CN1680047A

CN1680047A - Pretreatment method for painting

Info

Publication number: CN1680047A
Application number: CNA2005100651855A
Authority: CN
Inventors: 岸博之; 宫本诚司; 田中修; 八重樫英明; 小比贺正弘
Original assignee: Nissan Motor Co Ltd
Current assignee: Nissan Motor Co Ltd
Priority date: 2002-06-12
Filing date: 2003-06-12
Publication date: 2005-10-12
Also published as: US20040007249A1; EP1371756A2; CN1470673A

Abstract

Equipment of pretreatment before painting for a composite vehicle body comprises a treatment tank, an aluminum chemical conversion unit, and a rinse unit. The treatment tank is filled with a degreasing and chemical conversion solution containing a mixed solution of a polar organic solvent and water, any of sodium ion and lithium ion, phosphate ion, zinc ion, nickel ion, manganese ion, and any of nitrate ion and nitrite ion. The mixed solution has a weight ratio of the polar organic solution to the water in a range of 2.8:7.2 to 3.8:6.2. The aluminum chemical conversion unit treats the composite vehicle body with a chemical conversion solution for aluminum. The rinse unit washes the composite vehicle body with a washing solution.

Description

Pretreated method before the japanning

Background of the present invention

Technical field

Pretreated method before the present invention relates to paint, pretreated method before the japanning that relates more specifically to preferably to use on the pre-treatment line before japanning for example wherein moves on the hybrid Car Body On-line of iron and aluminium.

Background technology

For weight reduction, increase rigidity, or improve recyclability, checked the hood that uses aluminium parts to be used for vehicle body, boot-lid panel, inner plate of car door etc.

Pretreatment process as the hybrid vehicle body of such iron and aluminium, Japanese Patent translation issuing thing No.2001-515959 (PCT international publication No.WO99/12661) suggestion is only carried out chemical conversion with the iron parts in the first step, then in second step aluminium parts is carried out chemical conversion.

For etching aluminium and precipitation or shelter dissolved aluminium, the fluorion of free or complex-bound is joined in the chemical conversion solution that uses in pretreatment process.Free fluorine ionic concentration limit to be lower than 8/T (g/L, T: pretreatment temperature (℃)), make on the aluminium surface, not form excessive chemical conversion coating, promptly once do not accumulate a large amount of sludges.

General introduction of the present invention

Yet in the pretreatment process described in the above Japanese Patent translation issuing thing No.2001-515959, chemical conversion solution contains fluorion.Therefore, the sludge of aluminium accumulates in groove (tank), and must remove and get rid of this sludge.And, as mentioned above,, the concentration of free fluorine is not lower than preset value if being controlled to, on the aluminium surface, formed excessive aluminium conversion coating so.Therefore, need be used to the operation and the system that control and manage free fluorine concentration and be used to control and manage make-up solution.

In addition, because the chemical conversion process of aluminium is to provide, increased the total length of pretreatment process after the chemical conversion process of steel.Therefore, this method is disadvantageous on space, treatment time and equipment cost.

The purpose of this invention is to provide japanning preceding equipment of pretreatment and method, described equipment and method can reduce assembly space for the hybrid vehicle body of iron and aluminium, boost productivity, and significantly reduce equipment cost, the chemical cost, the cost of management man-hour and wastewater treatment.

First aspect of the present invention provides the equipment of pretreatment before the japanning, comprise: treatment trough, it is equipped with the mixing solutions that contains polar organic solvent and water, sodium ion and lithium ion any or two kinds, phosphate anion, zine ion, nickel ion, mn ion, and the degreasing and the chemical conversion solution of nitrate ion and nitrite ion any or two kinds, this mixing solutions has the polar organic solvent in 2.8: 7.2 to 3.8: 6.2 scopes and the weight ratio of water, and workpiece is submerged in this treatment trough; With the aluminum chemistry conversion unit of the chemical conversion solution-treated workpiece of aluminium, this aluminum chemistry conversion unit provides in the subsequent segment of treatment trough; And with the rinse unit of washings washing workpiece, this rinse unit provides in the subsequent segment of this aluminum chemistry conversion unit.

Second aspect of the present invention provides the pretreated method before the japanning, comprise: hybrid vehicle body (it has any of the aluminium of at least a portion that is used for outer plate portion and aluminium alloy part) is impregnated into the mixing solutions that contains polar organic solvent and water at least, sodium ion and lithium ion any or two kinds, phosphate anion, zine ion, nickel ion, mn ion, and in the degreasing and chemical conversion solution of nitrate ion and nitrite ion any or two kinds, this mixing solutions has the polar organic solvent in 2.8: 7.2 to 3.8: 6.2 scopes and the weight ratio of water; In the chemical conversion solution of aluminium, handle vehicle body; With wash vehicle body with washings.

The 3rd aspect of the present invention provides the equipment of pretreatment before the japanning, comprise: treatment trough, it is equipped with the mixing solutions that contains polar organic solvent and water, sodium ion and lithium ion any or two kinds, phosphate anion, zine ion, nickel ion, mn ion, degreasing and chemical conversion solution with any of nitrate ion and nitrite ion or two kinds, this mixing solutions has the polar organic solvent in 2.8: 7.2 to 3.8: 6.2 scopes and the weight ratio of water, and workpiece is submerged in the treatment trough; With the aluminum chemistry conversion system (means) of the chemical conversion solution-treated workpiece of aluminium, this aluminum chemistry conversion system provides in the subsequent segment of treatment trough; And with the rinsing device of washings washing workpiece, this rinsing device provides in the subsequent segment of this aluminum chemistry conversion system.

The accompanying drawing summary

Now with reference to accompanying drawing the present invention is described, wherein:

Fig. 1 is the system view of first embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Fig. 2 A is the skeleton view that shows the embodiment of fly-ash separator of the present invention;

Fig. 2 B is the cross sectional view that shows the embodiment of fly-ash separator of the present invention;

Fig. 3 is the skeleton view that shows another embodiment of fly-ash separator of the present invention;

Fig. 4 is the cross sectional view that shows another embodiment of fly-ash separator of the present invention;

Fig. 5 is the system view of second embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Fig. 6 is used to illustrate according to the full dip treating of the equipment of pretreatment before the japanning shown in Fig. 5 and the view of half dip treating;

Fig. 7 is the system view of the 3rd embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Fig. 8 is the synoptic diagram that shows the embodiment of water of the present invention-polar organic solvent separator;

Fig. 9 is the synoptic diagram that shows the embodiment of ion eradicator of the present invention;

Figure 10 is the system view of the 4th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 11 is the synoptic diagram that shows the unitary embodiment of vacuum distilling of the present invention;

Figure 12 is the system view of the 5th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 13 is the system view of the 6th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 14 is the system view of the 7th embodiment of the pre-processing device before the demonstration japanning of the present invention;

Figure 15 is the system view of the 8th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 16 is the schema that is presented at the example that the control of the controller shown in Figure 15 moves;

Figure 17 is the plan view of the 9th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 18 is the system view of the 9th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention;

Figure 19 is presented at the schema that the control of controller is as shown in Figure 17 moved;

Figure 20 is the form that shows the result of embodiments of the invention; With

Figure 21 is the form that shows comparative example's result.

Detailed description of the preferred embodiments

Hereinafter, each embodiment of the present invention is described with reference to the accompanying drawings.

First embodiment

Fig. 1 is the system view of first embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.This accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.

Especially, have the hybrid vehicle body that is equipped with by iron and aluminum through the automobile body B of the lacquer wire of the present embodiment, hood wherein, boot-lid panel, the outer plate portion of door etc. uses aluminium parts and other parts are formed from steel.Yet in the equipment of pretreatment before japanning of the present invention, all workpiece are not necessarily limited to the hybrid vehicle body of this iron-aluminium, and the hybrid vehicle body of iron-aluminium and steel vehicle body can mix mobile.And the type of vehicle with hybrid vehicle bodies of iron-aluminium different on the part of using aluminium parts can mix mobile.In addition, can move the vehicle body that all components wherein comprises aluminum or aluminum alloy.

Hereinafter, for convenience's sake, all the vehicle body of being made by iron component is called as the iron vehicle body.The vehicle body of being made by the aluminum or aluminum alloy assembly is called as the aluminium vehicle body fully.Part is called as hybrid vehicle body by the vehicle body that the aluminum or aluminum alloy assembly is made and other assembly is fabricated from iron.

As shown in Figure 1, on being fixed on suspension bracket H in, automobile body B is carried by japanning travelling belt C.In this embodiment, two steeping vats are provided along japanning travelling belt C.Steeping vat by the upstream side in the throughput direction shown in the arrow X is the treatment trough 101 (hereinafter, also being referred to as degreasing and chemical conversion groove 101) that is used for skimming treatment and chemical conversion in the accompanying drawings.The rinse tank 201 of the automobile body B after the steeping vat in downstream side is to be used to wash skimming treatment and chemical conversion.This treatment trough 101 is equipped with degreasing and chemical conversion solution, and rinse tank 201 is equipped with deionized water.

Degreasing of using in the present embodiment and chemical conversion solution can carry out three kinds of processing such as skimming treatment in same process, the surface is adjusted, and chemical conversion.As this degreasing and chemical conversion solution, can use and contain polar organic solvent at least, water, sodium ion and/or lithium ion, phosphate anion, zine ion, nickel ion, mn ion, and the treatment soln of nitrate ion and/or nitrite ion.Use this treatment soln, degreasing process, surface conditioner can carry out in technology with chemical conversion technology simultaneously, so make treatment process significantly reduce, treatment facility is simplified, and floor space reduces, and productivity improves, the chemical cost reduces, and the management of chemical is simplified.

To the degreasing and the chemical conversion solution of the present embodiment be described in further detail.In the mixed solvent of polar organic solvent and water, the weight ratio of polar organic solvent and water is 2.8: 7.2 to 3.8: 6.2, preferred 3.0: 7.0 to 3.8: 6.2, and more preferably 3.3: 6.7 to 3.8: 6.2, also more preferably 3.3: 6.7 to 3.5: 6.5 and most preferably 3.5: 6.5.

As the example of the polar organic solvent in the present embodiment, enumerate usefulness (CH ₂-CH ₂-O) _nThe ethylene glycol of (n=1,2,3,4) expression or the lower alkyl ether or the lower alkyl esters of analogue, the lower alkyl ether of propylene glycol or lower alkyl esters, dipropylene glycol etc., low-grade alkylidene glycol such as glycol ether, triglycol, Tetraglycol 99, lower alcohol, or their ester.

Example as glycols lower alkyl ether or lower alkyl esters, enumerate glycol ether such as ethylene glycol monomethyl ether and glycol monomethyl n-butyl ether, glycol ether ether such as carbiphene and diglycol monotertiary n-butyl ether, triglycol list n-butyl ether, Tetraglycol 99 list n-butyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate or analogue.

As the lower alkyl ether of propylene glycol or dipropylene glycol or the example of lower alkyl esters, enumerate propylene glycol butyl ether, dipropylene glycol monomethyl ether, polypropylene glycol list ethyl ether or analogue.

As the example of lower alcohol, enumerate and have 1-8 carbon atom, preferred 1-5 the carbon atom and the more preferably alcohol of 1-4 carbon atom.As specific examples, enumerate alcohol as ethanol, Virahol, the trimethyl carbinol, methoxyl group dimethyl pentanol, diacetone alcohol, 2-methyl cellosolve and 2-oxyethyl group methyl alcohol or analogue.

As the example of ester, enumerate ethyl lactate, methoxy butyl acetate, n-Butyl lactate, or analogue.

In above-mentioned polar organic solvent, most preferably use and be selected from glycol ether, triglycol, Tetraglycol 99, propylene glycol, ethylene glycol monoalkyl ether, and be selected from the diglycol monotertiary alkyl oxide, glycol ether dialkyl ether, and propylene-glycol monoalky lether, or at least a diol compound in the mixed solvent of diol compound and lower alcohol.

Preferably, the alkyl in diol compound is the alkyl with 1-5 carbon atom.Preferably, lower alcohol is the alcohol with 1-8 carbon atom, more preferably has the alcohol of 1-5 carbon atom and most preferably has the alcohol of 1-4 carbon atom.

In the degreasing and chemical conversion solution of the present embodiment, the mixed solvent of above-mentioned polar organic solvent and water contains sodium ion and/or lithium ion at least, phosphate anion, zine ion, nickel ion, mn ion and nitrate ion and/or nitrite ion.

Preferably, the content of phosphate anion is the mixed solvent at 0.2 to 0.5 weight part (comprising end value)/100 weight part.If this content is not in this scope, the oil mass that is blended in the treatment soln increases, and has therefore caused stirring insufficient.Therefore, can not form good phosphoric acid zinc coating as target.The source of phosphate anion is not special restriction, and as their example, enumerates ortho-phosphoric acid, tetra-sodium, Tripyrophosphoric acid, three metaphosphoric acids, four metaphosphoric acids, Vanadium Pentoxide in FLAKES or analogue.Phosphate anion can be as the negatively charged ion supply of the metal ion that contains in degreasing and chemical conversion solution (sodium ion and/or lithium ion, zine ion, nickel ion, mn ion).

Zine ion has the function that forms the zinc phosphate conversion coating that has phosphate anion.Preferably, the content of zine ion is in the scope of the mixed solvent of 0.5-0.7 weight part (comprising end value)/100 weight part.Increase if this content not in this scope, is blended into the amount of the oil in the treatment soln, therefore cause stirring insufficient.Therefore, can not form good phosphoric acid zinc coating as target.As the example in the source of zine ion, enumerate inorganic salt such as zinc oxide, zinc carbonate, zinc nitrate, zinc chloride, zinc sulfate, zinc phosphate or analogue.

Nickel ion has the do not paint function of erosion resistance of workpiece of raising.Preferably, the amount of nickel ion is in the scope of the mixed solvent of 0.09 to 0.23 weight part (comprising end value)/100 weight part.If this content is outside this scope, the oil mass that is blended in the treatment soln increases, and therefore causes stirring insufficient.Therefore, can not form good phosphoric acid zinc coating as target.As the example in nickel ion source, enumerate inorganic salt such as nickelous nitrate and nickelous phosphate or analogue.

Mn ion has the function of the wet paint clinging power that improves the workpiece that contains metallic zinc.Preferably, the content of mn ion is in the scope of the mixed solvent of 0.03 to 0.16 weight part (comprising end value)/100 weight part.If this content is outside this scope, the oil mass that is blended in the treatment soln increases, and therefore causes stirring insufficient.Therefore, can not form good phosphoric acid zinc coating as target.As the example in the source of mn ion, enumerate inorganic salt such as manganous nitrate and manganous phosphate or analogue.

Preferably, the content of nitrate ion and/or nitrite ion is in the scope of the mixed solvent of 3.5 to 10.8 weight part (comprising end value)/100 weight parts.If this content is outside this scope, the oil mass that is blended in the treatment soln increases, and therefore causes stirring insufficient.Therefore, can not form good phosphoric acid zinc coating as target.

Preferably, the content of sodium ion and/or lithium ion is in the scope of the mixed solvent of 0.8 to 3.3 weight part (comprising end value)/100 weight part.This sodium ion and/or lithium ion have the crystalline function of the phosphoric acid zinc coating that forms with the water of degreasing and chemical conversion solution closely knit (densify) on the surface of workpiece.As the example in the source of sodium ion, enumerate SODIUMNITRATE, sodium phosphate, Sodium Nitrite or sodium hydroxide.Partly or entirely SODIUMNITRATE can substitute with Sodium Nitrite.By the effect of nitrite ion, the etching power of acid further increases, and can expect the acceleration of chemical conversion reaction.

Sodium ion can be used as monovalent alkali metal ionic lithium ion and substitute.Specifically, 50-98%, preferred 60-90% and more preferably the sodium ion of 70-80% amount substitute with lithium ion.In other words, sodium ion substitutes with lithium ion, makes that the mol ratio of sodium ion and lithium ion is 50: 50 to 2: 98, preferred 40: 60 to 10: 90 and more preferably 30: 70 to 20: 80.Because degreasing and chemical conversion solution contain lithium ion, the crystal of phosphoric acid zinc coating is further closely knit, and the japanning clinging power is further improved.As the example in the source of lithium ion, enumerate inorganic salt such as lithium nitrate, Trilithium phosphate and lithium nitrite.

Preferably, degreasing and chemical conversion solution were handled 3-10 minute under 40 to 60 ℃ temperature condition.

By using the degreasing and the chemical conversion solution of above-mentioned composition, even a large amount of oil is blended in degreasing and the chemical conversion solution, even or the stirring of degreasing and chemical conversion solution is inadequate, also can form zinc phosphate conversion coating with excellent anti corrodibility and paint film clinging power.

Referring to Fig. 1, degreasing in treatment trough 101 and chemical conversion solution aspirate with pipeline 105 and pump 106, and treated again solution supplemental tank 109 usefulness pipelines 111 and pump 110 turn back in the treatment trough 101.Along pipeline 105, provide fly-ash separator 102, chemical conversion sludge remover 103 and oil eliminator 104.The treatment soln process fly-ash separator 102 that contains polar organic solvent and water, chemical conversion sludge remover 103 and oil eliminator 104, and from treatment soln, remove dust such as iron powder, chemical conversion sludge and oil.This treatment soln temporarily is stored in the treatment soln supplemental tank 109 then.With pump 108 fresh degreasing and chemical conversion solution are added to the treatment soln supplemental tank 109 from the treatment soln groove 107 that new degreasing and chemical conversion solution are housed, regulate then.Degreasing and chemical conversion solution through regulating turn back to this degreasing and chemical conversion groove 101 by above-mentioned pipeline 111 and pump 110.

Fly-ash separator 102 has been removed the iron powder of foreign matter as containing in treatment trough 101.The foreign matter of being removed is excluded, and will therefrom remove the treatment soln of dust again and supply with next chemical conversion sludge remover 103.As the concrete device that can supply fly-ash separator 102 usefulness of the present embodiment, enumerate subsider, centrifuge separator or magnetic separator.

Shown in Fig. 2 A and 2B, be equipped with the stream 102A2 that is used for the making groove 102A1 mobile dividing plate 102A3 that wriggles as the subsider 102A of the example of fly-ash separator 102.Sinuous mobile in groove by the treatment soln that import 102A4 enters by dividing plate 102A3, arrive outlet 102A5.At this moment, the treatment soln mobile flow velocity that makes progress is suppressed to the settling velocity that is lower than foreign matter such as iron powder.Therefore, this foreign matter such as iron powder are deposited on the bottom of groove 102A1, and clean this treatment soln.Subsider 102A is the same with simple assembly cheap, and except the lightweight foreign matter that floats in treatment soln, is effective for the foreign matter of phase counterweight.

As shown in Figure 3, in the centrifuge separator 102B as other example of fly-ash separator 102, treatment soln that enters from import 102B1 and foreign matter such as iron powder are accelerated by the slit shape rotating mechanism 102B2 that provides at tangent direction.Therefore, be split into along among the collecting chamber 102B3 of inwall by centrifugal force, and discharge from solid outlet 102B4 than the heavier solid materials of this solution (foreign matter).Make this treatment soln upwards flow through in pipe 102B5 and from treatment soln outlet 102B6 discharging.Therefore, this treatment soln is cleared up.

As shown in Figure 4, in the magnetic separator 102C as another example of fly-ash separator 102, this treatment soln is introduced from import 102C2, and the rotary drum 102C1 that wherein contains magnet simultaneously is along in the accompanying drawings arrow Y direction rotation.Therefore, when this treatment soln through with stream 102C3 that this rotary drum 102C1 contacts the time, removed magnetic foreign matter such as iron.The foreign matter that is attached to rotary drum 102C1 by magnetic force strikes off by curette 102C4, and the treatment soln of having removed foreign matter is discharged from outlet 102C5.

These subsiders 102A, centrifuge separator 102B and magnetic separator 102C can independences or are used in combination.Especially, the fly-ash separator 102 that combines subsider 102A and magnetic separator 102C has the height removal speed of foreign matter, and is most preferred.

Fly-ash separator 102 according to this embodiment is not limited to above-mentioned three kinds of forms, but comprises other form.Provide fly-ash separator 102 to be used for pipeline 105 in this embodiment, but also can provide in treatment trough 101 inside or outsides own.

Chemical conversion sludge remover 103 is removed the chemical conversion sludge that contains in the treatment soln by above-mentioned fly-ash separator 102.The chemical conversion sludge of being removed is excluded, and the next oil eliminator 104 of treatment soln feeding that will remove the chemical conversion sludge.For chemical conversion sludge remover 103, can not be with any strainer that restrictedly uses, this strainer can be reduced to 150ppm with the concentration of the sludge of treatment soln in the treatment trough 101, makes treatment soln not contaminated.

Oil eliminator 104 is removed the oil that contains in the treatment soln by above-mentioned chemical conversion sludge remover 103.With the oil discharging of being removed, and will remove oil handling solution feeding treatment soln supplemental tank 109.As the example of available oil eliminator 104 in this embodiment, enumerate the hot type oil eliminator, coalescent type oil eliminator and ultrafiltration type oil eliminator.

The hot type oil eliminator is preferably applied to contain the aqueous solution of nonionogenic tenside as fat-free ingredient.The utilization of hot type oil eliminator is when being heated to above specified temperature with this aqueous solution, and become water insoluble and this aqueous solution of nonionogenic tenside is separated into the oil phase be made up of nonionogenic tenside and the biphase characteristic of water.

In coalescent type oil eliminator, the oil droplet with several micron-scales that is dispersed in the aqueous solution passes through strainer.Thereby water/fat liquor is broken, and oil droplet growth and expansion.Therefore, oil droplet can float and be collected.

Ultrafiltration type oil eliminator uses ultrafiltration, that is, use the strainer of being made up of the sieve aperture of the size of mesh with about 0.01 to 0.001 μ m and pass through with about 0.5 * 10 ^-5To 5 * 10 ^-5The press filtration of the low pressure of Pa or suction strainer separate the colloid particulate filtration from solvent.

Select the hot type oil eliminator according to required oil/water sepn degree, coalescent type oil eliminator and ultrafiltration type oil eliminator, and can separately or be used in combination.

Between treatment trough shown in Figure 1 101 and rinse tank 201, be provided for the chemical conversion solution spray of the aluminium aluminum chemistry zone of transformation 300 on the automobile body B.In aluminum chemistry zone of transformation 300, the floor surface of chamber (booth) tilts, and makes that in its center be minimum, so that the chemical conversion solution of spraying does not flow in the treatment trough 101 and back one section rinse tank 201 of the last period as far as possible.

Be used for the chemical conversion solution spray of aluminium is connected in pipeline 302 to the nozzle 304 of the automobile body B of passing aluminum chemistry zone of transformation 300.Nozzle 304 usefulness pumps 303 are supplied with the chemical conversion solution from the aluminium of the chemical conversion solution supplemental tank 301 of the chemical conversion solution that aluminium is housed.In example shown in Figure 1, provide a plurality of nozzles 304 in the end face and the side of chamber, with the chemical conversion solution spray of the aluminium hood to the automobile body B that belongs to aluminium parts, boot-lid panel is on the door.

The chemical conversion solution of the aluminium of collecting on the floor surface of chamber is recovered in the accumulator tank 307, turns back to chemical conversion solution supplemental tank 301 with pipeline 308 and pump 309 again.Simultaneously, provide fly-ash separator 310, chemical conversion sludge remover 311 and oil eliminator 312 along the pipeline 308 that is connected in accumulator tank 307.Fly-ash separator 310 is removed the dust that contains in the chemical conversion solution of the aluminium that is reclaimed.Chemical conversion sludge 311 has been removed the chemical conversion sludge (producing in the treating processes in the treatment trough 101 of previous stage) of aluminium and iron.Oil eliminator 312 has been removed oil.These fly-ash separators 310, chemical conversion sludge remover 311 and oil eliminator 312 can use respectively at above-mentioned fly-ash separator 102, the specific examples shown in chemical conversion sludge remover 103 and the oil eliminator 104.

The chemical conversion solution of the aluminium that uses in the present embodiment is not special restriction, for example comprises hexafluoro titanate and fluorozirconate.The chemical conversion solution of the aluminium that this is fresh is loaded in the groove 305 of chemical conversion solution of aluminium, and transforms in the solution supplemental tank 301 by pump 306 providing chemicals.Regulate the chemical conversion solution that is sprayed to the aluminium on the automobile body B from nozzle 304 like this.

Preferably, the chemical conversion solution of aluminium is handled 20-100 second under the condition of the temperature of the pH of 2.5-10 and 20-70 ℃.

Back one section at aluminum chemistry zone of transformation 300 provides rinse tank 201.Rinse tank 201 usefulness deionized water wash have the automobile body B of the chemical conversion coating that forms in treatment trough 101 and aluminum chemistry zone of transformation 300.In the present embodiment, automobile body B is immersed in the rinse tank 201, with the interior and outside plate of washing automobile body B.Yet carrying out washing treatment can also be handled by the spraying except dip treating and carry out.

In the deionized water in rinse tank 201, the dust, chemical conversion sludge and the oil that adhere on the automobile body B are mixed.Deionized water aspirates with pipeline 202 and pump 203, resupplies the fly-ash separator 310 of the aluminum chemistry zone of transformation 300 of the last period.Removing these dusts, chemical conversion sludge and oil and deionized water re-uses as the deionized water of the chemical conversion solution of aluminium then.At the accumulator tank 307 that can supply with aluminum chemistry zone of transformation 300 with the washing water in the rinse tank 201 of pipeline 202 and pump 203 suctions.Now, fresh deionized water is supplied with rinse tank 201 by deionized water feedway (not shown).

Next, operation will be described.

Automobile body B by welding assembly is carried by japanning travelling belt C when being fixed on the japanning suspension bracket H in the vehicle body packaging technology, and at first is immersed in the treatment trough 101.Because automobile body B is immersed in the treatment trough 101, the foreign matter such as the iron powder that are attached to automobile body B are removed in the treatment trough 101 with the washing and the degreasing effect of oil by degreasing and chemical conversion solution.In addition, in the steel part of having removed oily automobile body B, degreasing and chemical conversion solution and iron reaction, the chemical conversion coating of formation zinc phosphate.

As for the aluminium parts of automobile body B, only carry out dedusting and degreasing.Aluminium parts not with degreasing and chemical conversion solution reaction, and do not form chemical conversion coating.In other words, because degreasing in the present embodiment and chemical conversion solution do not contain the fluorochemical of etching aluminium, the chemical conversion sludge of aluminium can not accumulate in treatment trough 101.Compare with disclosed pre-treatment usual way among the described Japanese Patent translation issuing thing No.2001-515959 in front, can reduce and remove and required working hour, system cost or the similar demand of discharging aluminium sludge.And, because aluminium sludge itself can not produce, compare with the common process method, can reduce the working hour or the system cost of control fluoride concn.

Degreasing in treatment trough 101 and chemical conversion solution are drawn in the pipeline 105 with pump 106.With degreasing and the chemical conversion solution fly-ash separator 102 that stimulates the menstrual flow, make the foreign matter such as the iron powder that in degreasing and chemical conversion solution, contain be removed.With degreasing and the chemical conversion solution chemical conversion eradicator 103 that stimulates the menstrual flow, make the chemical conversion sludge of the iron that in degreasing and chemical conversion solution, contains be removed.With degreasing and the chemical conversion solution oil eliminator 104 that stimulates the menstrual flow, make the oil such as the press oil that in degreasing and chemical conversion solution, contain be removed.

Degreasing and the chemical conversion solution of removing dust, chemical conversion sludge and oil are supplied with treatment soln supplemental tank 109, there, degreasing and chemical conversion solution replenish fresh degreasing and chemical conversion solution with pump 108 from treatment soln groove 107, and suitably regulate.With pipeline 111 and pump 110 degreasing and chemical conversion solution are turned back in the treatment trough 101 then.By this way, degreasing in treatment trough and chemical conversion solution stream are via

pipeline

105 and 111 loops that form.Therefore, can reduce cost by the minimizing of material cost, and the cost that can reduce wastewater treatment.And the use of degreasing and chemical conversion solution makes and can reduce management pretreatment condition used man-hour.In addition, the use of degreasing and chemical conversion solution has significantly reduced the number of washing process.Therefore, the cost of method of wastewater treatment is owing to the amount of used washings reduces.

With the automobile body B feeding aluminum chemistry zone of transformation by treatment trough 101 300 be used for chemical conversion solution spray from the aluminium of nozzle 304.Specifically, the chemical conversion solution in chemical conversion solution supplemental tank 301 is sprayed on the main aluminium parts of automobile body B by nozzle 304 by pump 303 suctions and through pipeline 302.The chemical conversion solution that is sprayed to the aluminium on the automobile body B is collected at the floor surface of chamber, is recovered in the accumulator tank 307 again, aspirates the solution that reclaims from this accumulator tank with pump 309.With the chemical conversion solution of aluminium stimulate the menstrual flow fly-ash separator 310, chemical conversion sludge remover 311 and oil eliminator 312, make their the chemical conversion sludge and the oil of dust, aluminium or iron be removed.With pump 308 the chemical conversion solution of aluminium is turned back to chemical conversion solution supplemental tank 301 then.

By the processing in aluminum chemistry zone of transformation 300, can handle by enough chemical conversion coatings as the aluminium parts of outside plate part such as hood, boot-lid panel and door.Especially, when these aluminium parts are used as the outside plate part of automobile body B, only just can form enough chemical conversion coatings by handling as the spraying of the present embodiment.Therefore, the time of the chemical conversion process of aluminium can be reduced to minimum.

At last, the automobile body B by aluminum chemistry zone of transformation 300 is immersed in the rinse tank 201, the chemical conversion solution that is attached to automobile body B is washed off.Automobile body B is transported in the drying oven, and drying is supplied with then as the electropaining technology of priming.At this moment, by pipeline 202 and pump 203 washings in the rinse tank 201 is incorporated into the upstream side of the fly-ash separator 310 of pipeline 308.By after fly-ash separator 310, chemical conversion sludge remover 310 and the oil eliminator 312, this washings providing chemical is transformed solution supplemental tank 301.Thus, can use deionized water in the rinse tank 201 effectively.

Second embodiment

Fig. 5 is second embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.The place that the present embodiment is different from above-mentioned first embodiment mainly is to use steeping vat 313 in aluminum chemistry zone of transformation 300.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

The aluminum chemistry zone of transformation 300 of the present embodiment is equipped with the aluminum chemistry conversion tank 313 (steeping vat 313) of the chemical conversion solution that aluminium is housed.According to the track of japanning travelling belt C, the full dipping of carrying by japanning travelling belt C of automobile body B or partly impregnated in the aluminum chemistry conversion tank 313.

Here, full dipping is that automobile body B all be impregnated in processing in the chemical conversion solution of aluminium.Part dipping is that the bottom (referring to the B1 among Fig. 6) of automobile body B that only will be under the reaching the standard grade of door skin impregnated in the processing in the chemical conversion solution of aluminium.Figure 6 illustrates the horizontal plane of the solution when carrying out each dip treating.When automobile body B door skin reach the standard grade more than the B1 without any the parts made by aluminum the time, for example when top board or post were fabricated from iron, automobile body B did not need full dipping, it is exactly enough flooding parts made of aluminum.Therefore can use half dip treating.When even top boards etc. are made up of aluminum, automobile body B can be in the bottom below the B1 of reaching the standard grade of door skin with half dip treating of the chemical conversion of aluminium parts, and do not have the impregnated top board etc. can be by the chemical conversion solution spray of atomizer with aluminium.

When use is partly flooded, the volume settings of deciding treatment trough or rinse tank can be the volume less than full dipping.Therefore, can reduce the initial cost of the chemical conversion solution of aluminium, and the required energy of chemical conversion solution that can also reduce heating aluminium.

The chemical conversion solution of the aluminium in steeping vat 313 turns back to chemical conversion solution supplemental tank 301 with pipeline 308 and pump 309.The pipeline 308 that is connected in steeping vat 313 is equipped with fly-ash separator 310, chemical conversion sludge remover 311 and oil eliminator 312.Fly-ash separator 310 has been removed the dust that contains in the chemical conversion solution of aluminium.Chemical conversion sludge remover 311 has been removed the chemical conversion sludge (producing in the treating processes in the treatment trough 101 of the last period) of aluminium and iron.Oil eliminator 312 has been removed oil.These fly-ash separators 310, chemical conversion sludge remover 311 and oil eliminator 312 can use respectively at the specific examples shown in above-mentioned fly-ash separator 102, chemical conversion sludge remover 103 and the oil eliminator 104.

The chemical conversion solution of the aluminium that uses in the present embodiment is not special restriction, for example comprises hexafluoro titanate and fluorozirconate.This fresh aluminum chemistry transforms in the groove 305 of chemical conversion solution that solution is loaded in aluminium, transforms in the solution supplemental tank 301 with pump 306 providing chemicals again.Suitably regulate the chemical conversion solution of aluminium, supply with steeping vat 313 with pipeline 302 and pump 303 then.

Because according to the device of the full steeping vat 313 that floods or partly flood of the use of the equipment of pretreatment before the japanning of the present embodiment as the aluminum chemistry conversion, equipment of pretreatment before this japanning is excellent on handling, especially in the use aluminum is used for during plate portion.

The 3rd embodiment

Fig. 7 is the system view of the 3rd embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.The place that the present embodiment is different from above-mentioned first embodiment mainly is to use rinse tank 120, water-polar organic solvent separator 112 and ion eradicator.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

As shown in Figure 7, on being fixed to suspension bracket H in, automobile body B is carried by japanning travelling belt C.In the present embodiment, provide three steeping vats 101,120 and 201 along the japanning transfer limes.The steeping vat of the upstream side on the throughput direction of being represented by arrow X is the treatment trough 101 that is used for skimming treatment and chemical conversion in the accompanying drawings.The rinse tank 120 of the automobile body B after the steeping vat in the downstream side of treatment trough 101 is to be used to wash degreasing and chemical conversion.Downstream steeping vat is the rinse tank 201 that is used to wash the automobile body B after aluminum chemistry transforms.Treatment trough 101 is equipped with degreasing and chemical conversion solution, and rinse

tank

120 and 201 is equipped with deionized water.

Treatment soln supplemental tank 109 is temporary transient to store a part partially skimmed and the chemical conversion solution of fly-ash separator 102, chemical conversion sludge remover 103 and the oil eliminator 104 by being used to remove foreign matter, chemical conversion sludge and oil, except degreasing and chemical conversion solution, treatment soln supplemental tank 109 is supplied to and removes polar organic solvent that anhydrates and the water that passes through ion eradicator 113 deionizing components by water-polar organic solvent separator 112 (back is described).With pump 108 fresh degreasing and chemical conversion solution are added to treatment soln supplemental tank 109 from treatment soln groove 107, regulate then.Treatment soln groove 107 is equipped with fresh degreasing and chemical conversion solution.This degreasing and chemical conversion solution turn back in degreasing and the chemical conversion groove 101.

Water-polar organic solvent separator 112 has passed through to divide the treatment soln of oil eliminator 104 dried up and polar organic solvent from a part.With isolating water supply ion eradicator 113, and isolating polar organic solvent is supplied with treatment soln supplemental tank 109 by pipeline 114 by pipeline 115.

The polar organic solvent that contains in degreasing of using in the present embodiment and the chemical conversion solution is aforesaid alcohol, glycol ethers, or glycol ether ether.Water-polar organic solvent the separator 112 of wishing the present embodiment uses cheaply the effectively method of separating polar organic solvent and water.For this separation method, can use the separation method that is called pervaporation.In pervaporation, as shown in Figure 8, the mixing solutions of separated polar organic solvent and water is supplied with the separatory membrane 1121 (non-porous film a: side (supply side) film with hole of the size that is lower than 1nm) with selective permeation.The opposite side of film 1121 (per-meate side) 1123 vacuumizes or reduces pressure.The pressure reduction of use between supply side 1122 and per-meate side 1123 makes this mixing solutions as motivating force, and (supply side) 1122 moves to low-tension side (per-meate side) 1123 from the high-tension side.At this moment, the separatory membrane with selective permeation 1121 that has remarkable different velocity of diffusion for various types of materials is inserted between high-tension side 1122 and the low-tension side 1123, to separate this polar organic solvent and water.

Example as above-mentioned separatory membrane 1121, enumerate " the composite membrane on carrier thin film (the open No.59-109204 of Japanese Patent) " with the crosslinked PVA film of toxilic acid, " laminated film (J.Memb.Sci.; 32; 207 (1987)) that the sylvite of 80% carboxymethyl cellulose and 20% polyacrylic ester is handled ", " the composite membrane on the PNA carrier film (J.Memb.Sci.; 36; 463 (1988)) " with crosslinked PVA film, " hollow fiber film of chitosane derivatives (National Meeting of The ChemicalSociety of Japan (1989)) ", " Lalgine cobalt film (Japanese Patent Application No.61-404) ", " chitosan vitriol film (InternationalCongress on Membranes (1987)) " and " by the polyacrylic polyion title complex composite membrane (Japanese Patent Application No.1-224003) of hydrolysis PNA type film surface and the acquisition of ionene class polycation ".

Ion eradicator 113 is from having removed ion component through the water of pipeline 114 by water-polar organic solvent separator 112 supplies.The ion component of removing is got rid of, and residuary water is supplied with treatment soln supplemental tank 109 and supplied with rinse tank 120 through pipeline 114 through pipeline 116.

Ion eradicator 113 in the present embodiment is not special.As shown in Figure 9, ion eradicator 113 is deionized water generators of being furnished with the ion eradicator, and this ion eradicator comprises ion exchange tower 1131 to 1133, decarbonater 1134 and anion exchange tower 1135.Ion exchange tower 1131 is equipped with resin cationoid exchange resin, and it can remove the cationic components that contains in degreasing and chemical conversion solution, zine ion for example, nickel ion, and mn ion.Ion exchange tower 1132 is equipped with the styrenic strong anion-exchange resin, and it can remove the anionic group that contains in degreasing and chemical conversion solution, phosphate anion for example, nitrate ion etc.Ion exchange tower 1133 is equipped with the strong-acid cation-exchange resin of H form, and it is the deionized water generator that is generally used for increasing water purity.Anion exchange tower 1135 is equipped with the styrenic strong anion-exchange resin of OH form.

Equipment of pretreatment before the japanning of the present embodiment is equipped with following three recycle systems.As shown in Figure 7, in first recycle system, the treatment soln in degreasing and chemical conversion groove 101 is by degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, treatment soln supplemental tank 109 and degreasing and 101 circulations of chemical conversion groove.

In second recycle system, the treatment soln in degreasing and chemical conversion groove 101 is by degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, water-polar organic solvent separator 112, ion eradicator 113 and rinse tank 120 circulations.

In the 3rd recycle system, with pipeline 121 and pump 122 solution in the rinse tank 120 is incorporated in the fly-ash separator 102, then by fly-ash separator 102, chemical conversion sludge remover 103 and oil eliminator 104 circulations.

Except above three recycle systems, make up the following recycle system.

The 4th recycle system is by being increased to above-mentioned first recycle system with water-polar organic solvent separator 112, that is, the loop of degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, treatment soln supplemental tank 109 and degreasing and chemical conversion groove 101 forms.So be supplied in the treatment soln supplemental tank 109 by water-polar organic solvent separator 112 isolating polar organic solvents.

The 5th recycle system is by being increased to treatment soln supplemental tank 109 above-mentioned second recycle system, that is, form in the loop of degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, water-polar organic solvent separator 112, ion eradicator 113 and rinse tank 120.The deionized water that a part is removed by ion eradicator 113 so is fed in the treatment soln supplemental tank 109.

The 6th recycle system is by being increased to water-polar organic solvent separator 112 above-mentioned the 3rd recycle system, that is, form in the loop of rinse tank 120 and degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, treatment soln supplemental tank 109 and degreasing and chemical conversion groove 101.Be supplied to like this in the treatment soln supplemental tank 109 by water-polar organic solvent separator 112 isolating polar organic solvents.

The 7th recycle system is by being increased to ion eradicator 113 above-mentioned the 6th recycle system, that is, form in the loop of rinse tank 120 and degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, water-polar organic solvent separator 112, treatment soln supplemental tank 109 and degreasing and chemical conversion groove 101.Deionizing from pass through water-polar organic solvent separator 112 isolating water, and incite somebody to action the water supply rinse tank 120 of deionizing.

The 8th recycle system is by being increased to ion eradicator 113 above-mentioned the 6th recycle system, that is, form in the loop of rinse tank 120 and degreasing and chemical conversion groove 101, fly-ash separator 102, chemical conversion sludge remover 103, oil eliminator 104, water-polar organic solvent separator 112, treatment soln supplemental tank 109 and degreasing and chemical conversion groove 101.Deionizing from pass through water-polar organic solvent separator 112 isolating water, and incite somebody to action the water supply treatment soln supplemental tank 109 of deionizing.

As mentioned above, the equipment of pretreatment before the japanning of the present embodiment comprises first three recycle systems to third circulation system of rough sort, and eight recycle systems of exhaustive division.Therefore, the composition of the treatment soln in the degassing and chemical conversion groove 101 is stable, and can form the excellent chemical conversion coating that quality does not change in handling continuously.

Because the equipment of pretreatment before the japanning of the present embodiment comprises the 3rd recycle system, the specific conductivity of the washings in rinse tank 120 can remain on below the 20 μ S/cm, and can prevent that oil, treatment soln or foreign matter such as iron powder are attached to the surface of workpiece.And, can reduce oil, treatment soln and the foreign matter such as the iron powder that take in the subsequent technique as far as possible.

Next, operation will be described.

Similar to first embodiment, carry by japanning travelling belt C by the automobile body B of welding assembly, in treatment trough 101, carry out the washing first time and degreasing.At this moment, on steel part, formed the zinc phosphate chemical conversion coating.

Use deionized water wash by the automobile body B of treatment trough 101 by being immersed in the rinse tank 120.Therefore degreasing that is attached to automobile body B and brings and chemical conversion solution, dust, chemical conversion sludge and oil were removed before the aluminum chemistry zone of transformation 300 of follow-up phase.Therefore, except the quality-improving of the chemical conversion coating that forms with degreasing and chemical conversion solution, it can also prevent that the foreign matter that the chemical conversion solution of aluminium is wherein had from polluting.Therefore, lower the recirculation load of the chemical conversion solution of aluminium, improve recirculation efficient.

With the automobile body B feeding aluminum chemistry zone of transformation 300 by rinse tank 120 and by the chemical conversion solution spray of nozzle 304 usefulness aluminium.By this way, aluminium parts can be handled by enough chemical conversion coatings.

At last, the automobile body B by aluminum chemistry zone of transformation 300 is impregnated in the rinse tank 201, is attached to the treatment soln of automobile body B with washing.Then automobile body B is transported to drying oven, dry again.The feeding of exsiccant vehicle body is as the electropaining technology of priming.

The 4th embodiment

Figure 10 is the 4th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.

The present embodiment provides vacuum distilling unit 130, replaces the fly-ash separator 102 of the 3rd embodiment, chemical conversion sludge remover 103, oil eliminator 104, water-polar organic solvent separator 112 and oil eliminator 113.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

Treatment soln in degreasing and chemical conversion groove 101 and the solution in rinse tank 120 are respectively with

pump

106 and 122 suctions and supply vacuum distilling unit 130.Solution separating be will supply with and polar organic solvent, water and other material become.To in vacuum distilling unit 130, supply with treatment soln supplemental tank 109 by isolating polar organic solvent by pipeline 131.By pipeline 131 will be in vacuum distilling unit 130 isolating a part of water supply treatment soln supplemental tank 109, and residuary water is supplied with rinse tank 120 by pipeline 132.

Except polar organic solvent and water, isolating material is foreign matter such as iron powder, chemical conversion sludge and oil in vacuum distilling unit 130, and with 130 dischargings from the vacuum distilling unit of this sludge.

Figure 11 is the synoptic diagram that shows vacuum distilling unit 130.Vacuum distilling is wherein by pressure being reduced to approximately for example 10 ^-2Reduce the distillating method of boiling point to tens holders.In the present embodiment, because wish independent separate polar organic solvent and water from treatment soln, so two

vacuum distilling unit

1301 and 1302 are provided shown in same accompanying drawing.These two

vacuum distilling unit

1301 and 1302 have same structure, comprise to the cell cube 1303 of wherein supplying with treatment soln.1303 pressure lowers by vacuum pump 1304 in cell cube.Each

vacuum distilling unit

1301 and 1302 is equipped with well heater 1305, so that the temperature in the cell cube 1303 is increased to preset temperature separately.The treatment soln of introducing in each cell cube 1303 heats under reduced pressure by each well heater 1305.By preset temperature being set to the boiling point of each target substance, only target substance is evaporated and is introduced in the generating tube 1306, again by water cooler 1307 liquefaction.

As mentioned above, in the present embodiment, because wish from treatment soln separating polar organic solvent and water separately, so in first section vacuum distilling unit 1301 shown in the accompanying drawing, only polar organic solvent is separated and supply with as shown in figure 10 treatment soln supplemental tank 109.In second section vacuum distilling unit 1302, have only water separated from the treatment soln of the vacuum distilling unit 1301 that leaves the last period, supply with as shown in figure 10 treatment soln supplemental tank 109 and rinse tank 120 then.Sludge that will in vacuum distilling unit 1302, stay such as foreign matter, chemical conversion sludge and oil discharging.

Because boiling point under reduced pressure reduces, the heat energy of supply well heater 1305 is lower than the heat energy in the big steam distillation.Especially, wish to use from the used heat that paints drying oven as the energy of supplying with well heater 1305.

According to the equipment of pretreatment of the present embodiment, the solution in treatment trough 101 and rinse tank 120 only is recovered and recirculation by vacuum distilling unit 130.Therefore, compare with the 3rd embodiment, total system can be simplified and reduce cost.

The 5th embodiment

Figure 12 is the system view of the 5th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.

In the present embodiment, carrying out washing treatment is undertaken by spraying, replaces the dip treating with rinse tank 120 of above-mentioned the 3rd embodiment.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

Specifically, next section at treatment trough 101 provides rinsing district 140.The floor surface of chamber tilts, so that heart place is minimum therein, makes the deionized water of spraying flow to the treatment trough 101 of the last period and back one section aluminum chemistry zone of transformation 300 hardly.

Be used for the nozzle 141 that deionized water is sprayed on the automobile body B of passing rinsing district 140 is connected in pipeline 114.Employed deionized water obtains by ion eradicator 113.In example shown in Figure 12, a plurality of nozzles 141 that are used for deionized water is sprayed on the whole automobile body B are provided in the end face of chamber and side.

Reclaim in washings accumulator tank 142 at the employed water of collecting on the floor surface of chamber, turn back to fly-ash separator 102 by pipeline 143 and pump 144 again, this is the upstream in first recycle system.

The 6th embodiment

Figure 13 is the system view of the 6th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.

In the present embodiment, carrying out washing treatment is undertaken by atomizer, replaces the dip treating with the rinse tank 120 of above-mentioned the 4th embodiment.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

Be used for the nozzle 141 that deionized water is sprayed on the automobile body B of passing rinsing district 140 is connected in pipeline 132.Employed deionized water obtains by vacuum distilling unit 130.In example shown in Figure 13, a plurality of nozzles 141 that are used for deionized water is sprayed on the whole automobile body B are provided in the end face of chamber and side.

Reclaim in washings accumulator tank 142 at the employed water of collecting on the floor surface of chamber, turn back in the vacuum distilling unit 130 by pipeline 143 and pump 144 again.

The 7th embodiment

Figure 14 is the system view of the 7th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out skimming treatment, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.

In the present embodiment, the rinsing with rinse tank 120 or rinsing district 140 of the above-mentioned the 3rd to the 6th embodiment is handled and is carried out in aluminum chemistry zone of transformation 300.Those of other assembly and above-mentioned embodiment are similar, and identical assembly provides identical Reference numeral.

Shown in same accompanying drawing, automobile body B transmits by japanning travelling belt C on being fixed to suspension bracket H.In the present embodiment, the steeping vat of the upstream side in the throughput direction of representing with arrow X is the treatment trough 101 that is used for degreasing and chemical conversion in the accompanying drawings.The rinse tank 201 of the automobile body B after the steeping vat in downstream side is to be used to wash degreasing and chemical conversion.Treatment trough 101 is equipped with degreasing and chemical conversion solution, and this is the sort of identical with above-mentioned first to the 6th embodiment, and rinse tank 201 is equipped with deionized water.

Between treatment trough shown in Figure 14 101 and rinse tank 201, provide to be used for selectivity with the chemical conversion solution spray of deionized water and the aluminium rinsing-aluminum chemistry zone of transformation 400 on the automobile body B.In rinsing-aluminum chemistry zone of transformation 400, the floor surface of chamber tilts, so that heart place is minimum therein, makes the deionized water of spraying not flow to the treatment trough 101 of the last period and back one section rinse tank 201 as far as possible.

Be used for the chemical conversion solution spray of deionized water or aluminium is connected in pipeline 402 to the nozzle 401 on the automobile body B of passing rinsing-aluminum chemistry zone of transformation 400.Nozzle 401 usefulness pumps 404 and 406 are supplied with the chemical conversion solution of deionized water or aluminium respectively by washings supplemental tank 403 that deionized water is housed and chemical conversion solution supplemental tank 405.Here,, provide T-valve 407, so that at the solution of conversion supplying-nozzle 401 from the deionized water of washings supplemental tank 403 and between from the chemical conversion solution of the aluminium of chemical conversion solution supplemental tank 405 at the middle part of pipeline 402.Pump 404,406 and this T-valve are by operating from the command signal of controller 502 described below.

Chemical conversion solution at used deionized water of collecting on the floor surface of chamber and aluminium independently is recovered to by pipeline 408,409 and 410 in washings accumulator tank 412 and the chemical conversion solution accumulator tank 418 respectively.In this, pipeline 408 is equipped with the T-valve 411 that is used to change each accumulator tank.This T-valve also command signal of the controller 502 by is hereinafter described operated.

The used deionized water that is recovered to washings accumulator tank 412 through pipeline 408,409 turns back to washings supplemental tank 403 by pipeline 414 and pump 413.The pipeline 414 that is connected in washings accumulator tank 412 is equipped with fly-ash separator 415, chemical conversion sludge remover 416 and oil eliminator 417.Fly-ash separator 415 has been removed the dust that contains in the used deionized water that reclaims.This chemical conversion sludge remover 415 has been removed the chemical conversion sludge (producing in the treating processes in the treatment trough 101 of the last period) of aluminium and iron.Oil eliminator 417 has been removed oil.

On the other hand, the chemical conversion solution that is recovered to the used aluminium in the chemical conversion solution accumulator tank 418 through pipeline 408 and 410 turns back to chemical conversion solution supplemental tank 405 by pipeline 420 and pump 419.The pipeline 420 that is connected in chemical conversion solution accumulator tank 418 is equipped with fly-ash separator 421, chemical conversion sludge remover 422 and oil eliminator 423.Fly-ash separator 421 has been removed the dust that contains in the chemical conversion solution of the used aluminium that reclaims.Chemical conversion sludge remover 422 has been removed the chemical conversion sludge (producing in the treating processes in the treatment trough 101 of the last period) of aluminium and iron.Oil eliminator 423 has been removed oil.

These fly-ash separators 415,421, chemical conversion sludge remover 416,422, and oil eliminator 417,423 can use at above-mentioned fly-ash separator 102 specific examples shown in chemical conversion sludge remover 103 and the oil eliminator 104 respectively.

The chemical conversion solution of the aluminium that uses in the present embodiment is not special restriction, for example, comprises hexafluoro titanate and fluorozirconate.The chemical conversion solution of this fresh aluminium is loaded in the groove 424 of chemical conversion solution of aluminium and with pump 425 providing chemicals and transforms solution supplemental tank 405.The chemical conversion solution that is sprayed to the aluminium of automobile body B by nozzle 401 is regulated by the chemical conversion solution of this fresh aluminium.

Preferably, the chemical conversion solution of aluminium is handled 20-100 second under the temperature of the pH of 2.5-10 and 20-70 ℃.

In back a section of rinsing-aluminum chemistry zone of transformation 400, provide rinse tank 201.Rinse tank 201 usefulness deionized water wash have the automobile body B of the chemical conversion coating that forms in treatment trough 101 and rinsing-aluminum chemistry zone of transformation 400.In the present embodiment, automobile body B is immersed in the rinse tank 201, with the interior and outside plate of washing automobile body B.Yet carrying out washing treatment can also be handled by the spraying except dip treating and realize.

In the deionized water in rinse tank 201, the dust, chemical conversion sludge and the oil that are attached to automobile body B are mixed.Deionized water aspirates by pipeline 202 and pump 203, resupplies the washings accumulator tank 412 (or fly-ash separator 415) in the rinsing-aluminum chemistry zone of transformation 400 in the last period.After removing these dusts, chemical conversion sludge and oil, this deionized water re-uses with deionized water as washing then.Fresh deionized water is supplied with rinse tank 201 by deionized water feeding unit that show, that do not provide separately in the accompanying drawings.

In the present embodiment, the beginning of pump 404,406 and stop and the operation of T-valve 407,411 by carrying out from command signal based on the controller 502 of the technical parameter of the type of vehicle that detects by type of vehicle detector 501.For example, provide type of vehicle detector 501 in the technology before automobile body B is immersed in treatment trough 101.Type of vehicle detector 501 has been read the technical parameter of relevant type of vehicle from the technical parameter storage media, this medium has been stored the technical parameter of each automobile body B and has been installed on each automobile body B.Here, whether type of vehicle detector 501 detects automobile body B at least is the iron vehicle body, and aluminium vehicle body, or hybrid vehicle body are transferred to controller 502 with detected technical parameter then.This is controlled at and will describes in detail later on.

Next, operation will be described.

Automobile body B by welding assembly is carried by japanning travelling belt C when being fixed on the japanning suspension bracket H in the vehicle body packaging technology, and at first is immersed in the treatment trough 101.Because automobile body B is immersed in the treatment trough 101, be removed in the treatment trough 101 with the washing and the degreasing effect of oil by degreasing and chemical conversion solution so be attached to the foreign matter such as the iron powder of automobile body B.In addition, in the steel part of the automobile body B of removing oil, degreasing and chemical conversion solution and iron reaction, the chemical conversion coating of formation zinc phosphate.Yet,, only carry out dedusting and degreasing as for the aluminium parts of automobile body B.This aluminium parts not with degreasing and chemical conversion solution reaction, do not form chemical conversion coating.

Will be automobile body B feeding rinsing-aluminum chemistry zone of transformation 400 by treatment trough 101, be used for any spraying from the chemical conversion solution of the deionized water of nozzle 401 and aluminium then.In other words, when the material technology parameter of the automobile body B that detects by type of vehicle detector 501 was the iron vehicle body, the chemical conversion of aluminium was unnecessary, made rinsing-aluminum chemistry zone of transformation 400 as the rinsing district.Therefore, controller 502 is transferred to starting command pump 404 simultaneously and will ceases and desist order and is transferred to pump 406.And, T-valve 407 is transformed into washings supplemental tank 403, and this T-valve 411 is transformed into washings accumulator tank 412.

Deionized water in washings supplemental tank 403 is sprayed on the whole iron automobile body B from nozzle 401 through pipeline 402 by pump 404 suctions again.On the floor surface of chamber, collect the deionized water that is sprayed on the automobile body B, be recovered in the washings accumulator tank 412, then with pump 413 suctions through pipeline 408,409.Subsequently, deionized water is by fly-ash separator 415, chemical conversion sludge remover 416 and oil eliminator 417, removing dust, chemical conversion sludge such as aluminium and the iron that in deionized water, contains, and oil.Deionized water turns back to washings supplemental tank 403 then.

On the other hand, when the material technology parameter of the automobile body B that detects by type of vehicle detector 501 was those of the vehicle body made by aluminum or aluminum alloy, rinsing-aluminum chemistry zone of transformation 400 was as the aluminum chemistry zone of transformation.Therefore, controller 502 is transferred to stop instruction pump 404 and simultaneously starting order is transferred to pump 406.And, T-valve 407 is transformed into chemical conversion solution supplemental tank 405, and T-valve 411 is transformed into conversion solution accumulator tank 418.

The chemical conversion solution of the aluminium in chemical conversion solution supplemental tank 405 is sprayed to by nozzle 401 on the whole automobile body B (or main aluminium parts) with pump 406 suctions with through pipeline 402.On the floor surface of chamber, collect the chemical conversion solution that is sprayed to the aluminium on the automobile body B, be recovered to chemical conversion solution accumulator tank 418, then with pump 419 suctions.Subsequently, the chemical conversion solution that makes aluminium is by fly-ash separator 421, chemical conversion sludge remover 422 and oil eliminator 423, removing dust, chemical conversion sludge such as aluminium and the iron that in the chemical conversion solution of aluminium, contains, and oil.Allow the chemical conversion solution of aluminium turn back to chemical conversion solution supplemental tank 405 through pipeline 420 then.

During in rinsing-aluminum chemistry zone of transformation 400 this handled, when automobile body B is the iron vehicle body, the automobile body B deionized water wash.Therefore, the phosphoric acid zinc coating that forms in handling in front can improve quality, and can be suppressed at follow-up phase and take treatment soln in the rinse tank 201 to.When automobile body B was aluminium vehicle body or hybrid vehicle body, as outside plate part, as hood, the aluminium parts of boot-lid panel and door can be handled with chemical conversion coating in rinsing-aluminum chemistry zone of transformation 400.Especially, when these aluminium parts are used as the outside plate part of automobile body B, can only form sufficient chemical conversion coating by handling as the spraying of the present embodiment.Therefore, the time of the chemical conversion process of aluminium can be minimized.In addition, because accumulator tank 412 and 418 is used for using respectively the chemical conversion solution washing of deionized water and aluminium separately, the recirculation of the chemical conversion solution of the aluminium that is reclaimed load reduces and recirculation efficient increases.

At last, the automobile body B by rinsing-aluminum chemistry zone of transformation 400 is impregnated in the rinse tank 201, is attached to treatment soln on the automobile body B with washing.Then automobile body B is transported in the drying oven, and dry.The exsiccant vehicle body is supplied with as the electropaining technology of priming.

The 8th embodiment

Figure 15 is the system view of the 8th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention.Similar to first embodiment, this accompanying drawing has shown the pretreated method before the japanning, wherein at workpiece, for example carries out degreasing, surface adjustment and chemical conversion coating on the vehicle body, prepares as the surface of electropaining.

The place that the present embodiment is different from above-mentioned first embodiment mainly is to provide a plurality of

nozzles

304 and 315 and use type of vehicle detector 501 and controller 502 at the aluminum chemistry zone of transformation.Because other component class is similar to above-mentioned embodiment those, same components has provided same reference numerals.

In the present embodiment, as shown in figure 15, be used for the chemical conversion solution spray of aluminium is connected to pipeline 302 and pipeline 316 to the

nozzle

304 and 315 on the automobile body B of passing aluminum chemistry zone of transformation 300.

Nozzle

304 and 315 usefulness pumps 303 and pump 314 are supplied with the chemical conversion solution of aluminium by the chemical conversion solution supplemental tank 301 of the chemical conversion solution that aluminium is housed.Example shown in Figure 15 has the configuration of two sections, wherein is being provided on the end face of each chamber and the side the chemical conversion solution spray of the aluminium a plurality of nozzles on hood, boot-lid panel and the door (they are aluminium parts of automobile body B).In first section, nozzle 304 so that they with the chemical conversion solution spray of aluminium to arranging corresponding to the mode on the part of the aluminium parts of hybrid vehicle body.In second section, nozzle 315 so that they the chemical conversion solution spray of aluminium is arranged to the mode of the part except the aluminium parts of hybrid vehicle body.

Especially, in the present embodiment, pump 303 and 314 is by starting based on the command signal of coming self-controller 502 of the technical parameter of the type of vehicle that detects with type of vehicle detector 501 and stopping.For example, provide type of vehicle detector 501 in the technology before automobile body B is immersed in treatment trough 101.Type of vehicle detector 501 has been read the technical parameter of relevant type of vehicle from the technical parameter storage media, this medium has been stored the technical parameter of each automobile body B and has been installed on each automobile body B.Here, it is the iron vehicle body that type of vehicle detector 501 detects automobile body B at least, the aluminium vehicle body, and still hybrid vehicle body is transferred to controller 502 with detected technical parameter then.The details of this control will be described afterwards.

Rinse tank 201 is provided after aluminum chemistry zone of transformation 300.Rinse tank 201 usefulness deionized water wash have the automobile body B of chemical conversion coating on it.In the present embodiment, automobile body B is immersed in the rinse tank 201, with the interior and outside plate of washing automobile body B.Yet this carrying out washing treatment can also be handled by the spraying except dip treating and carry out.

Next, operation will be described.

In on being fixed to japanning suspension bracket H, the white automobile body B by welding assembly is carried with japanning travelling belt C in the vehicle body packaging technology, at first is immersed in the treatment trough 101.Because automobile body B is immersed in the treatment trough 101, the foreign matter such as the iron powder that are attached to automobile body B are removed in the treatment trough 101 with the washing and the degreasing effect of oil by degreasing and chemical conversion solution.In addition, removing on the steel part of the automobile body B of deoiling, degreasing and chemical conversion solution and iron react and have formed the chemical conversion coating of zinc phosphate.

Automobile body B by treatment trough 101 is transported to aluminum chemistry zone of transformation 300, there, carries out control as shown in figure 16.

Specifically, the type of vehicle detector 501 that is arranged on the inlet of the preceding equipment of pretreatment of japanning detects the material technology parameter of automobile body B, more particularly, automobile body B is the iron vehicle body, aluminium vehicle body, or hybrid vehicle body, and continue the test material technical parameter is transferred to controller 502.Be transferred to the data and the japanning travelling belt C stores synchronized of carrying automobile body B of the relevant material technology parameter of controller 502 from type of vehicle detector 501.Controller 502 is identified in the pretreatment process data corresponding to each vehicle body.

As shown in figure 16, when the data of relevant material technology parameter by type of vehicle detector 501 (S1) when drawing, controller 502 has passed through the judgement among step 2 (S2) and 4 (S4) before automobile body B is transported to aluminum chemistry zone of transformation 300.Specifically, whether the automobile body B of the mensuration data that draw is iron vehicle body (it all is made up of iron component) in step 2 (S2).When automobile body B was the iron vehicle body, operation proceeded to step 3 (S3), and its middle controller 502 is transferred to pump 303 and 314 with stop signal, so as not with the chemical conversion solution spray of aluminium on automobile body B.

In step 2 (S2), when automobile body B was not the iron vehicle body, operation proceeded to step 4 (S4), and wherein it measures whether automobile body B is aluminium vehicle body (all being made up of the aluminium assembly).Here, when automobile body B was the aluminium vehicle body, operation proceeded to step 6 (S6), and its middle controller 502 is transferred to pump 303 and 314 with actuate signal, was sprayed on the interior and outside plate of aluminium vehicle body from all

nozzles

304 and 315 with the chemical conversion solution with aluminium.

In step 4 (S4), when vehicle body was not the aluminium vehicle body, this vehicle body was identified as hybrid vehicle body, and operation proceeds to step 5 (S5).Controller 502 is transferred to actuate signal pump 303 and stop signal is transferred to pump 314, with only by nozzle 304 with the chemical conversion solution spray of aluminium to the aluminium parts of hybrid vehicle body.

As mentioned above, in aluminum chemistry zone of transformation 300, can be according to the material of the assembly of automobile body B only with the chemical conversion solution spray of aluminium to necessary part, and the consumption that can reduce the chemical conversion solution of aluminium.When the automobile body B in being transported to aluminum chemistry zone of transformation 300 was hybrid vehicle body, configuration in the above-described embodiment should make that only pump 303 is driven, and other pump 314 is stopped.Yet, the invention is not restricted to this.This configuration can so that

pump

303 and 314 the two be driven, and a selecteed mode in the

nozzle

304 and 315 of discharging chemical conversion solution is set.

By the processing in aluminum chemistry zone of transformation 300, can handle by enough chemical conversion coatings as the aluminium parts of outside plate such as hood, boot-lid panel and door use.When especially being used as the outside plate part of automobile body B, these aluminium parts can only form enough chemical conversion coatings by handling as the spraying of the present embodiment.Therefore, the time of aluminum chemistry conversion process can be reduced to minimum.

At last, the automobile body B by aluminum chemistry zone of transformation 300 is immersed in the rinse tank 201, the chemical conversion solution that is attached to automobile body B is washed off.Automobile body B is transported in the drying oven, drying, feeding belongs to the electropaining technology of priming again.

The 9th embodiment

Figure 17 is the plan view of the 9th embodiment of the equipment of pretreatment before the demonstration japanning of the present invention, and Figure 18 is the system view that shows it.Similar to first embodiment, this accompanying drawing has shown to be workpiece, and for example the preceding pretreated method of japanning that is used to carry out degreasing, surface adjustment and chemical conversion that prepare on the surface is done in the electropaining of vehicle body.The place that the present embodiment is different from above-mentioned the 8th embodiment is that mainly the japanning travelling belt C in aluminum chemistry zone of transformation 300 is separated, and uses steeping vat 313 in aluminum chemistry zone of transformation 300.Other component class is similar to those of above-mentioned embodiment, and identical assembly provides identical Reference numeral.

As shown in figure 17, the japanning travelling belt C of the present embodiment is divided into two conveying belt C1 and C2, and connects between treatment trough 101 and rinse tank 201.Provide aluminum chemistry zone of transformation 300 a travelling belt C1 side.In another travelling belt (bypass line of the present invention) C2 side, automobile body B is transferred in just on being fixed to suspension bracket H.In the technology on this another travelling belt C2, can carry out deionized water spraying, so that prevent the drying of the phosphoric acid zinc coating that on the surface of iron parts, forms.

Japanning travelling belt C is equipped with travelling belt separate units 503 and is equipped with travelling belt connector element 504 in the ingress of rinse tank 201 in the exit of treatment trough 101.Travelling belt separate units 503 and travelling belt connector element 504 each controller that can comprise the converting unit of conveyor track and control this converting unit.The controller 502 of the present embodiment is transferred to converted command signal the controller of this converting unit.Specifically, when detecting the material technology parameter of automobile body B, the type of vehicle detector 501 that provides in the ingress of treatment trough 101 is transferred to controller 502 with the test material technical parameter.According to the material technology parameter of vehicle body, controller 502 decision automobile body B are transported on travelling belt C1 or the travelling belt C2.Below this control will be described.

As shown in figure 18, the aluminum chemistry zone of transformation 300 of the present embodiment is equipped with the aluminum chemistry conversion tank 313 of the chemical conversion solution that aluminium is housed.The automobile body B of carrying by travelling belt C1 is flooded entirely according to the track of travelling belt C1.

Because the device that the equipment of pretreatment before the japanning of the present embodiment uses full dipping to transform as aluminum chemistry with steeping vat 313, the equipment of pretreatment before this japanning is excellent in processing, especially in aluminum is used for during plate portion.

In the present embodiment, dip treating is used in aluminum chemistry zone of transformation 300.Yet the

nozzle

304 and 315 shown in the 8th embodiment that aluminum chemistry zone of transformation 300 that can be by being provided for travelling belt C1 is handled in spraying carries out.

Next, operation will be described.Because the treatment process in treatment trough 101 and rinse tank 201 is similar in the 8th embodiment those, so be described in treatment process in its method with reference to Figure 19.

The type of vehicle detector of arranging in the import of the equipment of pretreatment before japanning 501 detects the material technology parameter of automobile body B, specifically, automobile body B is the iron vehicle body actually, the aluminium vehicle body, or hybrid vehicle body, the material technology parameter that continues to detect is transferred to controller 502.Be transferred to the data and japanning travelling belt C stores synchronized of the relevant material technology parameter of controller 502 by type of vehicle detector 501.Which vehicle body in the controller 502 identification pretreatment processs is corresponding to which data.

As shown in figure 19, when drawing the data of relevant material technology parameter by type of vehicle detector 501 (S11), the judgement of the step 12 (S12) when controller 502 is worked as automobile body B and is suggested from treatment trough 101.Specifically, it judges in step 12 (S12) whether the automobile body B of the data that draw is iron vehicle body (it is made up of iron component fully).When automobile body B was the iron vehicle body, operation proceeded to step 13 (S13), and its middle controller 502 is transferred to travelling belt separate units 503 and travelling belt connector element 504 with command signal, so that this iron automobile body B is transported to bypass line.Therefore, the iron vehicle body is without the chemical conversion solution spray of aluminium.

At step 12 (S12), when automobile body B was not the iron vehicle body, this automobile body B was identified as aluminium vehicle body or hybrid vehicle body.Therefore, this operation continues to step 14 (S14), and controller 502 is transferred to travelling belt separate units 503 and travelling belt connector element 504 with command signal, so that this aluminium vehicle body or hybrid vehicle body are transported on the line of aluminum chemistry zone of transformation 300.Therefore, this vehicle body is impregnated in the steeping vat 313, and carries out the aluminum chemistry conversion.

In the present embodiment,, only need the aluminium vehicle body and the hybrid vehicle body process travelling belt C1 of aluminum chemistry conversion and allow the iron vehicle body avoid bypass line by the travelling belt C that separately paints.Therefore, the transfer rate of travelling belt C1 and C2 can be lowered to the only about half of of japanning travelling belt C V-bar, makes the length of aluminum chemistry conversion tank 313 to be shortened.

Once in a while, when using the spraying shown in Figure 15 to handle in aluminum chemistry zone of transformation 300, the aluminium treatment condition of aluminium vehicle body and hybrid vehicle body can further change.

Notice that the above embodiment of having narrated helps to understand the present invention, but does not limit the present invention.Therefore, disclosed in the above-described embodiment each assembly is used for being included in all design variant and the equivalent in the technology of the present invention scope.

In the automobile body B of above-mentioned embodiment, parts such as hood, boot-lid panel and door are made of aluminum, but can be made by aluminium alloy.

Hereinafter, prove effect of the present invention with further embodying embodiments of the invention and comparative example.Following examples are used for determining the degreasing of use in the above-described embodiment and the effect of chemical conversion solution.

Embodiment

The degreasing of embodiment and chemical conversion solution use carbiphene (DEGMEE) as polar organic solvent with the basis that consists of shown in Figure 20, SODIUMNITRATE is as the sodium compound in sodium ion source, lithium nitrate is as the lithium compound in lithium source, ortho-phosphoric acid is originated as phosphate anion, zinc nitrate is as the zn cpds in zine ion source, the manganic compound that nickelous nitrate is originated as mn ion as the nickel compound and the manganous nitrate in nickel ion source prepares.

Fluorozirconate (Deoxylyte 54C is produced by Henkel Corp.) is as the chemical conversion solution of the aluminium of embodiment.

Preparation cold-rolled steel (Fe), galvanized steel (Zn), three class test specimens of aluminium 6111 (Al) are also used the acetone degreasing.Then, this test specimen 0.5g/m ²The mixing oil coating, this mixing oil contains three rust-proof oils of roughly the same measuring (by Ciosmo oil Co., the Rustclean K that Ltd produces, by Idemitsu Kosan Co., the NR3 that Ltd produces, the Nonrust PN-1 that produces by Nippon oil Corp.), thus prepare the test specimen that has the test oil surface separately.These test specimens are with the chemical conversion solution-treated of above-mentioned degreasing and chemical conversion solution and aluminium.Estimate the characteristic and the performance of gained phosphoric acid zinc coating, specifically, the density of glue spread, crystallization coating, slubbing japanning clinging power and two roads japanning clinging power.Their result is illustrated among Figure 20.

Processing with degreasing and chemical conversion solution is undertaken by each test specimen is impregnated in degreasing and the chemical conversion solution.Treatment time is set to 300 seconds, and the temperature of degreasing and chemical conversion solution is set to 40 ℃.Processing with the chemical conversion solution of aluminium is carried out to each test specimen by the chemical conversion solution spray with aluminium.Spray time is 20,30 and 100 seconds.The pH of the chemical conversion solution of aluminium is set to 4.0, and its temperature is set to 40 ℃.

With A (very good), B (well), the result of the density of glue spread, crystallization coating, slubbing japanning clinging power and two roads japanning clinging power is estimated in four classification of C (poor slightly) and D (poor).

After respectively handling test specimen, measure glue spread with the moisture eliminator drying.Convert glue spread to weight (g)/1m ²Here, have excellent erosion resistance and bounding force, need have about 2 to 3.5g/m in order to make the zinc phosphate chemical conversion coating ²Glue spread evenly and fine and close crystallization coating.Therefore, 2-2.5g/m ²Glue spread be evaluated as A (very good); 2.6-3.5g/m ²Glue spread be evaluated as B (well); 1.5-1.9g/m ²Glue spread be evaluated as C (poor slightly); Be lower than 1.5g/m ²Glue spread be evaluated as D (poor).

For the density of crystallization coating, after processing from the center draw samples of each test specimen, and with the shape and size of scanning electronic microscope (SEM) observation zinc phosphate crystallization coating.

In an embodiment, estimate each sample, show that the crystalline size of the density that 5 μ m or 5 μ m are following is be evaluated as A (very good) according to following standard; 5 μ m are above to be evaluated as B (well) to 10 μ m or the density below the 10 μ m; 10 μ m are above to be evaluated as C (poor slightly) to 20 μ m or the density below the 20 μ m; The above density of 20 μ m or 20 μ m is be evaluated as D (poor).

Slubbing japanning clinging power is estimated by painting to test specimen after processing.Specifically, the test specimen after handling is immersed in the electrocoating paint (by Herberts-Shinto AutomotiveSystems Co., the Succeed#80V that Ltd produces), the voltage with 200V is applied thereto so that energy supply reaches 3 minutes then.Subsequently, test specimen was toasted 20 minutes down at 170 ℃, so formed the electropaining film of thickness with 15-20 μ m.Use the test specimen that has formed the electropaining film on its that obtains like this, according to cross-hatching test (JIS K5600-5-6, ISO2409), the painted surface of each test specimen provides line with the NT cutting knife with the spacing of 1mm, to form 100 lattice, and a zona pellucida (18mm is wide, and by Nichiban Co., Ltd makes) attached thereon.After 2 minutes, peel off this part zona pellucida, and estimate with the number that wherein stays the grid of filming.When the number that leaves the grid of filming was 100, evaluation was A (very good); 95-99 grid is be evaluated as B (well); 85-94 grid is be evaluated as C (poor slightly); 84 grid or 84 are be evaluated as D (poor) below the grid.

In two roads japanning clinging power, form and the similar electropaining film of electropaining film in above-mentioned slubbing japanning adhesion test, be immersed in the hot water then.Therefore, in the clinging power of being filmed by the postevaluation that deliberately degenerates.In the immersing in hot water, each test specimen that has formed the electropaining film on it was immersed in 40 ℃ ± 1 ℃ hot water 1000 hours.(JIS K5600-5-6 ISO2409) carries out according to the cross-hatching test that is similar to slubbing japanning bounding force in the evaluation of clinging power.

The comparative example

With those identical conditions of embodiment under preparation degreasing and chemical conversion solution and aluminium conversion process solution, just the polar organic solvent in degreasing and chemical conversion solution and the weight ratio of water are set at 1: 9 in the comparative example, and the evaluation that is similar to embodiment.Their result provides in Figure 21.

Thinking

From the result shown in Figure 20 and 21 as can be seen, in the pretreatment process before comparative example's japanning, the density of glue spread, crystallization coating, slubbing japanning clinging power and two roads japanning clinging power any all is be evaluated as " poor slightly " or " poor ".Yet, by the pretreated method before the japanning among the use embodiment, any all be evaluated as " well " or " very good " of the density of glue spread, crystallization coating, slubbing japanning clinging power and two roads japanning clinging power.Therefore, proved there are not quality problems.

The applying date is the Japanese patent application No.P2002-171075 on June 12nd, 2002, and the full content of No.P2002-171080 and No.P 2002-171081 is here introduced for reference.

Though above by having described the present invention with reference to certain embodiments of the present invention, according to these instructions, those of skill in the art will appreciate that, the invention is not restricted to above-mentioned embodiment.Scope of the present invention is determined with reference to following claims.

Claims

1, the pretreated method before the japanning comprises:

To have the aluminium of at least a portion that is used for outer plate portion and any hybrid vehicle body of aluminium alloy part and be impregnated into the mixing solutions that contains polar organic solvent and water at least, sodium ion and lithium ion any or two kinds, phosphate anion, zine ion, nickel ion, mn ion, and in the degreasing and chemical conversion solution of nitrate ion and nitrite ion any or two kinds, this mixing solutions has the polar organic solvent in 2.8: 7.2 to 3.8: 6.2 scopes and the weight ratio of water;

In the chemical conversion solution of aluminium, handle vehicle body; With

Wash vehicle body with washings.

2, according to the pretreated method before the japanning of claim 1,

Wherein polar organic solvent contains at least a of glycol ethers and glycol ether ether.

3, according to the pretreated method before the japanning of claim 1,

The polar organic solvent of wherein per 100 weight parts and the mixing solutions of water contain any in the sodium ion of 0.8-3.3 weight part and the lithium ion or two kinds.

4, according to the pretreated method before the japanning of claim 3,

Wherein the mol ratio of sodium ion and lithium ion is in 50: 50 to 2: 98 scope.

5, according to the pretreated method before the japanning of claim 1,

The polar organic solvent of wherein per 100 weight parts and the mixing solutions of water contain the phosphate anion of 0.2-0.5 weight part and the zine ion of 0.5-0.7 weight part.

6, according to the pretreated method before the japanning of claim 1,

The polar organic solvent of wherein per 100 weight parts and the mixing solutions of water contain the nickel ion of 0.09-0.23 weight part.

7, according to the pretreated method before the japanning of claim 1,

The polar organic solvent of wherein per 100 weight parts and the mixing solutions of water contain the mn ion of 0.03-0.16 weight part.

8, according to the pretreated method before the japanning of claim 1,

The polar organic solvent of wherein per 100 weight parts and the mixing solutions of water contain the nitrate ion of 3.5-10.8 weight part and any one or two kinds in the nitrite ion.

9, according to the pretreated method before the japanning of claim 1,

The temperature of degreasing of wherein being equipped with in treatment trough and chemical conversion solution is in 40-60 ℃ scope and the dipping time of each workpiece is in 3-10 minute scope.

10, according to the pretreated method before the japanning of claim 1,

Wherein the chemical conversion solution of aluminium contains at least a of hexafluoro titanate and fluorozirconate.

11, according to the pretreated method before the japanning of claim 1,

The chemical conversion solution that wherein is sprayed to the aluminium on the workpiece has pH and the temperature in 20-70 ℃ of scope in the 2.5-10 scope, and with the chemical conversion solution spray of aluminium to the time on the workpiece be in the 20-100 scope of second.

12, according to the pretreated method before the japanning of claim 1, further comprise:

Behind dipping, wash vehicle body with washings.

13, according to the pretreated method before the japanning of claim 12,

14, according to the pretreated method before the japanning of claim 12,

15, according to the pretreated method before the japanning of claim 14,

16, according to the pretreated method before the japanning of claim 12,

17, according to the pretreated method before the japanning of claim 12,

18, according to the pretreated method before the japanning of claim 12,

19, according to the pretreated method before the japanning of claim 12,

20, according to the pretreated method before the japanning of claim 12,

21, according to the pretreated method before the japanning of claim 12,

22, according to the pretreated method before the japanning of claim 12,