CN1047331A

CN1047331A - Improved method is made the composition and the method for cold-forming metal

Info

Publication number: CN1047331A
Application number: CN90103585A
Authority: CN
Inventors: 鲍尔·A·库龙欧斯基
Original assignee: Henkel Corp
Current assignee: Henkel Corp
Priority date: 1989-05-18
Filing date: 1990-05-18
Publication date: 1990-11-28
Also published as: JPH02305897A; ZA903494B; BR9002320A; CA2017014A1; EP0398201A1; AU5507390A; AU624710B2

Abstract

The active lubricated improved method of phosphated metal surfaces is to adopt (A) to dissolve in the divalent metal coordination agent of lubricating fluid and (B) with the mixture of the organic molecule of at least one hydroxyl or ether oxygen atom/8 carbon atom from phosphate coating with conventional soluble soap in active lubricating fluid.Be more preferably with EDTA or its salt as coordination agent, polyoxyethylene glycol is as composition (B), EDTA concentration is regulated on demand so that titratable metal total concn is lower than below the 0.05wt% in this method, and the polyoxyethylene glycol amount is regulated the optimization ratio of optimizing lubricating fluid viscosity and reaction lubricator and non-reaction lubricator and reaction lubricator and conversion coating loss to reach on demand.

Description

Improved method is made the composition and the method for cold-forming metal

The present invention relates to lubricated metal is controlled or other cold-forming first being processed is lubricated phosphated metal surfaces composition and method.

For many years, but lubricated and make the metal of cold-forming after the known phosphatization with the soap similar substance.In general, with containing zine ion, calcic sometimes, nickel, manganese, copper, and/or the solution of other divalent-metal ion to carry out phosphatization be preferred phosphatization step.The alkali metal soap aqueous solution that can form so-called " reaction lubricator " extremely favourable Zinic stearas form with the zinc phosphate reaction from the teeth outwards on the spot is generally preferred lubricated step.

Prima facie, the simple solution of active soap can realize utmost point effective lubricating in the water.But known this lubrication can make the dissolving of bonderizing layer segment.For this reason also may be because of other reason, divalent-metal ion can be assembled in lubricating fluid along with the carrying out of this technology, thereby makes the lubricant film of formation unsatisfactory.

The USP4199381 that authorizes Nuss et al. on April 22nd, 1980 has illustrated when the surface that forms in the phosphatization that contains the divalent-metal ion that infiltrates phosphate coating is bathed is lubricated, and this divalent ion coordination agent is added in the lubricating fluid can improve the result.As long as consistent clearly demonstrating of this with the present invention, this specification sheets this with reference to the Nuss patent specification with the lower section: it is capable that the 1st hurdle 10 walks to the 2nd hurdle 4; The 2nd hurdle 33-49 is capable; And the 3rd hurdle 6-11 capable.

By the described coordination agent of Nuss in the useful life that prolongs lubricating fluid with improve aspect the lubricant tectum weight extremely effective effectively, but this class coordination agent of life-time service finally can make lubricating fluid viscosity improve, the phosphate coating amount of dissolving in lubricating fluid increases, also has dry problem, the lubricant cohesive force reduces, and " non-reaction " the lubricator ratio that less needs in the lubricant film that forms improves.The present invention seeks to further to improve the method and composition of Nuss proposition to overcome these difficulties.

The USP 3556996 that authorizes Jones et al. on January 29th, 1971 has illustrated tensio-active agent, comprises the application of condenses in lubricating fluid of alcohol and oxyethane, wherein goes back coupling sugar and/or polyoxyethylene glycol in case of necessity.

Herein, except operational instances or offer some clarification in addition and, it is " approximately " that all numerical value that inventory or reaction or application conditions be described all are interpreted as.

Found that a large amount of coordination agents may be harmful to the active lubricating process after the phosphatization, wherein observed to reach in limited time on the coordination agent concentration of existence and can obtain better result, but the coordination divalent cation amount of upper limit introducing lubricating fluid when using is relevant.Also find to adopt moisture lubricating fluid can improve active lubricating process, say in the lubricating fluid except as the anionic soluble metal soap of the described band of Nuss 8-22 carbocyclic aliphatic and anti-hydrolysis coordination agent and, also contain water-soluble property or dispersed organic compound, this compounds is stable under should normal condition with lubricator on the phosphatization surface and contains at least one hydroxyl or ether oxygen atom/8 carbon atom.This back one composition is designated hereinafter simply as " OSOC " (being oxidation solubility organic compound).In the definition of OSOC composition, think that till the ass ascends the ladder the Sauerstoffatom in carbonyl or the carboxylate radical is ether or hydroxyl oxygen.Preferably, contain at least one hydroxyl or ether oxygen/2 carbon atom in the OSOC component molecules.

Be used for water-soluble soap of the present invention and can be this specialty any material commonly used, comprising the industrial sodium stearate that contains 40-90%18 carbon soap, with having crossed, but it is generally preferred to comprise the cuts of a large amount of sodium stearate in some example of above-mentioned Nuss patent for this.Equally, coordination agent also can be the known any material of this specialty, but preferably from ethylene diaminetetraacetic acid (calling " EDTA " in the following text) and its salt, nitrilotriacetic acid(NTA) (calling " NTA " in the following text) and its salt, N-hydroxyethyl ethylene amine triacetic acid (calling " NEDTA " in the following text) and its salt, diethylene triaminepentaacetic acid(DTPA) and its salt, di-alcohol glycine and CAS registration number 68611-02-9 ^*Material, the back a kind of by its manufacturers be illustrated as " glycine, N ', N '-1,2-ethane two base two (N-carboxymethyl)-, with the reaction product of citric acid, D-glyconic acid, and trolamine, sodium salt ".Most preferably be EDTA and its salt.

The OSOC composition is preferably from aklylene glycol, polyalkylene glycol, glycol ethers, ethoxylated alcohol, oxyethane and epoxypropane polymer and multipolymer, and glycerine.

For coordination agent and OSOC composition, the mixture of preferred feed is the same preferred with each single chemical substance, and other has except the explanation.

Poly-(ethylene glycol) calls " PEG " in the following text, and than other OSOC material more preferably, the PEG molecular weight is about 4000, call in the following text " PEG4000 " then more preferred.When the OSOC composition was made up of PEG4000 basically, preferred coordination agent concentration was 1-5 with the ratio of OSOC constituent concentration, and more preferably 2.5-3.5 most preferably is 2.9-3.1.

Active soap concentration is 5-150g/l solution in the solution preferably of the present invention.The coordination agent preferred concentration is by the following several respects factor decision of balance.

The phosphatization that will suit surface contacts with the invention described above lubricating fluid can realize the inventive method.It is believed that contact because of lubricating fluid and phosphatization surface gather capacity divalent metal ion therein before, exist coordination agent to there is no advantage at the newly formed lubricating fluid use initial stage.But, found that coordination agent initial stage concentration do not have obvious harm up to 0.1g/l yet, and the application initial stage contains approximately this amount, or the solution of a small amount of slightly coordination agent is generally also more preferred, and the utmost point adds coordination agent within the short period of time can to avoid coming into operation afterwards at new lubricating fluid like this.

The ideal lubricating process will reach the reaction lubricator of the high coating wt of unanimity, avoid in lubricating fluid, introducing the by product that disturbs the requirement reaction between phosphate coating composition and the lubricating fluid composition, and when phosphate coating enters lubricating fluid, do not remove this phosphate coating on the metallic surface basically or fully.No any known lubricating fluid can reach such lubricating at present, but preferred actual behaviour behaviour bathes the ratio that tends to make reaction lubricator weight and transform the deep layer loss amount reaches maximum, and considers the ratio optimization that makes reaction slip coating weight and non-reaction slip coating weight.

The inventive method most preferred embodiment is to use the initial stage to use coordination agent and OSOC composition in lubricating fluid in new bath formulation.In these embodiments, select " titratable metal " upper limit of concentration of following accurately definition and add coordination agent after being higher than the selected upper limit and can reach satisfied operational condition measuring titratable metal concentration at every turn.Coordination dosage is enough to make titratable metal concentration to be in below the higher limit at least.Test with each concrete lubricating fluid composition and matrix metal kind and lubricated phosphate coating and can the most accurately determine best higher limit, but preferred higher limit is generally 0.05wt% or following.

Most preferably, lubrication of the present invention and lubricating fluid should be used controlled at the very start from new obtain solution, and titratable like this metal concentration just will never rise to more than the selected upper limit during the whole application of lubricating fluid of the present invention.Therefore, the coordination agent that more preferably after at every turn measuring titratable metal, adds capacity, so that titratable metal concentration be lower than after just reinforced its higher limit 2/3rds or below, and measure titratable metal concentration with enough number of times and will never rise to more than the selected upper limit to guarantee this concentration.The most preferably general capacity coordination agent that adds in this solution is to make titratable metal concentration be lower than 0.01wt% after measuring the higher value of this concentration at every turn.

Although most preferably use at the beginning or close at lubricating fluid as stated above and begin to adopt the lubricating fluid that contains coordination agent and OSOC composition, but also available traditional lubrication liquid begins in the inventive method implementation process, wherein contain minute quantity or do not contain coordination agent, this be used for phosphatization to enough degree so that titratable metal concentration greater than the higher limit that requires of the inventive method.In this embodiment, found to add and titratable metal concentration can have been reduced to the utmost point to be bordering on zero a large amount of coordination agents that may require be disadvantageous.A large amount of like this coordination agents may cause excessive conversion coating loss between lubrication intervals.On the other hand, when method of the present invention begins with the lubricating fluid that contains the titratable metal more than the 0.05wt%, preferably begin to add and to make in the solution coordination agent concentration reach 5-9 doubly to the coordination dosage that records titratable metal concentration, most preferably than being 6.5-7.5.Simultaneously, also preferred adding can make coordination agent and OSOC composition keep the q.s OSOC composition of above-mentioned preferred ratio.The titratable metal concentration that stays after the initial stage adding coordination agent is preferably also measured then like this, and this concentration is generally 0.01-0.05.Initial stage adds after the coordination agent, preferably proceed the inventive method in the same operation mode of above-mentioned embodiment, just add coordination agent in the above-mentioned embodiment when lubricating fluid uses beginning, just the add-on of coordination agent should be limited so that titratable metal concentration was unlikely at the coordination agent initial stage and be reduced to below 3/4ths of its concentration after reinforced.

In all technologies of the present invention, the OSOC composition should be preferably and coordination agent add simultaneously among the lubricating fluid, present in an amount at least sufficient to make these two kinds to become the ratio of branches to reach above-mentioned preferable range.

Carry out after for some time operation with identical or similar metallic matrix and phosphatization condition, just can be easy to successfully operate the inventive method, wherein need not clearly to measure the titratable metal concentration of dissolved, only need add the coordination agent and the OSOC composition of appropriate amount to lubricating fluid in the spaced points that solution is used for lubricating.

The duration of contact on lubricating fluid temperature and lubricating fluid and phosphatization surface is generally in the industry is carried out active lubricated equal conditions scope in any technology of the present invention.For example, preferred temperature is generally 70-90 ℃, and be 1-10 minute duration of contact.

Below unrestricted operational instances the present invention is described in detail in detail.

Example

The general condition of all examples and comparative example

79 ℃ of lubricating fluid temperature, and the phosphating metal sample contacts 5 minutes with lubricating fluid, back in 121 ℃ of baking ovens dry 15 minutes.Test specimen is Type 1010 cold-rolled steels, has used Bonderite 181x is Henkel Corporation, and the commercially available zinc phosphatization liquid of the Parker+Amchem Division of Madison Heights.Michigan is phosphatization in 30 the solution at total acid value.(the point here is defined as the titration of 5ml phosphatization liquid sample to the required 0.1N NaOH liquid ml number of phenolphthalein end points).Average phosphate coating weight is 12.8g/m in all test specimens ²The surface has only embodiment 5 exceptions, and its average deep layer weight is 21g/m ²

Free acid or free alkali and titratable metal content are measured by laxative remedy in the lubricating fluid.

Free acid

The solution that contains 0.2wt% phenolphthalein in the 200ml Virahol is poured in the 400ml flask, after add the hot lubricating fluid of 10ml, measure with conical graduate or valinche.In beaker with mixture heating up to boiling point and make its boiling at least 1 minute.Remove the still solution of heat of thermal source and titration immediately, wherein, if the solution clarification, rather than pink, just with 0.1N NaoH liquid, titration is to showing permanent pale pink look.The titrating solution ml number that requires is free acid " point " number.If it is pink that solution has been after boiling, then disappear to pink is permanent with the titration of 0.1N sulfuric acid.Acid ml number is free alkali and counts.

Titratable metal

20g or 20ml homogenizing lubricating fluid sample are put into the 150ml beaker, with dilution of 20ml deionized water and the dense HCl of adding 1ml.That heats on hot plate tells fatty-acid layer.Cooling and filter in the high pin beaker of 200ml with Whatman #541 filter paper.In the glass stopper flask, cool off, be diluted to 100ml.The 25ml aliquot is changed over to the high pin beaker of 200ml from the glass stopper flask.Add 1 methyl red indicator liquid and use NH ₄The OH neutralization.Add 5ml " Reagent Solution 65 ", be 2wt% oxyamine hydrochloride liquid in the water, and mix.Add 2ml " Reagent Solution87 ", be 6.7wt% ammonium chloride, dense ammonium hydroxide water of 57wt% and the solution of 0.5wt%EDTA magnesium in water, and mix.Add the 10% ammonium cyanide solution of 2ml and mix." Indicator24 " that adds about 1/8th tea spoons, be the 99.6wt% dextrin, 0.2wt%EDTA magnesium, the solid mixture black with 0.2wt%Eriochrome, and carry out titration, and wherein adopt " Titratins Solntion 86 ", be the 0.4wt%EDTA sodium water solution, titration fades to light blue to color from scarlet, keep this sample in order to the zinc titration.

%(Ca+Mg)=(0.04(ml " Titrating Solntion 86 ")/(primary sample size)

N.B.: if sample iron content and/or aluminium, so when calcium+magnesium determination in adding " Reagent Solution 87 " adds 10ml before in sample the 30wt% trolamine aqueous solution, just can obtain most advanced and sophisticated point.

Drop-burette set to zero again and with several " Reagent Solution 88 ", for 18wt% formaldehyde and 2wt% methanol in water add in the sample after calcium+magnesium titration and with Titrating Solution 86 titration to new red to blue end points.Add one " Keagent Solution 88 " again and use " Titrating Solntion 86 " to carry out titration again.Repeat not require and carry out titration again until 1 " Reagent Solution 88 "." the Titrating Solntion 86 " of Xiao Haoing represented the zinc that discharges from cyanide complex in addition.

%Z _n=(" Titrating Solution86 " that 0.0654(ml adds)/(primary sample size)

The original filtered sample of 0.5ml aliquot is changed over to the 100ml glass-cover measuring cylinder from its original preparation 100ml glass stopper flask.Add 5ml " ReagentSolution 65 ", 10ml " Indicator 19 ", the aqueous solution for 1.5wt% ammonium citrate and 0.05wt% o-phenanthroline monohydrate, and 1.0ml " Reagent Solution 90 ", be the aqueous isopropanol of 5wt%1.10-phenanthroline.Be diluted to 100ml.Put upside down twice and allow it leave standstill 1 hour.Determine percent transmission at 510-525nm wavelength place then.Read mg Fe number from typical curve.Typical curve obtains by the following method: add 0,0.5,1.0,1.5 and " the Standard Solntion 91 " of 2.0ml in a series of 100ml glass-cover measuring cylinders, be the 0.03wt% ferrous sulfate and the 2wt% vitriolic aqueous solution.This tittle is corresponding to 0,0.5, and 0.1,0.15 and 0.2mgFe.Add 5ml " Reagent Solution 65 " and 10ml " Indicator 19 " then to each graduated cylinder.Be diluted to 100ml and put upside down twice and mix with deionized water.Allow it leave standstill at least 10 minutes, determine the percent transmission of each standard then, wherein adopt liquid at the bottom of the deionized water, measure in 510-525nm wavelength place (510nm is preferred).Adopt semilogarithmic paper to make the typical curve of mgFe amount to percent transmission, transmittance is in logarithm, and mgFe is to count.

%Fe=(mgFe on the 0.1(typical curve))/(primary sample ml number)

" titratable metal " concentration is defined as in the solution: %Z _n+ (1.64%(%Ca+Mg)+(1.16) (%Fe).

Lubricating fluid viscosity is measured with #2Zahn Cnp.

Sample coatings weight and the definition of other related characteristics and/or assay method are as follows:

W1=test piece and phosphate coating weight (g).

Test piece, phosphate coating and lubricant film weight (g) after W2=soaked in lubricating fluid.

The W3=test piece in phosphatization liquid and lubricating fluid, soaked and wash after weight (g).

Washing: will reach 3 minutes in the test piece immersion boiling deionized water, the water yield is enough to provide water/cm at least about 4.3ml ²The test piece area.Reach 3 minutes in taking-up test piece and the boiling deionized water, clean with this with its immersion equal volume.The test piece of take out cleaning is also dry in baking oven, weighs after being cooled to room temperature.

The W4=test piece was soaked in phosphatization liquid and lubricating fluid and was carried out weight (g) behind above-mentioned washing and the solvent wash.

Solvent wash: test piece is put among the extraction part of Soxhlet or similar extractor, wherein among a container, gathered new solvent distillation and reached specified level, overflow the solvent that gathers then, and repeat this circulation.Liquid level is filled into and just is in overflow position and will guarantees that all test pieces are all covered by solution fully when following in the container.Use the 55wt% Virahol, 32wt% normal heptane and all the other are that the abundant backflow mixture gained condensation product of cellosolvo extracted 30 minutes at least.Take out test piece, dry in the baking oven, be cooled to room temperature, and weigh.

The W5=test piece was soaked in phosphatization liquid and lubricating fluid also as the weight (g) after above-mentioned washing and solvent wash and the chromic acid washing.

Chromic acid washing: with 800gCrO ₃Be dissolved in and make 4l solution in the enough water.This solution is heated to 82 ℃ and keep under this temperature, wherein stir and thermostatic control.Test piece was soaked 5 minutes.Take out test piece from hot solution, washing is fast used the cleaning compressed air drying, and is weighed in cold water.

Surface-area is with m ²Meter.

A) conversion coating loss=((W1-W4))/(surface-area)

B) non-reaction lubricator=((W2-W3))/(surface-area)

C) reaction lubricator=((W3-W4))/(surface-area)

D) residue conversion coating=((W4-W5))/(surface-area)

E) total lubricator=non-reaction lubricator+reaction lubricator.

Special test

Newly formed initial stage lubricating fluid consists of 3.6wt% soda soap mixture, and with making with the commercial fatty acids mixture in the sodium hydroxide, at least 95% is stearic acid in the acid mixture, makes lubricating fluid in water.Solution 1 is newly prepared liquid for this reason, and solution 2-5 has experienced the process that is applied to lubricated phosphatization surface.These solution properties see Table 1 during beginning.Carry out following test then:

Test #1

Smear among the solution 1-4.

Measure coating wt.

Test #2

The 1.5g/lEDTA tetra-na salt is added in the solution 2.

The 4g/lEDTA tetra-na salt is added in the solution 3.

The 5.5g/lEDTA tetra-na salt is added in the solution 4.Test among the solution 2-4 of smear after reinforced the improvement as the above-mentioned first time.

Measure coating wt.

Test #3

The PEG4000 of 0.5g/l is added in the solution 2.

The PEG4000 of 1.25g/l is added in the solution 3.

The PEG4000 of 1.8g/l is added in the solution 4.

Test among the solution 2-4 of coating after reinforced as the above-mentioned second time.

Measure coating wt.

Test #4

The EDTA tetra-na salt (coordination agent) and the PEG4000 of difference amount are added in the solution 5 each reinforced back smear.

The 1st time reinforced: the coordination agent of 5g/l, the PEG of 2.5g/l.

The 2nd time reinforced: the coordination agent of 5g/l, no PEG.

The 3rd time reinforced: the coordination agent of 5g/l, the PEG of 2.5g/l.

Total reinforced: the coordination agent of 15g/l, the PEG of 5g/l.

Each reinforced back solution properties also sees table 1 in these tests.These test mid-deep strata weight result sees Table 2 with relevant observed value.

Test 1 is a comparative example, shows that the increase of divalent metal has reduced conversion coating loss and lubricator activity.Increase to 0.08% at divalent metal, the conversion coating loss is reduced to 1.7g/m from 2.6 ²Meanwhile, the reaction lubricator is reduced to 3.9g/m from 1.05 ²

Test 2 is a comparative example also, has shown to add the influence of EDTA tetra-na salt to coating process.Under all 3 kinds of divalent metal amounts, reaction lubricator amount increases.The maximum variation sees solution #4, wherein contains the maximum metal ion.Non-reaction lubricator amount increases considerably, because soltion viscosity increases to 16Sec from 14.

Test 3 is for the present invention, shown that polyoxyethylene glycol is that how soltion viscosity to be dropped to low-level, and improved the ratio of reaction lubricator and non-reaction lubricator and reaction lubricator and conversion coating loss.Non-reaction lubricator weight descends, and the reaction lubricator weight that more needs simultaneously increases, even lose when roughly the same at conversion coating, also can reach this effect.

Test 4 is also for the present invention, shown that it is the optimized coatings weight based on initial stage divalent-metal ion concentration how that the initial stage is suitably added EDTA tetra-na salt and polyoxyethylene glycol, and this should be the preferred practice.During as heavy addition EDTA tetra-na salt shown in reinforced for the third time in this test,, will increase the conversion coating loss, but can not improve the lubricator coating wt in a large number in case all divalent metals all are combined into title complex basically.Adding for the second time coordination agent makes total lubricity of this concrete solution more meet the requirements than the effect that reaches of feeding in raw material for the third time, even titratable metal concentration is much higher than 0.01wt% after feeding in raw material for the second time, but after feeding in raw material for the third time, be lower than again under the situation of this value, also can reach this effect.Therefore, when this added EDTA for the third time, even still be in the scope of the invention, coordination agent concentration had exceeded most preferred range in this solution but make.

Although as above-mentionedly can make preferably that titratable divalent-metal ion concentration remains on below the 0.05wt% in the solution of the present invention, the present invention also can be used for containing at most the solution of the titratable divalent-metal ion of this class of 0.2wt%.

Claims

1, liquid substance composition, it basic composition is: (A) water; (B) reactive metal soap composition; (C) coordination agent composition; (D) OSO composition, by normal at least one hydroxyl or ether oxygen atom/8 carbon atom and in the solution of said composition or dispersion stable organic molecule form; And (E) the titratable metal of about at most 0.2wt%.

2, the composition of claim 1, wherein the OSOC composition is selected from the molecule that contains at least one hydroxyl or ether oxygen atom/2 carbon atom.

3, the composition of claim 2, wherein coordination agent is selected from EDTA and its salt, NTA and its salt, NEDTA and its salt, diethylene triaminepentaacetic acid(DTPA) and its salt, the di-alcohol glycine, and the CAS registration number is the material of 68611-02-9.

4, the composition of claim 1, wherein coordination agent is selected from EDTA and its salt, NTA and its salt, NEDTA and its salt, diethylene triaminepentaacetic acid(DTPA) and its salt, the di-alcohol glycine, and the CAS registration number is 68611-02-9 ^*Material.

5, the composition of claim 4, wherein the OSOC composition is by being selected from aklylene glycol, poly-(aklylene glycol), glycol ethers, ethoxylated alcohol, the polymkeric substance of oxyethane and propylene oxide and multipolymer, and the molecular composition of glycerine.

6, the composition of claim 1, wherein the OSOC composition is by being selected from aklylene glycol, poly-(aklylene glycol), glycol ethers, ethoxylated alcohol, the polymkeric substance of oxyethane and propylene oxide and multipolymer, and the molecular composition of glycerine.

7, the composition of claim 6, wherein (I) active soap concentration is the about 150g/l of about 5-, (II) coordination agent constituent concentration is not more than (A) about 0.1g/l and (B) titratable metal concentration in the composition is reduced to the bigger value upper limit in the required minimum quantity below the 0.05wt%, and (III) OSOC composition is made up of PEG4000 basically, and its concentration in composition should make the coordination agent constituent concentration and the ratio of OSOC constituent concentration reach about 1-about 5.

8, the composition of claim 4, wherein (I) active soap concentration is the about 150g/l of about 5-, (II) coordination agent constituent concentration is not more than (A) about 0.1g/l and (B) titratable metal concentration in the composition is reduced to the bigger value upper limit in the required minimum quantity below the 0.05wt%, and (III) OSOC composition is made up of PEG4000 basically, and its concentration in composition should make the coordination agent constituent concentration and the ratio of OSOC constituent concentration reach about 1-about 5.

9, the composition of claim 8, wherein the coordination agent composition is selected from EDTA and its salt.

10, the composition of claim 7, wherein the coordination agent composition is selected from EDTA and its salt.

11, the phosphate coating that will form like this behind the phosphated metal surfaces contacts with the moisture lubricating fluid of any divalent metal coordination agent composition in this phosphate coating with the active lubricant composition and form the method for reaction lubricant film on this metallic surface, it is characterized in that wherein said lubricating fluid also contains the OSOC composition, by forming with the organic molecule of at least one hydroxyl or ether oxygen atom/8 carbon atom.

12, the method for claim 11, wherein the OSOC composition is selected from the molecule that contains at least one hydroxyl or ether oxygen atom/2 carbon atom.

13, the method for claim 12, wherein coordination agent is selected from EDTA and its salt, NTA and its salt, NEDTA and its salt, diethylene triaminepentaacetic acid(DTPA) and its salt, the di-alcohol glycine, and the CAS registration number is 68611-02-9 ^*Material.

14, the method for claim 11, wherein the OSOC composition is by being selected from aklylene glycol, poly-(aklylene glycol), glycol ethers, ethoxylated alcohol, the polymkeric substance of oxyethane and propylene oxide and multipolymer, and the molecular composition of glycerine.

15, the method for claim 14, wherein (I) active soap concentration is the about 150g/l of about 5-in the lubricating fluid, (II) coordination agent constituent concentration is not more than (A) about 0.1g/l and (B) titratable metal concentration in the composition is reduced to the bigger value upper limit in the required minimum quantity below the 0.05wt%, and (III) OSOC composition is made up of PEG4000 basically, and its concentration in composition should make the coordination agent constituent concentration and the ratio of OSOC constituent concentration reach about 1-about 5.

16, the method for claim 15, wherein titratable metal concentration remains on below the higher limit of preliminary election by adding coordination agent between the usage period at lubricating fluid in the lubricating fluid.

17, the method for claim 14, wherein titratable metal concentration remains on below the higher limit of preliminary election by adding coordination agent between the usage period at lubricating fluid in the lubricating fluid.

18, the method for claim 13, wherein titratable metal concentration remains on below the higher limit of preliminary election by adding coordination agent between the usage period at lubricating fluid in the lubricating fluid.

19, the method for claim 11, wherein titratable metal concentration remains on below the higher limit of preliminary election by adding coordination agent between the usage period at lubricating fluid in the lubricating fluid.

20, the method of claim 11, wherein lubricating fluid contained the titratable metal more than 0 0.05wt% before this method begins, titratable metal concentration is minimized by adding coordination agent when this method begins in the lubricating fluid, coordination dosage be enough to make its concentration in solution reach about 5-about 9 times before this method begins in the lubricating fluid in the scope of titratable metal concentration, and between the follow-up usage period of lubricating fluid when adding more coordination agent and make titratable metal concentration be maintained at about the upper limit of 0.05wt% and this method to begin within about 2/3rds of the titratable metal concentration in reinforced for the first time back the lower range.