embodiment 1 in identical method measure free acidity.
With with embodiment 1 in the weight of identical test determines chemical conversion layer.In this testing method, carry out coating stripping with following method.
(1) SPC plate
The coating stripping treatment solution:
5% chromic acid aqueous solution
The treatment solution condition:
Temperature: 75 ℃
Time: 15 minutes
Method: dipping
(2) galvanized sheet
Treatment solution: 2% (weight) ammonium dichromate, 49% (weight) concentration are 28% ammonia soln, the aqueous solution in 49% (weight) purified water.
Treatment condition:
Temperature: room temperature
Time: 15 minutes
Method: soak clearly
(3) Al-Mg alloy sheets
Treatment solution: 5% chromic acid aqueous solution
Treatment condition:
Temperature: room temperature
Time: 5 minutes
Method: soak clearly
(SEM) observes coated crystal under 1000 ratio of enlargement with scanning electronic microscope.Measure coated crystal size and fineness, and use following standard evaluation.Equally, with the coverage of following standard evaluation chemical conversion layer at metal material surface.
(1) evaluation of coated crystal fineness size
Be lower than 30 μ m: satisfied
30 μ m or higher but be lower than 50 μ m: not too satisfied
50 μ m or higher: dissatisfied
(2) to the evaluation of chemical conversion layer in the coverage of metal material surface
Metal material surface is covered fully: satisfied
The metal material surface sub-fraction is not capped: not too satisfied
Metal material surface is not capped: dissatisfied
Among the embodiment 16, with the preparation of following composition please wash with chemical conversion treatment solution 6.
Phosphate anion 15g/l
Zine ion 1.3g/l
Nickel ion 0.5g/l
Fluorochemical composition 1.0g/l
Uncle's fourth is crossed pure 500ppm
Trimethyl carbinol 4.0g/l
Molecular-weight average is 10,000
Ethylene oxide content is 80% polyoxy
Ethene-polyoxypropylene block polymer 1.0g/l
Oil component (trade mark: NOX-RUST 550) 2.0g/l
Free acidity 0.6 point
In treatment solution preparation 6., phosphate anion derives from 75% phosphate aqueous solution, and zine ion is produced by dissolved oxygen zinc, and nickel ion derives from nickelous carbonate, and the fluorochemical composition derives from sodium silicofluoride.
The SPC plate treatment solution 6. in the dipping 180 seconds.The chemical conversion layer that obtains is 1.2g/m
2The fineness of coated crystal and the chemical conversion layer coverage on metal material surface is good.
Test result is shown in table 6.
In embodiment 17, carry out with embodiment 16 in identical step and test, different is, steel plate galvanized is cleaning and chemical conversion treatment solution flooded 180 seconds in 6..The chemical conversion layer that obtains is 3.5g/m
2Coating fineness and chemical conversion coating are good in the coverage of metal material surface.
Test result is shown in table 6.
Real in example 18, with the preparation of following composition clean and chemical conversion treatment solution 7..
Phosphate anion 14g/l
Zine ion 1.3g/l
Cobalt ion 0.5g/l
Ditertiary butyl peroxide 1000ppm
Trimethyl carbinol 2.0g/l
Oxyethane adduction mole number is 20 1.0g/l
Tween-20
Oxyethane adduction mole number is 3 0.5g/l
Polyethylene lauryl ether sulphonate
Oil component (trade mark: NOX-RUST 550) 3.0g/l
Free acidity 0.5 point
In treatment solution preparation 7., phosphate anion derives from 75% phosphate aqueous solution, and zine ion is produced by dissolved oxygen zinc, and cobalt ion derives from cobaltous dihydroxycarbonate.
7. 40 ℃ of following heat treated liquid sprayed 120 seconds on SPC plate surface.
The chemical conversion layer that obtains is 1.2g/m
2The fineness of coated crystal and chemical transformation coating are good in the coverage of metal material surface.
Test result is shown in table 6.
Among the embodiment 19, carry out with embodiment 18 in identical step and test, different is, with cleaning and 7. chemical conversion treatment solution carried out spray treatment 120 seconds to steel plate galvanized.The gained chemical conversion layer is 3.3g/m
2The fineness of coated crystal and the chemical conversion coating coverage on metal material surface is good.
Test result is shown in table 6.
Among the embodiment 20, with the preparation of following composition clean and chemical conversion treatment solution 8..
Phosphate anion 17g/l
Zine ion 1.5g/l
Fluorochemical composition 0.4g/l
Acetylacetone peroxide 100ppm
Oil component (trade mark: NOX-RUST 550) 2.0g/l
7 l.5g/l oxyethane adduction mole number is
Polyoxyethylene-oily ether
Lauryl dimethyl betaine 0.5g/l
Free acidity 0.7 point
In treatment solution preparation 8., phosphate anion derives from 75% phosphate aqueous solution, and zine ion is produced by dissolved oxygen zinc, and the fluorochemical composition derives from Sodium Fluoride.
8. 43 ℃ of following heated wash and chemical conversion treatment solution spray to it on SPC plate surface in 30 seconds, then, plate in treatment solution 8. in dipping 90 seconds.The gained chemical conversion layer is 1.3g/m
2The fineness of coated crystal and chemical conversion layer are good in the lip-deep coverage of SPC plate.
Test result is shown in table 6.
Among the embodiment 21, carry out with embodiment 20 in identical step and test, different is, with cleaning and 8. chemical conversion treatment solution carried out spray treatment 30 seconds to steel plate galvanized, floods 90 seconds in 8. in treatment solution again.The gained chemical conversion layer is 3.6g/m
2The fineness of coated crystal and the coverage of chemical transformation coating on metal material surface are good.
Test result is shown in table 6.
Among the embodiment 22, carry out with embodiment 20 in identical step and test, different is, with cleaning and 8. chemical conversion treatment solution carried out spray treatment 30 seconds to aluminium-magnesium alloy plate, floods 90 seconds in 8. in treatment solution again.The gained chemical conversion layer is 2.5g/m
2The fineness of coated crystal and the chemical conversion layer coverage on metal material surface is good.
Test result is shown in table 6.
In Comparative Examples 10, prepare chemical conversion treatment solution 9. with following composition.
Phosphate anion 15g/l
Zine ion 1.3g/l
Nickel ion 0.5g/l
Fluorochemical composition 1.0g/l
Nitrate ion 7.0g/l
Nitrite ion 100ppm
Oil component (trade mark: NOX-RUST 550) 2.0g/l
Free acidity 0.6 point
In treatment solution preparation 9., phosphate anion derives from 75% phosphate aqueous solution, and zine ion is produced by dissolved oxygen zinc, nickel ion derives from basic nickel carbonate, the fluorochemical composition derives from sodium silicofluoride, and nitrate ion derives from SODIUMNITRATE, and nitrite ion derives from Sodium Nitrite.
The SPC plate 45 ℃ of following heat treated liquid 9. in the dipping 180 seconds.Because 9. treatment solution does not contain chemical conversion promotor and clean surface promoting agent, oily substance is not removed, and does not form coating.
Test result is shown in table 6.
In Comparative Examples 11, with the preparation of following composition clean and chemical conversion treatment solution 10..
Phosphate anion 15g/l
Zine ion 1.3g/l
Nickel ion 0.5g/l
Fluorochemical composition 1.0g/l
Nitrate ion 7.0g/l
Nitrite ion 100ppm
Molecular-weight average is 10,000
Ethylene oxide content is 80%
Polyoxyethylene-polyoxypropylene
Block polymer 1.0g/l
Oil component (trade mark: NOX-RUST 550) 2.0g/l
Free acidity 0.6 point
In treatment solution preparation 10., phosphate anion derives from 75% phosphate aqueous solution, and zine ion is produced by dissolved oxygen zinc, nickel ion derives from basic nickel carbonate, the fluorochemical composition derives from sodium silicofluoride, and nitrate ion derives from SODIUMNITRATE, and nitrite ion derives from Sodium Nitrite.
Galvanized sheet 45 ℃ down the treatment solutions of heating flooded 180 seconds in 10..The gained chemical conversion layer is 5.3g/m
2Although the coverage of chemical conversion layer on metal material surface is good, coated crystal is thick, and owing to lack organic peroxide compounds, the fineness of coated crystal is poor.
Test result is shown in table 6.
In Comparative Examples 12, with the preparation of following composition clean and chemical conversion treatment solution _.
Phosphate anion 14g/l
Zine ion 1.3g/l
Cobalt ion 0.5g/l
Oxyethane adduction mole number is 1.0g/l
20 polyoxyethylene sorbose 7.0g/l
Alcohol acid anhydride mono-laurate
Oxyethane adduction mole number is 0.5g/l
3 polyoxyethylene lauryl ether sulphonate
Oil component (trade mark: NOX-RUST 550) 3.0g/l
Free acidity 0.5 point
Treatment solution _ preparation in, phosphate anion derives from 75% phosphate aqueous solution, zine ion is produced by dissolved oxygen zinc, cobalt ion derives from cobaltous dihydroxycarbonate.
With the treatment solution _ SPC plate was carried out spray treatment 120 seconds.The gained chemical conversion layer is 0.3g/m
2Owing to lack organo-peroxide, the fineness of coated crystal and chemical conversion layer are poor in the coverage of metal material surface.
Test result is shown in table 6.
In Comparative Examples 13, with the preparation of following composition clean and chemical conversion treatment solution _.
Phosphate anion 14g/l
Zine ion 1.3g/l
Cobalt ion 0.5g/l
Chloranion 1.5g/l
Oxyethane adduction mole number is 1.0g/l
Polyoxyethylene-sorbose of 20
Alcohol acid anhydride mono-laurate
Oxyethane adduction mole number is 0.5g/l
Polyoxyethylene-lauryl ether of 3
Sulphonate salt
Oil component (trade mark: NOX-RUST 550) 3.0g/l
Free acidity 0.5 point
Treatment solution _ preparation in, phosphate anion derives from 75% phosphate aqueous solution, zine ion is produced by dissolved oxygen zinc, cobalt ion derives from cobaltous dihydroxycarbonate, chloranion derives from sodium chlorate.
Treatment solution _ galvanized sheet was carried out spray treatment 120 seconds with heating below 40 ℃.The gained chemical conversion layer is 2.1g/m
2Owing to lack the organo-peroxide composition, the fineness of coated crystal is poor, and also some is poor in the margin of covering of metal material surface for the chemical transformation coating.
Test result is shown in table 6.
In Comparative Examples 14, carry out with Comparative Examples 13 in identical step and test, different is, with clean and chemical conversion treatment solution _ aluminium-magnesium alloy plate was carried out spray treatment 120 seconds.Owing to lack organo-peroxide, do not form chemical conversion layer.
Test result is shown in table 6.
Table 6
Annotate: (
*)
5-SPC: cold-rolled steel sheet (
*)
7-A: polyoxyethylene-polyoxypropylene block polymer
| Embodiment number | Metallic substance ( *) 5 | Chemical conversion promotor | The clean surface promoting agent | The coated crystal fineness ( *) 3 | The metallic surface coverage ( *) 3 | |||
| Type ( *) 6 | Content (ppm) | Type ( *) 7 | Content (g/l) | |||||
| Embodiment | 16 | SPC | a | 500 | A | 1.0 | Satisfied | Satisfied |
| 17 | EG | a | 500 | A | 1.0 | Satisfied | Satisfied | |
| 18 | SPC | f | 1000 | B C | 1.0 0.5 | Satisfied | Satisfied | |
| 19 | EG | f | 1000 | B C | 1.0 0.5 | Satisfied | Satisfied | |
| 20 | SPC | g | 100 | D E | 1.5 0.5 | Satisfied | Satisfied | |
| 21 | EG | g | 100 | D E | 1.5 0.5 | Satisfied | Satisfied | |
| 22 | AL | g | 100 | D E | 1.5 0.5 | Satisfied | Satisfied | |
| Comparative Examples | 10 | SPC | h d | 7000 100 | - | - | There is not coating | Dissatisfied |
| 11 | EG | h d | 7000 100 | A | 1.0 | Dissatisfied | Satisfied | |
| 12 | SPC | - | - | B C | 1.0 0.5 | Dissatisfied | Dissatisfied | |
| 13 | EG | e | 1500 | B C | 1.0 0.5 | Dissatisfied | Not too satisfied | |
| 14 | AL | e | 1500 | B C | 1.0 0.5 | There is not coating | Dissatisfied | |
EG: electrogalvanizing steel plate B: polyoxyethylene-Span-20
AL: aluminium-magnesium alloy plate C: polyoxyethylene laurel ether sulfuric acid
(
*)
6-a: tert-butyl hydroperoxide D: polyoxyl 10 oleyl ether
F: ditertiary butyl peroxide E: polyoxyethylene lauryl dimethyl betaine
G: acetylacetone peroxide
H: nitrate ion
D: nitrite ion
E: chloranion
As the clear expression of table 6, the embodiment 16 to 22 that chemical conversion treatment solution contains organo-peroxide and tensio-active agent (wherein, chemical conversion treatment solution contains organo-peroxide and tensio-active agent) in, the metal material surface that is polluted by oily matter is cleaned, and is formed uniformly fine and close zinc phosphate chemical conversion layer on clean Surface.
In the Comparative Examples 10, because do not use tensio-active agent, and replace organo-peroxide, so surface of cold-rolled steel plate does not form chemical conversion layer with inorganic oxidizer.
(wherein, replace in the organo-peroxide with inorganic oxidizer, the fineness of the coated crystal that galvanized steel sheet surface forms is unsatisfactory in Comparative Examples 11.
In Comparative Examples 12 (wherein, without oxygenant), the fineness of gained coated crystal and the chemical conversion layer coverage on surface of cold-rolled steel plate is unsatisfactory.
In Comparative Examples 13 (wherein, replacing the organo-peroxide composition with inorganic oxidizer), the fineness of gained coated crystal is unsatisfactory, and the coverage of chemical conversion layer on galvanized steel sheet surface is not too satisfactory.
In Comparative Examples 14 (wherein, replacing organic peroxide compounds), on the aluminium-magnesium alloy steel plate, do not form chemical conversion layer with inorganic oxidizer.
Claims (15)
1. aqueous zinc phosphate chemical conversion treatment solution that is used for metallic substance, comprise: concentration is that the zine ion of 0.5-15 grams per liter and phosphate anion that concentration is the 5.0-30.0 grams per liter are formed as main, and the chemical conversion promotor that contains at least a organo-peroxide of 50-1500ppm.
2. according to the aqueous zinc phosphate chemical conversion treatment solution of claim 1, wherein nitrogenous compound and ionic total content in nitrogen, are limited in 0-200ppm.
3. according to the aqueous zinc phosphate chemical conversion treatment solution of claim 1, organo-peroxide water soluble wherein, and oxide structure was arranged or cross carboxyl structure.
4. according to the aqueous zinc phosphate chemical conversion treatment solution of claim 1, wherein the content of chemical conversion promotor is 80-200ppm.
5. according to the aqueous zinc phosphate chemical conversion treatment solution of claim 1, wherein organo-peroxide is to be selected from that cross alcohol, uncle oneself is pure with excessivelying, diethyl superoxide, ditertiary butyl peroxide, acetylacetone peroxide, cumene hydroperoxide, t-butylperoxy toxilic acid by ethyl hydroperoxide, different third pure excessively, uncle's fourth, peracetic acid, single peroxide phthalic acid and mistake succsinic acid composition one group.
6. according to the aqueous zinc phosphate chemical conversion treatment solution of claim 1, it also comprises tensio-active agent.
7. the method for metallic substance is handled in a zinc phosphate chemical conversion, comprise: make to comprise that concentration is that the zine ion of 0.5-15 grams per liter and phosphate anion that concentration is the 5.0-30.0 grams per liter are as main ingredient, and the aqueous treatment that 50-1500ppm contains the chemical conversion promotor of at least a organo-peroxide contacts with the surface of metallic substance, to form the zinc phosphate chemical conversion layer at metal material surface.
8. according to the method for claim 7, wherein nitrogenous compound and ionic total content are limited in 0-200ppm in the aqueous treatment.
9. according to the method for claim 7, organo-peroxide water soluble wherein, and oxide structure was arranged or cross carboxyl structure.
10. according to the method for claim 7, wherein the content of chemical conversion promotor in chemical conversion treatment solution is 80-200ppm.
11. according to the method for claim 7, wherein the pH value of moisture chemical conversion treatment solution is 2.0-4.0.
12. according to the method for claim 7, wherein the temperature of moisture chemical conversion treatment solution is 25-50 ℃.
13., wherein before chemical conversion is handled, metallic substance is carried out surface cleaning according to the method for claim 7.
14. according to the method for claim 7, wherein aqueous treatment also comprises tensio-active agent, and metal material surface cleaned simultaneously with chemical conversion applies.
15. according to the method for claim 13, wherein the content of tensio-active agent in aqueous treatment is the 0.5-5 grams per liter.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP302289/94 | 1994-12-06 | ||
| JP30228994 | 1994-12-06 | ||
| JP4760595 | 1995-03-07 | ||
| JP47605/95 | 1995-03-07 | ||
| JP47195/95 | 1995-03-07 | ||
| JP4719595 | 1995-03-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1132268A CN1132268A (en) | 1996-10-02 |
| CN1093891C true CN1093891C (en) | 2002-11-06 |
Family
ID=27292906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95120534A Expired - Fee Related CN1093891C (en) | 1994-12-06 | 1995-12-06 | Aqueous zinc phosphate chemical conversion treatment liquid and process |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR960023240A (en) |
| CN (1) | CN1093891C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4233565B2 (en) * | 2002-07-10 | 2009-03-04 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for coating a metal surface |
| CN101824614B (en) * | 2010-04-15 | 2012-08-08 | 吉林大学 | Magnesium alloy surface conversion coating treating fluid and treating process thereof |
| CN102719819B (en) * | 2011-03-30 | 2014-10-29 | 重庆市荣时金属表面处理剂有限公司 | General phosphating agent |
| CN102719874A (en) * | 2011-03-30 | 2012-10-10 | 重庆市荣时金属表面处理剂有限公司 | Cathode electrophoretic phosphatizing agent |
| CN109487260B (en) * | 2018-12-28 | 2021-01-12 | 湖北博新材料保护有限公司 | Liquid surface conditioning agent and preparation method thereof |
| CN110747452A (en) * | 2019-12-12 | 2020-02-04 | 汉德车桥(株洲)齿轮有限公司 | Phosphorization method for precision forging gear |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2471908A (en) * | 1948-04-08 | 1949-05-31 | American Chem Paint Co | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| US5312492A (en) * | 1989-04-21 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | Process not using chlorate or nitrite for the production of nickel and manganese containing zinc phosphate films |
-
1995
- 1995-12-06 CN CN95120534A patent/CN1093891C/en not_active Expired - Fee Related
- 1995-12-06 KR KR1019950047005A patent/KR960023240A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2471908A (en) * | 1948-04-08 | 1949-05-31 | American Chem Paint Co | Method of and material for preparing surfaces of ferriferous metals for the reception of a siccative finishing coat |
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| US5312492A (en) * | 1989-04-21 | 1994-05-17 | Henkel Kommanditgesellschaft Auf Aktien | Process not using chlorate or nitrite for the production of nickel and manganese containing zinc phosphate films |
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| Publication number | Publication date |
|---|---|
| KR960023240A (en) | 1996-07-18 |
| CN1132268A (en) | 1996-10-02 |
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