CN1197849A - Metallic surface pretreating liquid and method before formation and treatment of phosphate coating - Google Patents
Metallic surface pretreating liquid and method before formation and treatment of phosphate coating Download PDFInfo
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- CN1197849A CN1197849A CN98105466A CN98105466A CN1197849A CN 1197849 A CN1197849 A CN 1197849A CN 98105466 A CN98105466 A CN 98105466A CN 98105466 A CN98105466 A CN 98105466A CN 1197849 A CN1197849 A CN 1197849A
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- metallic surface
- pretreatment fluid
- phosphate coating
- phosphate
- divalence
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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
- C23C22/78—Pretreatment of the material to be coated
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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
Abstract
Provided is a pretreating liquid and pretreatment method for accelerating chemical reaction and making phosphate film crystals finer in phosphate film chemical conversion treatment of metallic materials. This pretreating liquid is characterized in that, containsmore than one kinds selected from phosphate contg. at least one kind among bivalent or tervalent metals including particles having a grain size of less than 5mu m and alkaline metal salts or ammonium salts or their mixtures and is adjusted in its pH to 4 to 13. The pretreatment method may be executed by previously bringing the metallic surfaces into contact with the pretreating liquid.
Description
The present invention forms in the processing about implement phosphate coating in metallic surfaces such as steel, steel plate galvanized and aluminium, before it is handled, in order to promote chemical reaction and phosphate coating crystalline miniaturization employed metallic surface pretreatment fluid and pretreatment process.
Recently, form with the phosphate coating of metal sheet at automobile and to handle, require to form in order to improve solidity to corrosion or the friction when reducing punching press after covering with paint, lacquer, colour wash, etc. and to prolong the phosphate coating that is fine and compact crystal in punching die life-span.So, for making the metallic surface activation, forming the nuclear that phosphate crystal is separated out usefulness, finally obtain the phosphate coating of fine and compact crystal, before the phosphate coating of being everlasting forms treatment process, adopt surface preparation.Following example forms operation for the general phosphate coating that phosphate coating carried out that obtains fine and compact crystal.
(1) degreasing
(2) washing (multistage)
(3) surface preparation
(4) phosphate coating forms and handles
(5) washing (multistage)
(6) wash with pure water
Surface preparation is used to make phosphate crystal fine and fine and close.Become separatory about this pre-treatment, for example be well known that by United States Patent (USP) No. 2874081, No. 2322349 and No. 2310239 etc., open with titanium, pyrophosphate ion, ortho-phosphoric acid ion and sodium ion etc. as main constituent.Above-mentioned pre-treatment becomes separatory to be called as " with Rostand (Jansted) salt, and to contain titanium ion and titanium colloid in its aqueous solution.The metal that has carried out degreasing, washing becomes in the aqueous solution of separatory dipping or metal is sprayed pretreatment fluid in aforementioned pre-treatment, makes metallic surface absorption titanium colloid thus.Adsorbed titanium colloid forms in the treatment process at the phosphate coating of subsequent processing, becomes the nuclear that the phosphate coating crystallization is separated out, and can promote reaction and make phosphate crystal miniaturization, densification.The pre-treatment of present industrial use becomes separatory all to utilize Rostand salt.Yet, when use contains by the titanium colloidal pretreatment fluid that Rostand salt is constituted, have following problem.
First problem is, pretreatment fluid through the time worsen.Previous pretreatment fluid is brought into play significant effect making in the short period of time of the aqueous solution miniaturization and the densification for phosphate crystal.But, to make behind the aqueous solution through a few days, the aggegation of titanium colloid causes having or not use all to lose effect no matter therebetween, makes the phosphate crystal that is obtained become thick.So the spy opens clear 63-76883 communique and proposes following method, in preprocessing process, measure titanium colloidal median size, and discarded continuously part pretreatment fluid, make median size under certain value, replenish with waste part simultaneously and divide suitable pretreatment fluid, keep pretreating effect with this.Yet,, must discard pretreatment fluid for keeping effect though this method can quantitatively be controlled for the factor of pretreatment fluid effect.Therefore, this method must be discarded a large amount of pretreatment fluids.Thereby, be actually and keep its effect, adopt continuously discarded pretreatment fluid simultaneously and upgrade whole amounts.
Second problem be, during because of the preparation pretreatment fluid employed water quality so, its effect and life-span are influenced very big.When forming the pre-treatment bath of liquid, use process water usually.But, well-known, contain cation constituents such as calcium, magnesium in the process water, its content is difference according to the water source of the process water that uses.On the other hand, known pretreatment fluid principal constituent titanium colloid has the electric charge of anionic property in the aqueous solution, is not precipitated and is disperseed by the event of its electric exclusion power.
If have cation constituent calcium and magnesium in a large number in the process water, then the titanium colloid is by the cation constituent charge neutrality, and loses repulsive force, causes coagulation sedimentation, thereby loses its effect.So the someone proposes,, in pretreatment fluid, add condensed phosphates such as pyrophosphate salt for shielding cation constituent, keeping titanium colloidal stability.But, when in pretreatment fluid, adding a large amount of condensed phosphate, then, form in the treatment process the bad drawback of formation of generation phosphate coating at the phosphate coating that is carried out thereafter because of condensed phosphoric acid and surface of steel plate reaction form the inertia tunicle.In addition, the many areas of magnesium and calcium contents then must use pure water to set up the pre-treatment bath of liquid in water, and are totally unfavorable economically.
The 3rd problem be, in the working conditions, and the restriction of temperature, pH.Particularly, in the scope of temperature more than 35 ℃, beyond pH8.0～9.5, the aggegation of titanium colloid can't be brought into play effects of pretreatment.Therefore, must be in narrow temperature range, use in the narrow pH scope, and can not become the same solution of feasible usefulness such as adding grease-removing agent in the separatory to bring into play the purification and the activation effect of metallic surface for a long time in pre-treatment.
The 4th problem is that because of the event of pretreatment fluid, the miniaturization of the formed phosphate crystal of subsequent processing has a limit.Effects of pretreatment is adsorbed to the metallic surface and forms phosphate crystal the nuclear when separating out by the titanium colloid and reaches.Therefore, many more as if the titanium colloid quantity that is adsorbed to the metallic surface in the preprocessing process, then can obtain fine and fine and close phosphate crystal the more.For this reason, consideration improves the titanium colloid concentration in the pretreatment fluid.But if concentration increases, then the frequency to each other of the titanium colloid in the pretreatment fluid increases, and by collision titanium colloidal coagulation sedimentation takes place.The upper limit of present employed titanium colloid concentration is calculated as below the 100ppm with the titanium pattern, in the prior art, the titanium colloid concentration can't be increased to and make phosphate coating crystallization miniaturization more than this value.
So, the spy opens clear 56～No. 156778 communiques and the spy opens in the clear 57-23066 communique, disclose conduct with the pretreatment fluid beyond the Rostand salt, the suspension that will contain divalence or trivalent metal insoluble phosphate is depressed the pretreatment process of spraying plating to steel strip surface in adding.But this pre-treatment is because need suspension spraying plating to object being treated can be brought into play its effect adding to depress, so handle the phosphate coating of implementing through dipping and spraying and form use in the pretreatment process of handling common.
In addition, in the public clear 40-1095 communique of spy, disclose steel plate galvanized and impregnated in pretreatment process in high density divalence or the trivalent insoluble phosphate suspension.But the embodiment shown in this method only limits to steel plate galvanized, and in order to obtain pretreating effect, must use the insoluble phosphate suspension of the above high density of minimum 30g/L.
Therefore, although propose various shortcomings, up to now, the innovative techniques that can replace it is not arranged yet by industrialization with Rostand salt.
The objective of the invention is to, solve the aforementioned problems of prior art, be provided at phosphate coating and form in the processing in order to promote chemical reaction and to make the crystallization miniaturization of gained phosphate coating, pretreatment fluid and pretreatment process the ageing stability excellence, novel.
Present inventors etc. attentively study for the means that solve aforementioned problems, have solved the problem points of previous method, and have finished the pretreatment fluid and the pretreatment process of the novelty that the crystalline quality that can make phosphate coating more improves.Promptly, the characteristic that phosphate coating of the present invention forms the metallic surface pretreatment fluid before handling is: containing more than one, to be selected from divalent metal phosphoric acid salt and particle diameter be that the following particle of 5 μ m and trivalent metal phosphoric acid salt and particle diameter are particle and the alkali metal salts or ammonium salt or their mixture of the following particle of 5 μ m, and pH is adjusted to 4～13.
Aforementioned particle size is that the following particle concentration of 5 μ m is 0.001～30g/L, and aforementioned divalence or trivalent metal are preferably and are selected from least a of Zn, Fe, Mn, Ni, Co, Ca and Al.Aforementioned alkali metal salts or ammonium salt is preferably and is selected from orthophosphoric acid salt, metaphosphate, ortho-silicate, silicate, carbonate, hydrocarbonate and boratory at least a above salt, and its concentration is preferably 0.5～20g/L.And preferably contain the material of water soluble organic polymer, anionic surfactant and the nonionic surfactant of the water soluble organic polymer that is selected from the charged and dispersive oxide microparticle of anionic property, anionic property more than at least a, nonionic.Charged and the median size dispersive oxide microparticle of aforementioned anionic property is below the 0.5 μ m, and its concentration is preferable with 0.001～5g/L.Charged and the dispersive oxide microparticle of preferred aforementioned anionic property is to be selected from least a in Si, B, Ti, Zr, Al, Sb, Mg, Se, Zn, Sn, Fe, Mo and the V oxide compound.
The metal pretreatment methods that phosphate coating of the present invention forms before handling is characterised in that: this metallic surface is contacted with aforesaid pretreatment fluid.
In addition, because stability and stability high temperature under of pretreatment fluid of the present invention under high pH zone is more more excellent than previous product, so by adding nonionic surfactant or anionic surfactant or its mixture and washing assistant, possess purification and the activatory effect of carrying out the metallic surface simultaneously, can be used in the pretreatment process before phosphate coating forms processing.
Describe the effect of each composition among the present invention in detail.
The phosphoric acid salt of divalent metal, the phosphoric acid salt of trivalent metal are the necessary composition of pretreatment fluid of the present invention.In these metal phosphates of the present invention, comprise for example Zn
3(PO
4)
2Deng phosphoric acid salt that contains a kind of metal and for example Zn
2Fe (PO
4)
2Deng phosphoric acid salt that contains metal more than two kinds etc.Below only summary be " phosphoric acid salt of divalence or trivalent metal ".Purpose of the present invention is used for the metallic surface activation before being to provide phosphate coating to form to handle and forms the pretreatment fluid that the nuclear of usefulness is separated out in the phosphate coating crystallization as described above.The phosphoric acid salt that present inventor etc. have invented the divalence of certain concentration, particle diameter or trivalent metal is adsorbed to the surface of object being treated in containing the aqueous solution of certain additive, and become the nuclear when thereafter phosphate coating forms phosphate coating crystallization in handling and separates out, and improve the method for the speed of response that forms phosphate coating.
Simultaneously, because bath is handled in the phosphoric acid salt of divalence or trivalent metal and the formation of phosphate coating and phosphate coating is similar composition, so its advantage has: also can not cause detrimentally affect to this processing bath even put into the formation processing bath of phosphate coating, in addition, also wrapped into and can not caused detrimentally affect even in phosphate coating, become nuclear the performance of formed phosphate coating.The phosphoric acid salt of divalence used in the present invention or trivalent metal can be listed below example.Zn
3(PO
4)
2, Zn
2Fe (PO
4)
2, Zn
2Ni (PO
4)
2, Ni
3(PO
4)
2, Zn
2Mn (PO
4)
2, Mn
3(PO
4)
2, Mn
2Fe (PO
4)
2, Ca
3(PO
4)
2, Zn
2Ca (PO
4)
2, FePO
4, AlPO
4, CoPO
4And Co
3(PO
4)
2
Again, be known that, the crystallization number of the unit surface that initial reaction stage is separated out the more, then the formed phosphate coating crystalline in metallic surface particle diameter becomes finer.This be because, the phosphate coating crystalline is grown up that crystallization in adjacency contacts with each other and is finished during covered with the metallic surface, thus if the crystallization number that initial reaction stage is separated out diminishes in abutting connection with knot intergranular distance at most, and can the short period of time in the fine crystallization of metallic surface covering.Therefore, separate out in order to make fine phosphate crystal in the short period of time, it is that effectively for this reason, the material particle diameter that becomes nuclear is comparatively favourable with little person that many nuclei of crystallization are arranged before phosphate coating forms processing.Again, stably disperse in the aqueous solution in order also to make insoluble substance, the phosphoric acid salt particle diameter of wishing divalence used in the present invention or trivalent metal is below the 5 μ m.Even but the divalence of the above particle diameter of 5 μ m or the phosphoric acid salt of trivalent metal exist in pretreatment fluid of the present invention, also can not have any impact, can bring into play its significant effect when the following micropartical of 5 μ m in the pretreatment fluid reaches certain concentration effect of the present invention.
Again, among the present invention, through the phosphoric acid salt particle diameter of control divalence or trivalent metal, i.e. the phosphate coating crystalline particle diameter of may command gained.The divalence through using fine pulverizing or the phosphoric acid salt of trivalent metal can make atomic thin phosphate crystal separate out based on aforementioned reason.
The reactive phosphate ionic weight that the speed of response of phosphate coating formation reaction can arrive object being treated surface (metallic surface) by the unit time is determined, and is observed Fu Shi (Fick) rule.
d
n: the reactive phosphate ionic weight that can arrive the metallic surface
D: spread coefficient
O: metallic surface is long-pending
C
A: the reactive phosphate ionic concn in the bath
C
B: the reactive phosphate ionic concn of metallic surface
S: the thickness of adhesive layer
In the formula (1), dn is bigger, and the speed of response that then forms phosphate coating becomes big.For the dn that makes formula (1) becomes big, be the reactive phosphate ionic concn C that considers to make in the phosphate coating formation liquid
ABecome big.But, C
AExcessive, hydrolysis then takes place, the problem of slurry increase, and the problem of the overgrowth of crystals of phosphate coating thus.
If use pretreatment fluid of the present invention, then can not make C
AUnder excessive, the speed of response that order forms phosphate coating significantly becomes greatly.On the metallic surface with pretreatment fluid processing of the present invention, the phosphate particle of divalence or trivalent metal is adsorbed.The particle that is adsorbed is because of the little event of pH of phosphate coating formation liquid, and some dissolves on the metallic surface in phosphate coating formation liquid.Through dissolving thus, it is big that dn significantly becomes.
As a result, use in the situation of pretreatment fluid of the present invention, it is big that the formation speed of phosphate coating significantly becomes.Among the present invention, needn't make the C that forms phosphate coating
AExcessive.Therefore, rare slurry during phosphate coating forms and bathes, and can prevent thickization of phosphate coating crystalline., in the pretreatment fluid of the present invention, the phosphate particle composition of divalence or trivalent metal and the composition of phosphate coating are similar, and the effect that pretreatment fluid then of the present invention promotes phosphate coating to form is bigger.
For improving the speed that forms phosphate coating, the phosphatic particle concentration of divalence or trivalent metal is preferable with 0.001～30g/L.In the situation less than 0.001g/L, because the amount of adsorbed divalence in metallic surface or trivalent metal phosphorus particle is few, so do not promoted on the contrary.On the other hand, even greater than 30g/L, also do not have again and to promote to form the more effect of polyphosphate tunicle, only for being unfavorable for economy.
Secondly, enumerate must composition as the present invention alkali metal salts or ammonium salt or its mixture (below, singly be called " alkali metal salts or ammonium salt ").As shown in prior art, the past attempts depressing spraying plating and carrying out pretreated method in adding with the insoluble phosphate of divalence or trivalent metal.But the method in past all the time must be in adding the insoluble phosphate of depressing spraying plating divalence or trivalent metal.In adding the spraying plating reason of depressing be,, insoluble phosphate must be beaten to the metallic surface to make its reaction in order to bring into play effects of pretreatment, perhaps must as the emission sandblast as the metallic surface is injured.Again, in order to obtain effects of pretreatment via dip treating, previous method must make the insoluble phosphate concentration of divalence or trivalent metal extremely improve.
Even present inventor etc. have invented under the low situation of the phosphate concn of alkali metal salts or ammonium salt existence and divalence or trivalent metal, and effects of pretreatment also can be brought into play in the metallic surface not in addition in the dip treating of physical property strength in the metallic surface.Therefore, the present invention only makes pretreatment fluid contact object being treated get final product, and is and the diverse reaction mechanism of prior art.For this reason, must be with alkali metal salts or ammonium salt as necessary composition.
If alkali metal salts or ammonium salt is selected from orthophosphoric acid salt, metaphosphate, ortho-silicate, silicate, carbonate, hydrocarbonate and borate, then be not particularly limited.The combination of this type of alkali metal salts or ammonium salt is used more than two kinds also do not had any problem again.
The concentration expectation of alkali metal salts or ammonium salt is 0.5～20g/L.Concentration when then only making object being treated contact pretreatment fluid, is not brought into play pretreating effect less than 0.5g/L, more than 20g/L, then also can't expect better effect, only for being unfavorable for economy.
Pretreatment fluid of the present invention must be adjusted to the scope of pH4～13.In less than pH4 the time,, and cause that probably the formation of phosphate coating is bad then because of oxide film takes place in the metallic corrosion that is caused in the pretreatment fluid.Again, for surpassing in 13 the situation,, form and handle when bathing, phosphate coating is formed handle to bathe to be neutralized, and probably the balance of order bath is collapsed so pretreatment fluid is taken in phosphate coating then because of phosphate coating forms treating water solution for being acid in pH.
Among the present invention, preferably add the charged and dispersive oxide microparticle of anionic property.The below effect of explanation oxide microparticle.
The first, oxide microparticle is adsorbed to the metallic surface, becomes the nuclear that phosphate crystal is separated out, and promptly becomes micro anode (micro cathode), becomes the starting point that phosphate coating forms reaction.
The second, make the phosphatic dispersion stabilization of divalence in the pretreatment fluid or trivalent metal improve.Oxide microparticle is adsorbed on the phosphoric acid salt of institute's dispersive divalence in the pretreatment fluid or trivalent metal, perhaps stops the phosphoric acid salt of divalence or trivalent metal to collide to each other, prevents the phosphoric acid salt coagulation sedimentation of divalence or trivalent metal thus and improves stability.Therefore, the particle diameter of oxide microparticle must be littler than the phosphatic particle diameter of divalence or trivalent metal.
Particularly, being preferable below the 0.5 μ m.Oxide microparticle used in the present invention is if satisfy the requirement of particle diameter and anionic property, and then the metal for oxide microparticle is unrestricted.Oxide microparticle for cationic is implemented surface treatment, and it is also harmless to make its surface charge be transformed into anionic property with this.If the example of oxide microparticle used in the present invention is shown, then as following.SiO
2, B
2O
3, TiO
2, ZrO
2, Al
2O
3, Sb
2O
5, MgO, SeO
2, ZnO, SnO
2, Fe
2O
3, MoO
3, Mo
2O
5, V
2O
5In addition, the effect of the phosphoric acid salt dispersion stabilization of the divalence of raising pretreatment fluid or trivalent metal among the present invention also can be reached by water soluble organic polymer, anionic surfactant and the nonionic surfactant etc. of the water soluble organic polymer that uses anionic property, nonionic.
Charged and the concentration dispersive oxide microparticle of anionic property is preferably 0.001～5g/L.
Less than 0.001g/L, then can't make the phosphatic dispersion stabilization of divalence in the pretreatment fluid of the present invention or trivalent metal improve.Become big even add the effect that also can't make the phosphatic dispersion stabilization that improves divalence or trivalent metal more than the 5g/L again.
Pretreatment fluid of the present invention is under the environment for use of the broadness different with previous method, can continue its effect.That is, compare, have following advantage with previous method.
(1) ageing stability height.
(2) also can not weaken effect even sneak into hardness components such as Ca, Mg.
(3) can use down in high temperature.
(4) can add various an alkali metal salts.
(5) stability under the pH zone is high widely in amplitude.
(6) particle diameter of the phosphate crystal of may command gained.
Therefore, also can be used as previous the pretreatment fluid that has degreasing concurrently that can't continue to keep stabilizing quality.At this moment, in order to improve the clearing power in the pretreatment process that has degreasing concurrently, also can add known inorganic alkaline washing assistant, organic washing-assisting detergent and tensio-active agent etc.Again, the influence that the cation constituent of bringing in order to eliminate in the pretreatment fluid etc. is caused also can be added known sequestrant, condensed phosphate etc.
Again, pre-treatment of the present invention only makes pretreatment fluid contact with the metallic surface and gets final product, and there is no big restriction for temperature of duration of contact, pretreatment fluid etc.Moreover pre-treatment of the present invention is implemented phosphatizing to iron steel, steel plate galvanized, aluminum or aluminum alloy etc., can be applicable to various metals.
[embodiment]
Below, use embodiment and comparative example to describe the effect of pretreatment fluid of the present invention in detail.But, be treated to example though form with the zinc phosphate tunicle of metal sheet with automobile, be not in order to limit the purposes of pretreatment fluid of the present invention.Embodiment and comparative example employed abbreviation and its implication for the examination metal sheet are shown below (for test plate (panel)).
SPC (the cold steel plate that prolongs: JIS-G-3141)
EG (two sides electrogalvanizing steel plate: plating amount 20g/m
2)
GA (two sides alloy galvanized steel plate: plating amount 45g/m
2)
Zn-Ni (two sides electro-galvanizing nickel steel plate: plating amount 20g/m
2)
Al (aluminium sheet: JIS-5052) (alkaline degreasing fluid)
Embodiment, comparative example all are diluted to 2% for using with Fine Cleaner L4460 (registered trademark: Japanese PERCARIZING (strain) system) with tap water.(pretreatment fluid)
Table 1 illustrates the composition of the employed pretreatment fluid of embodiment, and table 2 illustrates the composition of the employed pretreatment fluid of comparative example.In addition, test of time is implemented after making pretreatment fluid immediately, and in the empty warm 1 week back enforcement of placing down.Embodiment 1
With Zn
3(PO
4)
24H
2O uses the ball mill of zirconium white grain to pulverize 10 minutes, as the phosphoric acid salt of divalence or trivalent metal.After the phosphoric acid salt of this divalence or trivalent metal is made suspension, with the filter paper filtering of 5 μ m, and with the Submicron particle analyzer (the CoalterN4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.After in the liquid of this adjustment concentration, adding tertiary sodium phosphate, make the pretreatment fluid shown in the table 1 that pH is a designated value as an alkali metal salt.Embodiment 2
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.After the phosphoric acid salt of this divalence or trivalent metal is made suspension, it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer with the filter paper of 5 μ m.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system), and after the tertiary sodium phosphate reagent as an alkali metal salt, make the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 3
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 1 minute with mortar, as the phosphoric acid salt of divalence or trivalent metal.After the phosphoric acid salt of this divalence or trivalent metal makes suspension, it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 4.2 μ m with the Submicron particle analyzer with the filter paper of 5 μ m.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 4
With Zn
3(PO
4)
24H
2The O reagent uses the ball mill of zirconium white grain to break into pieces 1 hour, as the phosphoric acid salt of divalence or trivalent metal.After the phosphoric acid salt of this divalence or trivalent metal makes suspension, it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.09 μ m with the Submicron particle analyzer with the filter paper of 5 μ m.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 5
In heating to 1 liter of 50 ℃ 0.5M ferric sulfate (II) solution, with 100 milliliters of the disodium-hydrogen solution of 100 milliliters of the solution of zinc sulfate of 1M and 1M mutual add to make produce precipitation.After will containing the sedimentary aqueous solution and making the precipitation particles slaking in 1 hour, heavily cover 10 times and tilt to clean in heating under 90 ℃.The throw out universe that filters gained is dry and analyzed with X-ray diffraction, and throw out is the Phosphofirite[Zn that contains part phosphoric acid three-iron as a result
2Fe (PO
4)
24H
2O].This Phosphofirite was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.29 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system), and after the tertiary sodium phosphate reagent as an alkali metal salt, make the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 6
In heating to 1 liter of 50 ℃ 0.1M manganese nitrate solution, add 200 milliliters of the zinc nitrate solutions of 1M, and add 200 milliliters of the sodium hydrogen phosphate solution of 1M again, the order precipitation produces.To contain the sedimentary aqueous solution and under 90 ℃, heat and made the precipitation particles slaking in 1 hour, and heavily cover 10 times and tilt to clean.The partly precipitated thing that filters gained is dissolved in hydrochloric acid, and uses atomic absorption spectrum analysing arrangement that composition is analyzed, throw out is [Zn as a result
xMn
y(PO
4)
2].With this [Zn
xMn
y(PO
4)
2] broke into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension, with the filter paper of 5 μ m it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.32 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system), and after the tertiary sodium phosphate reagent as an alkali metal salt, make the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 7
In heating to 1 liter of 50 ℃ 0.1M ca nitrate soln, add 200 milliliters of the zinc nitrate solutions of 1M, and add 200 milliliters of the sodium hydrogen phosphate solution of 1M again, the order precipitation produces.To contain the sedimentary aqueous solution and under 90 ℃, heat and made the precipitation particles slaking in 1 hour, and heavily cover 10 times and tilt to clean.The throw out universe that filters gained is dry and analyzed with X-ray diffraction, and throw out is Shortite[Zn as a result
2Ca (PO
4)
24H
2O.This Shortite was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.30 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 8
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 0.02g/L again.In the liquid of this adjustment concentration, add ZrO as oxide microparticle
2Colloidal sol (NZS-30B: daily output chemical industry (strain) system), reach tertiary sodium phosphate reagent, make the pretreatment fluid shown in the table 1 that pH is a designated value as an alkali metal salt.Embodiment 9
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension Hou, with the filter paper of 5 μ m it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 30g/L again.In the liquid of this adjustment concentration, add Sb as oxide microparticle
2O
5Colloidal sol (A-1530: daily output chemical industry (strain) system), reach tertiary sodium phosphate reagent, make the pretreatment fluid shown in the table 1 that pH is a designated value as an alkali metal salt.Embodiment 10
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches water glass reagent Hou as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 11
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the concentrated crystal soda reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 12
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension Hou, with the filter paper of 5 μ m it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 13
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal filters it with the filter paper of 5 μ m after making suspension, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Embodiment 14
Use is same as the pretreatment fluid of embodiment 2, carries out preprocessing process under 40 ℃ of temperature.Embodiment 15
In the pretreatment fluid of embodiment 14, add 2g/L tensio-active agent (polyoxyethylene nonylphenyl ether: the EO11 mole), and under 40 ℃ of temperature, do not supplied test piece by oiled, have the preprocessing process of degreasing concurrently for carrying out remaining unchanged of degreasing.Embodiment 16
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphate concn of this divalence or trivalent metal is adjusted into 2g/L.Particle diameter in the suspension with the Submicron particle analyzer (Coalter N4 type: Coalter company) and Coalter counter (Coalter company) measure, the result contains 20% 6.5 μ m particles in the crest that 0.31 μ m and 6.5 μ m have size-grade distribution.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 1 that pH is a designated value.Comparative example 1
With previous pretreatment fluid Preparene ZN (registered trademark: Japanese PERCARIZING (strain) system) aqueous solution, under standard conditions, carry out preprocessing process.Comparative example 2
In the previous pretreatment fluid Preparene ZN aqueous solution, adding as shown in table 2 is as the SiO of oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) also carries out preprocessing process.Comparative example 3
The pH of the previous pretreatment fluid Preparene ZN aqueous solution is adjusted to the value shown in the table 2, and carries out preprocessing process.Comparative example 4
The pH of the previous pretreatment fluid Preaparene ZN aqueous solution is adjusted to the value shown in the table 2, and carries out preprocessing process.Comparative example 5
The treatment temp of the previous pretreatment fluid Preparene ZN aqueous solution is made 40 ℃, and carry out preprocessing process.Comparative example 6
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension Hou, with the filter paper of 5 μ m it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) makes the pretreatment fluid shown in the table 2 that pH is a designated value.Comparative example 7
With Zn
3(PO
4)
24H
2The O reagent is as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension, is scattered in once again with the filter paper filtering of 5 μ m and the particle that filter paper is residual to make suspension in the water.With the median size of the particle in Coalter counter (Coalter company) the mensuration suspension, the result is 6.5 μ m.Secondly the phosphate concn with divalence in the suspension or trivalent metal is adjusted into 2g/L.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system), and after the tertiary sodium phosphate reagent as an alkali metal salt, make the pretreatment fluid shown in the table 2 that pH is a designated value.Comparative example 8
With Zn
3(PO
4)
24H
2The O reagent was broken into pieces 10 minutes with the ball mill that uses the zirconium white grain, as the phosphoric acid salt of divalence or trivalent metal.The phosphoric acid salt of this divalence or trivalent metal is in making suspension Hou, with the filter paper of 5 μ m it is filtered, and (Coalter N4 type: measure the median size of particle in the filtrate Coalter company), the result is 0.31 μ m with the Submicron particle analyzer.Phosphate concn with divalence in the filtrate or trivalent metal is adjusted into 2g/L again.In the liquid of this adjustment concentration, add SiO as oxide microparticle
2(AEROSIL #300: Japanese AEROSIL (strain) system) reaches the tertiary sodium phosphate reagent as an alkali metal salt, makes the pretreatment fluid shown in the table 2 that pH is a designated value.(the zinc phosphate tunicle forms treatment solution)
Embodiment, comparative example all are diluted to 4.8% with Palbond L3020 (registered trademark: Japanese PERCARIZING (strain) system) with tap water, and constituent concentration, full acidity, free acidity, promoter concentration be adjusted at present as automobile with the zinc phosphate tunicle of metal sheet form handle in the general concentration of using of institute, for use.Treatment process below is shown.20 seconds (4) zinc phosphate tunicles of 30 seconds (3) surface preparation room temperatures of 42 ℃ of (treatment process) (1) alkali degreasings, spraying 120 seconds (2) washing room temperature, spraying, dipping form and handled 30 seconds (6) deionized water chamber wash temperature of 42 ℃, dipping (5) washing in 120 seconds room temperature, spraying, spraying 30 seconds (form the covering with paint behind the zinc phosphate tunicle and estimate operation)
All (Elecuron 2000: Northwest PAINT corporate system) cover with paint, lacquer, colour wash, etc. with thickness 20 μ m, and, after 25 minutes a part is supplied in salt spray testing and the test of salt tolerant warm water in 180 ℃ of following roastings with cation electrodeposition coating for embodiment, comparative example.Being coated with plaque by deposition (automobile inter coat coating: Northwest PAINT corporate system) covering with paint, lacquer, colour wash, etc. into inter coat, to cover with paint, lacquer, colour wash, etc. thickness be 40 μ m, and carry out roasting in 30 minutes under 140 ℃ with inter coat coating of residue.Again in inter coat cover with paint, lacquer, colour wash, etc. to end for test plate (panel), (automobile is used coated coating to above coated coating: Northwest PAINT corporate system) cover with paint, lacquer, colour wash, etc. to become to go up coating to cover with paint, lacquer, colour wash, etc. thickness be 40 μ m, and carry out roasting in 30 minutes under 140 ℃.With three paint sheets of the total film thickness 100 μ m of gained in an adherence evaluation test, the evaluation test of secondary adherence.(evaluation method of zinc phosphate tunicle) (1) outward appearance
With visual observation, confirm that the zinc phosphate tunicle has or not scale, spot.Be evaluated as following.
The even good surface appearance of ◎
Zero part has spot
△ has spot, scale
* scale is many * * do not form zinc phosphate tunicle (2) zinc phosphate tunicle weight (C.W.)
Measure to form plate weight behind the zinc phosphate tunicle (be W1[g]), secondly with stripping liquid, the stripping conditions of this plate shown in following, enforcement zinc phosphate tunicle lift-off processing measure its weight (be considered as W2[g]), and use formula (I) is calculated.The cold situation stripping liquid that prolongs steel plate: 5% chromic acid aqueous solution stripping conditions: the situation stripping liquid of galvanized sheet is peeled off in 75 ℃, 15 minutes, dipping: ammonium dichromate 2 weight %+28% ammoniacal liquor 49 weight %+ pure water 49 weight % stripping conditions: normal temperature, 15 minutes, dipping are peeled off
Tunicle weight [g/m
2The crystallite size (C.S.) of]=(W1-W2)/0.021 formula (I) (3) zinc phosphate tunicle
Formed zinc phosphate tunicle uses scanning electronic microscope (SEM) to observe the picture of 1500 times of amplifications, and investigates its crystallization particle diameter.(4) P ratio
Embodiment, comparative example use Phosphofirite crystalline X ray intensity (P) and Hopaite crystalline X ray intensity (H) in the X-ray diffraction device mensuration zinc phosphate tunicle all only to the SPC steel plate.Use formula (II) to calculate the P ratio by the X ray intensity of gained.
P ratio=P/ (P+H) formula (II) (evaluation method of filming after the covering with paint)
Embodiment, comparative example are all implemented the evaluation of filming according to the evaluation method shown in following.(1) salt spray testing (JIS-Z-2371)
In carrying out on the plate that galvanic deposit covers with paint, lacquer, colour wash, etc. of incision crosscut, with 5% brine spray 960 hours.Measure get rusty amplitude and estimating of the one-sided maximum that begins by crosscut in the spraying back of ending.(2) salt tolerant warm water test
The plate that carries out the galvanic deposit covering with paint of incision crosscut was flooded 240 hours in 5% salt solution.Measure get rusty amplitude and estimating of the one-sided maximum that begins by crosscut in the dipping back of ending.(3) adherence evaluation tests
On three paint sheets, be cut into 100 at interval checkers of 2mm, and whole checkers covered with adhesive tape and bonding, then self adhesive tape is peeled off, and estimate the checker of the peeling off number of filming with sharp keen pocket knife.(4) secondary adherence evaluation test
Three paint sheets were flooded 240 hours in 40 ℃ deionized water and end according to the same program of an adherence evaluation test, implement the checker stripping test, and estimate the checker of the peeling off number of filming in dipping.
After using the pretreatment fluid of embodiment shown in the table 3, zinc phosphate handle gained phosphate coating by membrane property.
After using the pretreatment fluid of comparative example shown in the table 4, zinc phosphate handle gained phosphate coating by membrane property.
After using the pretreatment fluid of embodiment shown in the table 5, zinc phosphate handles the phosphate coating of gained, the performance evaluation result after the covering with paint when covering with paint, lacquer, colour wash, etc.
After using the pretreatment fluid of comparative example shown in the table 6, zinc phosphate handles the phosphorus phosphate coating of gained, the performance evaluation result after the covering with paint when covering with paint, lacquer, colour wash, etc.
Can confirm that by table 3 and table 4 pretreatment fluid of the present invention significantly improves previous pretreatment fluid shortcoming ageing stability.Can learn that by embodiment 1 and embodiment 2 oxide microparticle is for the effect of ageing stability again.Moreover, even change oxide microparticle and alkali-metal kind, treatment temp, also can not change its effect, can obtain and the equal above fine and close and fine crystallization of previous product, and by the phosphatic median size of employed divalence of control or trivalent metal, the also crystallite size of the phosphate coating of may command gained.
By table 5 and table 6 as can be known, use pretreatment fluid of the present invention, can give and use the equal above covering with paint performance of previous pretreatment fluid.[effect of invention]
As previously mentioned, the present invention can make previous product shortcoming ageing stability improve extraordinarily, and also can reach previous product impossible crystallite size of freely controlling phosphate coating.Therefore, the present invention than before product and can give with previous product performance more than equal in favourable economically.[table 1]
* the pretreatment fluid of embodiment 14 composition is identical with embodiment 2, and the essentially consist of the pretreatment fluid of 40 ℃ of material of treatment temp embodiment 15 is identical with embodiment 14 with treatment temp, adds the tensio-active agent (polyoxyethylene nonylphenol ether EO11mol) of 2g/L again.[table 2]
*The pretreatment fluid of comparative example 5 is formed identical with comparative example 1,40 ℃ of treatment temps.[table 3]
[table 4]
[table 5]
[table 6]
Claims (8)
1. a phosphate coating forms and handles preceding metallic surface pretreatment fluid, it is characterized in that it contains that to be selected from the phosphatic particle diameter of divalent metal be that following particle of 5 μ m and the phosphatic particle diameter of trivalent metal are that more than one particle diameter of the following particle of 5 μ m is the following particles of 5 μ m, and alkali metal salts or ammonium salt or its mixture, and pH is 4～13.
2. phosphate coating as claimed in claim 1 forms the metallic surface pretreatment fluid before handling, it is characterized in that the following particle content of particle diameter 5 μ m is 0.001～30g/L, and divalent metal or trivalent metal are more than one the metal that is selected among Zn, Fe, Mn, Ni, Co, Ca, the Al.
3. phosphate coating as claimed in claim 1 forms the metallic surface pretreatment fluid before handling, it is characterized in that alkali metal salts or ammonium salt is to be selected from orthophosphoric acid salt, metaphosphate, ortho-silicate, silicate, carbonate, hydrocarbonate, boratory more than one alkali metal salts or ammonium salt, and its concentration is 0.5～20g/L.
4. a phosphate coating forms the metallic surface pretreatment fluid before handling, and the pretreatment fluid that it is characterized in that claim 1 contains more than one materials that are selected from the charged and dispersive oxide particle of anionic property, anionic property water soluble organic polymer, nonionic water soluble organic polymer, anionic surfactant, nonionic surfactant again.
5. phosphate coating as claimed in claim 4 forms the metallic surface pretreatment fluid before handling, and it is characterized in that the charged and dispersive oxide particle of anionic property for below the flat footpath particle diameter 0.5 μ m, and its content is 0.001～5g/L.
6. phosphate coating as claimed in claim 4 forms the metallic surface pretreatment fluid before handling, and it is characterized in that the charged and dispersive oxide particle of anionic property is to be selected from the oxide compound of Si, B, Ti, Zr, Al, Sb, Mg, Se, Zn, Sn, Fe, Mo and V more than one.
7. a phosphate coating forms the metallic surface pretreatment process before handling, and it is characterized in that making in advance each pretreatment fluid of metallic surface and claim 1～6 to contact, to form phosphate coating on the metallic surface.
8. a phosphate coating forms and handles preceding metallic surface pretreatment process, it is characterized in that making in advance the metallic surface to contact, on the metallic surface, to merge the activation and the purification of the metallic surface that forms phosphate coating with the pretreatment fluid of one of claim 1～6 that contains nonionic surfactant or anionic surfactant or its mixture and washing assistant.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52181/97 | 1997-03-07 | ||
| JP52181/1997 | 1997-03-07 | ||
| JP05218197A JP3451334B2 (en) | 1997-03-07 | 1997-03-07 | Pretreatment liquid for surface conditioning before phosphate conversion treatment of metal and surface conditioning method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197849A true CN1197849A (en) | 1998-11-04 |
| CN1198958C CN1198958C (en) | 2005-04-27 |
Family
ID=12907647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981054668A Expired - Lifetime CN1198958C (en) | 1997-03-07 | 1998-03-09 | Metallic surface pretreating liquid and method before formation and treatment of phosphate coating |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0977908B1 (en) |
| JP (1) | JP3451334B2 (en) |
| KR (1) | KR100473603B1 (en) |
| CN (1) | CN1198958C (en) |
| AU (1) | AU6673698A (en) |
| CA (1) | CA2283387C (en) |
| DE (1) | DE69817803T2 (en) |
| ES (1) | ES2205456T3 (en) |
| ID (1) | ID20532A (en) |
| MY (1) | MY124633A (en) |
| TW (1) | TW371675B (en) |
| WO (1) | WO1998039498A1 (en) |
| ZA (1) | ZA981796B (en) |
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Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT429345A (en) | 1941-10-25 | 1900-01-01 | ||
| US2322349A (en) | 1941-10-25 | 1943-06-22 | Westinghouse Electric & Mfg Co | Corrosion resistant coating for metal surfaces |
| US2456947A (en) * | 1944-12-21 | 1948-12-21 | Westinghouse Electric Corp | Corrosion resistant coating for metal surfaces |
| US2874081A (en) | 1956-08-02 | 1959-02-17 | Parker Rust Proof Co | Pretreatment solution for phosphate coating, method of preparing the same and process of treating metal surfaces |
| GB1084017A (en) * | 1963-09-30 | 1967-09-20 | Jawata Iron & Steel Co Ltd | Pretreating process for phosphate-treating steel sheets or plated steel sheets |
| DE1521889B1 (en) * | 1966-11-30 | 1972-01-13 | Metallgesellschaft Ag | METHOD OF PHOSPHATING IRON AND STEEL |
| US3728163A (en) * | 1970-05-25 | 1973-04-17 | Balm Paints Ltd | Alkaline liquids for cleaning metals |
| US3847663A (en) * | 1970-07-24 | 1974-11-12 | Lubrizol Corp | Cleaning of metals with compositions containing alkali metal silicate and chloride |
| DE2207047A1 (en) * | 1972-02-15 | 1973-08-30 | Metallgesellschaft Ag | PROCESS FOR THE PREPARATION OF STEEL PIECES FOR CHIPLESS COLD FORMING |
| JPS50153736A (en) * | 1974-06-03 | 1975-12-11 | ||
| JPS5140342A (en) * | 1974-10-04 | 1976-04-05 | Nippon Packaging Kk | Tetsukonokaseishoriho |
| FR2375340A1 (en) | 1976-12-23 | 1978-07-21 | Produits Ind Cie Fse | Iron and steel activation pretreatment prior to phosphating - by treating with magnesium ortho:phosphate suspension allowing good coverage and finer phosphating coating |
| FR2461020A1 (en) * | 1979-07-06 | 1981-01-30 | Produits Ind Cie Fse | IMPROVEMENTS IN METHODS OF MANGANESE PHOSPHATION OF IRON AND STEEL SURFACES |
| JPS56156778A (en) * | 1980-05-02 | 1981-12-03 | Nippon Steel Corp | Manufacture of continuously annealed steel strip with superior suitability to phosphating and superior corrosion resistance after coating |
| JPS5723066A (en) * | 1980-07-17 | 1982-02-06 | Nippon Steel Corp | Preparation of box annealed steel plate with excellent phosphate treating property and corrosion resistance after painting |
| DE3307158A1 (en) * | 1983-03-01 | 1984-09-06 | Hilti Ag, Schaan | METHOD FOR ACTIVATING PHOSPHATE LAYER TRAINING ON METALS AND MEANS FOR CARRYING OUT SUCH METHODS |
| US4497667A (en) * | 1983-07-11 | 1985-02-05 | Amchem Products, Inc. | Pretreatment compositions for metals |
| JPS6039170A (en) * | 1983-08-10 | 1985-02-28 | Toyota Motor Corp | Method and aqueous solution for surface regulation of steel plate before phosphate coating conversion treatment |
| JPH0674507B2 (en) | 1986-09-19 | 1994-09-21 | 日本パ−カライジング株式会社 | Management method of surface conditioning liquid for phosphate coating chemical conversion treatment |
| FR2612947A1 (en) * | 1987-03-27 | 1988-09-30 | Siderurgie Fse Inst Rech | PROCESS FOR CHEMICAL SURFACE TREATMENT OF AN ALUMINOUS PRODUCT WITH A VIEW TO ITS PHOSPHATION |
| DE4012795A1 (en) * | 1990-04-21 | 1991-10-24 | Metallgesellschaft Ag | ACTIVATING AGENT FOR PHOSPHATING |
| CA2169927A1 (en) * | 1993-09-17 | 1995-03-23 | Kevin Brown | Pre-rinse for phosphating metal surfaces |
-
1997
- 1997-03-07 JP JP05218197A patent/JP3451334B2/en not_active Expired - Lifetime
-
1998
- 1998-02-18 MY MYPI98000677A patent/MY124633A/en unknown
- 1998-03-03 ZA ZA981796A patent/ZA981796B/en unknown
- 1998-03-04 TW TW087103138A patent/TW371675B/en not_active IP Right Cessation
- 1998-03-06 KR KR10-1998-0007469A patent/KR100473603B1/en not_active IP Right Cessation
- 1998-03-06 ID IDP980332A patent/ID20532A/en unknown
- 1998-03-09 EP EP98908792A patent/EP0977908B1/en not_active Revoked
- 1998-03-09 CA CA002283387A patent/CA2283387C/en not_active Expired - Fee Related
- 1998-03-09 DE DE69817803T patent/DE69817803T2/en not_active Revoked
- 1998-03-09 AU AU66736/98A patent/AU6673698A/en not_active Abandoned
- 1998-03-09 WO PCT/US1998/003934 patent/WO1998039498A1/en active IP Right Grant
- 1998-03-09 CN CNB981054668A patent/CN1198958C/en not_active Expired - Lifetime
- 1998-03-09 ES ES98908792T patent/ES2205456T3/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430518C (en) * | 2002-06-13 | 2008-11-05 | 日本油漆株式会社 | Surface conditioner containing zinc phosphate, phosphate chemical conversion treatment steelboard, coating steelboard and zinc phosphate dispersion liquid |
| CN101243208B (en) * | 2005-08-19 | 2010-11-24 | 日本油漆株式会社 | Surface-conditioning composition and surface conditioning method |
| CN101376970B (en) * | 2007-08-28 | 2011-05-11 | 宝山钢铁股份有限公司 | Surface conditioning solution used before manganese series phosphating, preparation and use |
| CN101952479B (en) * | 2008-02-18 | 2013-06-19 | 新日铁住金株式会社 | Plated steel sheet for can and process for producing the plated steel sheet |
| CN102011111A (en) * | 2009-09-03 | 2011-04-13 | 马自达汽车株式会社 | Surface treatment method of metal material |
| CN102011111B (en) * | 2009-09-03 | 2015-01-14 | 马自达汽车株式会社 | Surface treatment method of metal material |
| CN106471157A (en) * | 2014-04-11 | 2017-03-01 | 蒂森克虏伯钢铁欧洲股份公司 | Parkerized metal surface, the method for preferably zinc-plated steel plate are treated in activation |
| CN106471157B (en) * | 2014-04-11 | 2019-08-30 | 蒂森克虏伯钢铁欧洲股份公司 | Activation is to parkerized metal surface, the method for preferably zinc-plated steel plate |
| US10480080B2 (en) | 2014-04-11 | 2019-11-19 | Thyssenkrupp Steel Europe Ag | Method for activating metal surfaces to be phosphated |
| CN109072442A (en) * | 2016-04-25 | 2018-12-21 | Ppg工业俄亥俄公司 | Reactivity purificant and method for handling substrate |
| CN107460468A (en) * | 2016-06-06 | 2017-12-12 | 李力 | A kind of iron-based antirust complex oxide film |
| CN107460468B (en) * | 2016-06-06 | 2019-04-09 | 李力 | A kind of iron-based antirust complex oxide film |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6673698A (en) | 1998-09-22 |
| TW371675B (en) | 1999-10-11 |
| CA2283387C (en) | 2007-07-03 |
| CN1198958C (en) | 2005-04-27 |
| MY124633A (en) | 2006-06-30 |
| EP0977908A4 (en) | 2000-06-07 |
| JP3451334B2 (en) | 2003-09-29 |
| ES2205456T3 (en) | 2004-05-01 |
| JPH10245685A (en) | 1998-09-14 |
| EP0977908B1 (en) | 2003-09-03 |
| DE69817803D1 (en) | 2003-10-09 |
| ZA981796B (en) | 1998-09-07 |
| CA2283387A1 (en) | 1998-09-11 |
| WO1998039498A1 (en) | 1998-09-11 |
| ID20532A (en) | 1999-01-07 |
| EP0977908A1 (en) | 2000-02-09 |
| KR100473603B1 (en) | 2005-08-29 |
| KR19980079984A (en) | 1998-11-25 |
| DE69817803T2 (en) | 2004-07-01 |
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