JP2004018865A - Coating pretreatment apparatus and coating pretreatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pretreatment apparatus to coating by which space saving, the improvement of productivity, and the remarkable reduction in equipment expense/chemicals cost/the number of management stages/a load of waste water treatment can be attained even to a composite body of iron and aluminum. <P>SOLUTION: The apparatus is composed of a treatment tank 101 in which a degreasing/chemical conversion treatment liquid at least comprising a mixed solvent of a polar organic solvent and water in a weight ratio of 2.8:7.2 to 3.8:6.2 in a weight ratio, and sodium ions and/or lithium ions, phosphoric ions, zinc ions, nickel ions, manganese ions, nitrate ions and/or nitrite ions are filled, and an automobile body 9 is dipped, an aluminum chemical conversion treatment zone 300 provided on the poststage of the treatment tank 101 and spraying a chemical conversion treatment liquid for aluminum on the automobile body 9, and a rinse tank 201 provided on the poststage of the aluminum chemical conversion treatment zone 300 and in which a cleaning liquid is filled and the automobile body 9 is dipped. The apparatus is further provided with an automobile body conveying device C having a rotary driving device 90 of rotating the automobile body 9, and allowing the same to enter and leave to the treatment tank 101 and the rinse tank 201. <P>COPYRIGHT: (C)2004,JPO

Description

比較例
【００９７】
実施例における脱脂兼化成処理液の極性有機溶剤と水との重量比率を１：９とした以外は実施例と同じ条件で脱脂兼化成処理液及びアルミニウム化成処理液を作製し、同様の評価を行った。その結果を表２に示す。
【表２】

考察
【００９８】
表１及び表２の結果からも明らかなように、比較例の塗装前処理方法では、皮膜重量、結晶皮膜の緻密度合い、一次塗装密着性、二次塗装密着性の何れにおいても少々劣る〜不良であったのに対し、実施例の塗装前処理方法を採用することで、皮膜重量、結晶皮膜の緻密度合い、一次塗装密着性、二次塗装密着性の何れについても極めて良好〜少々劣るとなり、品質的にも問題がないことが確認された。
【図面の簡単な説明】
【図１】本発明の塗装前処理装置の第１実施形態を示すシステム図である。
【図２】本発明の第１実施形態における処理槽への入槽、浸漬、出槽工程を概略的に図示した図である。
【図３】図２の概略平面図である。
【図４】図２及び図３に示す車体搬送装置の回転駆動装置の周囲の要部断面図である。
【図５】本発明の塗装前処理装置の第２実施形態を示すシステム図である。
【符号の説明】
１０１…処理槽
２０１…リンス槽（リンス手段）
３００…アルミニウム化成処理ゾーン（アルミニウム化成処理手段）
３０１…アルミニウム用化成処理液補給タンク
３０２…配管
３０３…ポンプ
３０４…ノズル
３０７…回収槽
３０８…配管
３０９…ポンプ[0001]
【Technical field】
The present invention relates to a pre-painting apparatus and a pre-painting method, and more particularly to a pre-painting apparatus and a pre-painting method suitable for use in a pre-painting line in which a composite body of iron and aluminum flows.
[0002]
[Background Art]
From the viewpoint of reducing weight, improving rigidity, or improving recyclability, the use of aluminum parts such as hoods, trunk lids, door inners, etc. in automobile bodies is being studied.
[0003]
As a pretreatment liquid for such a composite body of iron and aluminum, for example, Japanese Patent Application Laid-Open No. 2001-515959 discloses that a chemical treatment is performed only on an iron part in a first step, and a chemical conversion treatment is performed on an aluminum part in a second step. It has been proposed to perform processing.
[0004]
In the chemical treatment solution used in this pretreatment method, free or complex-bonded fluoride ions are added in order to precipitate or mask aluminum that has been eluted and eluted. The free fluoride concentration is limited to less than 8 / T (g / L, where T is the processing temperature (° C.)) so as to prevent the formation of a conversion coating, that is, to prevent a large amount of sludge from accumulating at one time.
[0005]
However, in the pretreatment method described in JP-T-2001-515959, since the chemical conversion treatment solution contains fluoride ions, aluminum sludge is accumulated in the tank, and it is necessary to remove and discard the sludge. In addition, if the concentration of free fluoride is not controlled to a predetermined value or less as described above, a chemical conversion coating is formed on the aluminum surface more than necessary, so that an operation or system for controlling and controlling the concentration of fluoride and controlling and controlling the replenisher is required. become.
[0006]
Further, since the aluminum chemical conversion treatment step is provided after the steel sheet chemical conversion treatment step, the total length of the pretreatment step is increased, which is disadvantageous in terms of space, processing time and equipment cost.
[0007]
DISCLOSURE OF THE INVENTION
The present invention provides a coating pretreatment apparatus and a coating pretreatment method that can achieve a space saving, an improvement in productivity, and a significant reduction in equipment costs, chemical costs, management man-hours, and wastewater treatment load even for a composite body of iron and aluminum. The purpose is to provide.
[0008]
To achieve the above object, according to the present invention, a mixed solvent of a polar organic solvent and water having a weight ratio of 2.8: 7.2 to 3.8: 6.2, sodium ion and / or lithium A treatment tank filled with a degreasing / chemical conversion treatment solution containing at least ions, phosphate ions, zinc ions, nickel ions, manganese ions, nitrate ions and / or nitrite ions, and immersed in an object to be coated; An aluminum conversion treatment means provided at a subsequent stage and treating the article with a chemical conversion treatment solution for aluminum; a rinsing means provided at a subsequent stage of the aluminum conversion treatment means to wash the article with a cleaning liquid; An article transfer means for moving the article to be treated to the treatment tank, the aluminum conversion treatment means, and the rinsing means, wherein the article transfer means comprises the treatment tank, Bromide chemical treatment means, at least one, it said pre-painting processing apparatus having a coated article rotating means for rotating the object to be coated is provided out of the rinsing means (see claim 1).
[0009]
In order to achieve the above object, according to the present invention, a composite automobile body of iron and aluminum having a part made of aluminum or an aluminum alloy on at least a part of an outer plate part has a weight ratio of 2.8: A mixed solvent of 7.2 to 3.8: 6.2, a polar organic solvent and water, sodium ion and / or lithium ion, phosphate ion, zinc ion, nickel ion, manganese ion, nitrate ion and / or zinc ion. A first step of immersing the body in a degreasing and chemical conversion solution containing at least nitrate ions for treatment, a second step of treating the vehicle body with a chemical conversion solution for aluminum, and cleaning the vehicle body with a cleaning solution And a third step of rotating the vehicle body in at least one of the steps. It is the (see claim 35).
[0010]
In the coating pretreatment apparatus and the coating pretreatment method of the present invention, the degreasing treatment and the chemical treatment of the iron parts of the article to be coated are performed with the degreasing and chemical conversion treatment liquid filled in the treatment tank, and the degreasing treatment of the aluminum parts. I do. Since the degreasing / chemical conversion treatment liquid according to the present invention filled in the treatment tank does not contain a fluoride for etching aluminum, aluminum sludge does not accumulate in the treatment tank.
[0011]
With the degreasing and chemical conversion treatment liquid filled in the treatment tank of the present invention, aluminum components of the coating object are only subjected to degreasing treatment and no chemical conversion coating is formed. Spraying or immersing the chemical conversion treatment solution. In particular, when the aluminum component is on the outer plate portion of the object to be coated, a sufficient conversion coating can be formed only by spraying. Further, even when the aluminum component is on the inner plate portion of the object to be coated, a sufficient chemical conversion film can be formed by performing the immersion treatment or by considering the spraying method using a spray device.
[0012]
After the treatment with the chemical conversion treatment solution for aluminum, the entire object to be coated is washed by the next-stage rinsing means. Thus, the pre-coating process as a base such as the electrodeposition coating is completed. The object to be coated may be conveyed to a drying oven before being sent to the electrodeposition coating step.
[0013]
According to the present invention, since the degreasing and chemical conversion treatment liquid does not contain a fluoride for etching aluminum, accumulation of aluminum sludge in the treatment tank can be prevented. As a result, it is possible to reduce the number of work steps and system cost required for removing and disposing of aluminum sludge. Further, since the aluminum sludge itself is not generated, the number of man-hours and system cost related to the concentration control of the fluoride can be reduced as compared with the conventional pretreatment method.
[0014]
Furthermore, a chemical conversion treatment step for aluminum parts is provided at a stage subsequent to the degreasing and chemical conversion treatment tank. Particularly when a chemical conversion coating is formed by spray treatment, the process space and equipment costs can be significantly reduced as compared with immersion treatment. . By reducing the process space, the processing time is shortened, and the productivity of the automobile body is improved.
[0015]
Furthermore, by making the entry and exit tanks of the car body into and out of the dipping tank rotate, there is no need to provide an inclined surface at the entrance and exit of the dipping tank, and the length of the dipping tank in the transport direction can be shortened. The overall length can be reduced. Further, by rotating the automobile body in the dipping tank, the processing property and cleaning property of the air pocket generating portion in the bag structure and the like are improved.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0017]
First Embodiment FIG. 1 is a system diagram showing a first embodiment of a coating pretreatment apparatus of the present invention. For example, an object to be coated such as an automobile body is used as a base treatment for electrodeposition coating. Fig. 4 shows a pre-coating treatment step for performing degreasing treatment, surface conditioning, and chemical conversion treatment. FIG. 2 is a diagram schematically showing the steps of entering, immersing, and leaving the treatment tank in the first embodiment of the present invention, FIG. 3 is a schematic plan view of FIG. 2, and FIG. FIG. 4 is a sectional view of a main part around a rotation drive device of the vehicle body transfer device shown in FIG. 3.
[0018]
In particular, the automobile body 9 flowing through the coating line of the present example is an iron-aluminum composite body in which aluminum parts are used for outer plates such as a hood, a trunk lid, and a door, and other parts are made of a steel plate. In the coating pretreatment device of the present invention, all the objects to be coated need not be limited to such an iron-aluminum composite body, and may be a mixed line of an iron-aluminum composite body and a steel plate body. In addition, even in the same iron-aluminum composite body, vehicle types having different adoption portions of aluminum parts may be mixed and flow.
[0019]
As shown in FIG. 1, the vehicle body 9 is transported by the coating transport device C while being fixed to the skid 86. In the present embodiment, two dipping tanks 101 and 201 are provided along the coating transfer line C, and the upstream side in the transfer direction indicated by an arrow in the drawing is a processing tank 101 (hereinafter, referred to as a degreasing chemical treatment) for performing a degreasing treatment and a chemical conversion treatment. The downstream side is a rinse tank 201 for cleaning the processed body 9. The treatment tank 101 is filled with a degreasing / chemical conversion treatment liquid, and the rinsing tank 201 is filled with pure water.
[0020]
The degreasing and chemical conversion treatment liquid used in this example is a treatment liquid capable of performing three types of treatments such as degreasing treatment, surface conditioning, and chemical conversion treatment in the same step. As such a degreasing / chemical conversion treatment solution, for example, a polar organic solvent, water, sodium ion and / or lithium ion, phosphate ion, zinc ion, nickel ion, manganese ion, nitrate ion and / or nitrite ion are used. A processing solution containing at least can be used. By using this processing liquid, the degreasing step, the surface conditioning step, and the chemical conversion step can be collectively performed in one step at the same time, greatly reducing the processing steps, simplifying the processing equipment, saving space, and improving productivity. Improvement, reduction of drug cost, and simplification of drug management can be achieved.
[0021]
The degreasing and chemical conversion treatment liquid of this example will be described in more detail. The weight ratio of the mixed solvent of the polar organic solvent and water is 2.8: 7.2 to 3.8: 6.2, preferably 3.0: 7.2. 7.0-3.8: 6.2, more preferably 3.3: 6.7-3.8: 6.2, more preferably 3.3: 6.7-3.5: 6.5, Most preferably, it is 3.5: 6.5.
[0022]
Examples of the polar organic solvent of this example include ethylene glycol and other lower alkyl ethers or lower alkyl esters represented by (—CH ₂ —CH ₂ —O—) _n (where n = 1 to 4), propylene glycol or dipropylene. Glycols and other lower alkyl ethers or lower alkyl esters, diethylene glycol, triethylene glycol, tetraethylene glycol and other lower alkylene glycols, lower alcohols and esters thereof can be exemplified.
[0023]
As the ethylene glycol-based lower alkyl ether or lower alkyl ester, for example, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether and other ethylene glycol ethers, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether and the like diethylene glycol ether And triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and the like.
[0024]
Examples of the lower alkyl ether or lower alkyl ester of propylene glycol or dipropylene glycol include, for example, propylene glycol butyl ether, dipropylene glycol monomethyl ether, and polypropylene glycol monoethyl ether.
[0025]
In addition, examples of the lower alcohol include alcohols having 1 to 8, preferably 1 to 5, and more preferably 1 to 4 carbon atoms. Specific examples include glycol alcohols such as ethyl alcohol, isopropyl alcohol, tertiary butyl alcohol, methoxydimethylpentanol, diacetone alcohol, 2-methoxyethanol, and 2-ethoxymethanol.
[0026]
Examples of the esters include ethyl lactate, methoxybutyl acetate and butyl lactate.
[0027]
Among the above-mentioned polar organic solvents, at least one selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, and propylene glycol monoalkyl ether It is most preferred to employ more than one glycol compound or a mixed solvent of these glycol compounds and a lower alcohol.
[0028]
The alkyl group in these glycol compounds is preferably an alkyl group having 1 to 5 carbon atoms. The lower alcohol is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 5 carbon atoms, and most preferably an alcohol having 1 to 4 carbon atoms.
[0029]
The degreasing and chemical conversion solution of this example is obtained by adding sodium ion and / or lithium ion, phosphate ion, zinc ion, nickel ion, manganese ion, nitrate ion and / or nitrite ion to the above-mentioned mixed solvent of polar organic solvent and water. At least.
[0030]
It is preferable that the phosphate ion is contained in an amount of 0.2 to 0.5 part by weight based on 100 parts by weight of the mixed solvent. If the content is out of this range, the amount of oil mixed in is large, and the desired good zinc phosphate coating is not formed at the time of poor stirring. The source of the phosphate ions is not particularly limited, and examples thereof include orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, and phosphorus pentoxide. It is also possible to supply as an anion to metal ions (sodium ion and / or lithium ion, zinc ion, nickel ion, manganese ion) contained in the degreasing / chemical conversion treatment liquid.
[0031]
Zinc ions have a function of forming a zinc phosphate chemical conversion film together with phosphate ions. The zinc ion is preferably contained in an amount of 0.5 to 0.7 parts by weight based on 100 parts by weight of the mixed solvent. If the content is out of this range, the amount of oil mixed in is large, and the desired good zinc phosphate coating is not formed at the time of poor stirring. Examples of the supply source of the zinc ion include inorganic acid salts such as zinc oxide, zinc carbonate, zinc nitrate, zinc chloride, zinc sulfate, and zinc phosphate.
[0032]
Nickel ions have a function of improving the corrosion resistance of the uncoated object. Nickel ions are preferably present in an amount of 0.09 to 0.23 parts by weight based on 100 parts by weight of the mixed solvent. If the content is out of this range, the amount of oil mixed in is large, and the desired good zinc phosphate coating is not formed at the time of poor stirring. Examples of the supply source of the nickel ions include inorganic acid salts such as nickel nitrate and nickel phosphate.
[0033]
Manganese ions have a function of improving wet coating adhesion of an object containing zinc metal. Manganese ion is preferably used in an amount of 0.03 to 0.16 parts by weight based on 100 parts by weight of the mixed solvent. If the content is out of this range, the amount of oil mixed in is large, and the desired good zinc phosphate coating is not formed at the time of poor stirring. Examples of the source of the manganese ion include inorganic acid salts such as manganese nitrate and manganese phosphate.
[0034]
The nitrate ion and / or nitrite ion is preferably 3.5 to 10.8 parts by weight based on 100 parts by weight of the mixed solvent. If the content is out of this range, the amount of oil mixed in is large, and the desired good zinc phosphate coating is not formed at the time of poor stirring.
[0035]
It is preferable that sodium ion and / or lithium ion be contained in an amount of 0.8 to 3.3 parts by weight based on 100 parts by weight of the mixed solvent. The sodium ions and / or lithium ions have a function of making the zinc phosphate coating crystals formed on the surface of the article to be dense together with the water of the degreasing and chemical conversion treatment solution. Examples of the sodium ion supply source include sodium nitrate, sodium phosphate, sodium nitrite, and sodium hydroxide. Further, part or all of sodium nitrate can be replaced with sodium nitrite. By the action of nitrite ions, the etching power of the acid is further enhanced, and the promotion of the chemical reaction can be expected.
[0036]
Further, the sodium ion can be replaced with a lithium ion which is common as a monovalent alkali metal. Specifically, 50% to 98%, preferably 60% to 90%, more preferably 70% to 80% of the total amount of sodium ions and lithium ions is replaced with lithium ions. By including lithium ions in the degreasing and chemical conversion treatment liquid, the crystals of the zinc phosphate film become more dense and the coating adhesion is further improved. Examples of the supply source of lithium ions include inorganic acid salts such as lithium nitrate, lithium phosphate, and lithium nitrite.
[0037]
Incidentally, it is preferable that the degreasing and chemical conversion treatment liquid is treated at a temperature of 40 ° C to 60 ° C for 3 minutes to 10 minutes.
[0038]
By using the degreasing and chemical conversion treatment liquid having the above composition, even if a large amount of oil is mixed in the degreasing and chemical conversion treatment liquid, or even if the stirring state of the degreasing and chemical conversion treatment liquid is poor, corrosion resistance and A zinc phosphate conversion coating having excellent film adhesion can be formed.
[0039]
Returning to FIG. 1, the degreasing / chemical conversion treatment liquid in the treatment tank 101 is sucked by the pipe 105 and the pump 106, and is returned to the treatment tank 101 by the pipe 111 and the pump 110 via the treatment liquid supply tank 109. A dust removing device 102, a chemical sludge removing device 103, and an oil removing device 104 are provided in the middle of the pipe 105. The iron dust is passed through the dust removing device 102, the chemical sludge removing device 103, and the oil removing device 104. The processing liquid containing water, such as dust, chemical sludge, and a polar organic solvent from which oil has been removed, is temporarily stored in the processing liquid supply tank 109. A new degreasing / chemical conversion liquid is supplied and adjusted by a pump 108 from the processing liquid tank 107 containing the new degreasing / chemical conversion liquid to the processing liquid supply tank 109, and the adjusted degreasing / chemical conversion treatment is performed. The liquid is returned to the degreasing chemical treatment tank 101 by the piping 111 and the pump 110 described above.
[0040]
The dust removing device 102 is for removing dust particles such as iron powder contained in the processing liquid in the processing tank 101. The removed dust particles are discarded, and the processing liquid from which the dust particles are removed is used as the next chemical sludge removing device. 103. Specific devices that can be used as the dust removing device 102 of this example include a settling tank, a centrifugal separator, and a magnet separator. These settling tanks, centrifugal separators, and magnetic separators can be used alone or in combination, and in particular, the dust removal device 102 that combines the settling tank and the magnetic separator has a high dust removal rate, preferable.
[0041]
However, the dust removing device 102 according to the present example is not limited to the above-described three forms, but includes other forms. In addition, the dust removing device 102 of this example is provided in the pipe 105, but may be provided inside or outside the processing tank 101 itself.
[0042]
The chemical sludge removing device 103 is for removing chemical sludge contained in the processing liquid that has passed through the above-described dust removing device 102, and the removed chemical sludge is discarded. The oil is sent to the oil removing device 104. As the chemical sludge removal device 103, any filter can be used without particular limitation as long as the sludge concentration of the processing liquid in the processing tank 101 is suppressed to within 150 ppm and does not contaminate the processing liquid. .
[0043]
The oil removing device 104 removes the oil contained in the processing liquid that has passed through the chemical sludge removing device 103 described above. The removed oil is discarded, and the processing liquid from which the oil has been removed is supplied to the processing liquid supply tank 109. Sent to Examples of the oil removing device 104 that can be used in this example include a heated oil removing device, a coalescer oil removing device, and an ultrafiltration oil removing device.
[0044]
Of these, the heated oil removal device is preferably applied to an aqueous solution containing a nonionic surfactant as a degreasing component.When this is heated to a specific temperature or higher, it itself becomes insoluble in water, This is an oil-removing device that utilizes the characteristics of a nonionic surfactant, such as oil-water separation into two phases, an oil phase and a water phase, each of which is composed of a nonionic surfactant.
[0045]
In addition, the coalescer type oil removing device is a method of breaking down a water-oil emulsion by passing oil droplets dispersed in an aqueous solution with a size of several μm through a filter, thereby expanding and growing the oil droplets. It is an oil removal device that can float and recover.
[0046]
The ultrafiltration type oil removing device uses ultrafiltration, that is, using a filter having a mesh of about 0.01 to 0.001 μm, and applying pressure at a low pressure of about 0.5 to 5 × 10 ⁻⁵ Pa or This is an oil removing device using a filtration method of separating colloid particles from a solvent by suction filtration.
[0047]
These heated oil removal equipment, coalescer oil removal equipment, and ultrafiltration oil removal equipment are selected according to the required degree of oil-water separation, and can be used alone or in combination.
[0048]
Between the treatment tank 101 and the rinsing tank 201 shown in FIG. 1, an aluminum chemical treatment zone 300 for spraying a chemical conversion treatment liquid for aluminum onto the automobile body 9 is provided. The aluminum chemical conversion treatment zone 300 is inclined so that the floor surface of the booth is the lowest surface at the center thereof so that the sprayed chemical conversion treatment liquid for aluminum does not flow into the treatment tank 101 and the rinsing tank 201 of the preceding stage as much as possible. ing.
[0049]
Further, a nozzle 304 for spraying a chemical conversion liquid for aluminum onto the vehicle body 9 passing through the aluminum chemical conversion zone 300 is attached to the pipe 302, and an aluminum chemical conversion liquid supply tank containing the chemical conversion liquid for aluminum. The chemical conversion treatment liquid is supplied from 301 by a pump 303. In the example shown in FIG. 1, a plurality of nozzles 304 for spraying an aluminum chemical conversion liquid onto a hood, a trunk lid, and a door, which are aluminum parts, are provided on an automobile body 9 on each of a ceiling surface and a side surface of the booth. I have.
[0050]
The aluminum chemical treatment liquid collected on the floor of the booth is collected in the recovery tank 307 and returned to the aluminum chemical treatment liquid supply tank 301 by the pipe 308 and the pump 309. A pipe 308 connected to the collection tank 307 includes a dust removal device 310 for removing dust contained in the collected chemical conversion treatment liquid for aluminum, and aluminum and iron (produced by processing in the processing tank 101 in the preceding stage). A chemical sludge removing device 311 for removing chemical sludge and an oil removing device 312 for removing oil. As the dust removing device 310, the chemical sludge removing device 311 and the oil removing device 312, the specific examples exemplified as the dust removing device 102, the chemical sludge removing device 103 and the oil removing device 104, respectively, can be used.
[0051]
The chemical conversion treatment solution for aluminum used in this example is not particularly limited, and examples thereof include hexafluorotitanate and hexafluorozirconate. Such a new aluminum chemical conversion liquid is stored in an aluminum chemical conversion liquid tank 305 and supplied to an aluminum chemical conversion liquid supply tank 301 by a pump 306, whereby the aluminum chemical conversion liquid sprayed from the nozzle 304 to the automobile body 9 is adjusted. Is done.
[0052]
Incidentally, the chemical conversion treatment solution for aluminum is preferably treated at a pH of 2.5 to 10 and a temperature of 20 ° C to 70 ° C for 20 seconds to 100 seconds.
[0053]
A rinsing tank 201 is provided at a stage subsequent to the aluminum conversion treatment zone 300, and the body 9 on which the chemical conversion film is formed in the processing tank 101 and the aluminum conversion treatment zone 300 is washed with pure water. In the present embodiment, the outer plate and the inner plate of the vehicle body 9 are cleaned by immersing the vehicle body 9 in the rinsing tank 201, but it can be realized by a spraying process other than the dipping process.
[0054]
Since dust, chemical sludge, and oil adhering to the vehicle body 9 are mixed into the pure water in the rinsing tank 201, the pure water in the rinse tank 201 is sucked by the pipe 202 and the pump 203, and is removed by the dust removing device in the aluminum chemical treatment zone 300 in the preceding stage. After supplying the dust, the chemical conversion sludge, and the oil component to the liquid 310, the aluminum conversion liquid is reused as pure water. At this time, the cleaning liquid in the rinsing tank 201 sucked by the pipe 202 and the pump 203 may be supplied to the recovery tank 307 of the aluminum chemical conversion treatment zone 307. Although not shown, new pure water is supplied into the rinse tank 201 from a separately provided pure water supply device.
[0055]
As shown in FIGS. 1 to 4, in the first embodiment of the present invention, an automobile body 9 to be coated is moved to the above-mentioned two dipping tanks 101 and 201, rotated and immersed, and then subjected to aluminum conversion. A vehicle body transfer device C for passing through the processing zone 300 is provided. The vehicle body transfer means C includes a conveyor 80, a rotating shaft 85 and a skid 86, and a rotation driving device 90.
[0056]
The conveyor 80 is a means for moving the vehicle body 9 from the preceding process to the subsequent process via the upper part of the degreasing chemical treatment tank 101, the upper part of the aluminum chemical treatment zone 300, and the upper part of the rinsing tank 201. As shown in FIG. 1, from the front of the degreasing chemical treatment tank 101 to the rear of the rinsing tank 201 with respect to the transport direction, in parallel at a certain interval from each other, two upper parts of the degreasing chemical treatment tank 101 and the rinsing tank 201. A conveyor 80 is provided. Further, although not particularly shown, the conveyor 80 is inverted at the rear of the rinsing tank 201, and passes through the degreasing chemical treatment tank 101, the aluminum chemical treatment zone 300, and the lower side of the rinsing tank 201, and is located in front of the degreasing chemical treatment tank 101. It has an annular shape that circulates back. Note that the interval between the two conveyors 80 is an interval that allows the width of the automobile body 9 to be sufficient.
[0057]
As shown in FIG. 4, the conveyor 80 includes a conveyor chain 81, a conveyor rail 82, and a conveyor support member 83. A conveyor support member 83 fixedly supports the conveyor rail 82, and a conveyor chain 81 is movably supported on the conveyor rail 82. A plurality of first bearings 84 are fixed to the conveyor chain 81 at regular intervals, and the first bearings 84 rotatably support the rotating shaft 85. The conveyor chain 81 is driven by power (not shown), and the plurality of first bearings 84 provided on the conveyor chain 81 are moved in synchronization.
[0058]
The skid 86 is a means for fixing the automobile body 9 and moving together with the above-mentioned rotating shaft 85, for example, engaging the body fixing portion 86 a with a positioning hole (not shown) provided in the floor portion 9 a of the automobile body 9. Thereby, the skid 86 and the vehicle body 9 are fixed. Further, the skid 86 is fixed to the rotating shaft 85 by a rotating shaft connecting portion 86b, whereby the skid 86 and the vehicle body 9 fixed to the skid 86 rotate together with the rotating shaft 85, and as described later, the vehicle body 9 Is reversed and immersed in the degreasing chemical treatment tank 101. The car body 9 in the degreasing chemical treatment tank 101 shown in the center of FIG. 2 and the car body 9 shown by the dotted line in FIGS. 3 and 4 show the car body 9 rotated together with the rotating shaft 85. The rotating shaft 85 is rotatably supported by a plurality of first bearings 84 provided on the conveyor chain 81 as described above.
[0059]
As shown in FIG. 4, the rotation drive device 90 is a means for rotating the rotation shaft 85 to rotate the automobile body 9 fixed to the skid 86, and one side of the two parallel conveyors 80 described above. Are provided at the end (lower side in FIG. 3) of the rotary shaft 85. The rotation drive device 90 includes two bevel gears 91a and 91b, two gears 92a and 92b, three bearings 93a, 93b and 93c, two drive shafts 94a and 94b, a drive motor 95, And a device cover 96.
[0060]
A first spur gear 92a is attached to a first drive shaft 94a of the drive motor 95, and the first spur gear 92a is engaged with a second spur gear 92b. The drive motor 95 and the second bearing 93a are fixed to the drive device cover 96, and the end of the first drive shaft 94a of the drive motor 95 is rotatably supported by the second bearing 93a. ing. The second spur gear 92b that meshes with the first spur gear 92a is attached near one end of the second drive shaft 94b, and is attached to the other end of the second drive shaft 94b. , The first bevel gear 91a is fixed. The second drive shaft 94b is rotatably supported by a third bearing 93b and a fourth bearing 93c, and the third bearing 93b and the fourth bearing 93c are attached to a drive device cover 96. Fixed. The first bevel gear 91a is in mesh with a second bevel gear 91b attached to one end of the rotating shaft 85. The rotation drive of the drive motor 95 is transmitted to the rotation shaft 85 via the transmission means described above. These are housed inside the drive device cover 96, and the rotating shaft 85 passes through the drive device cover 96 and is rotatable. Further, the drive device cover 96 is fixed to a portion that does not rotate with the automobile body 9, for example, to a conveyor chain 81 by a drive device fixing portion 96 a. The drive motor 95 is supplied with power such as electric power from a power supply source (not shown). The rotation drive device 90 is provided on each rotation shaft 85 rotatably supported by first bearings 84 provided at predetermined intervals on a conveyor chain 81, and moves together with a skid 86 to which the automobile body 9 is fixed. I do.
[0061]
Further, as shown in FIG. 3, in the first embodiment of the present invention, the other side (upper side in FIG. 3) of the above-described two parallel conveyors 80 is provided with an automobile body at the time of entering and exiting the processing tank 101. Limit switches 98 for starting rotation of 9 are provided at predetermined locations near the inlet and the outlet of the degreasing chemical treatment tank 101, respectively. A limit switch pin 99 for turning on the limit switch 98 is provided at an end (upper side in FIG. 3) of each of the rotary shafts 85 on the other side of the two parallel conveyors 80 described above. . When the rotating shaft 85 is moved by the conveyor 80, the limit switch pin 99 comes into contact with the limit switch 98, and when the limit switch 98 is turned on, it is detected that the vehicle body 9 has reached a predetermined position. An instruction to start rotation is transmitted to the corresponding rotation driving device 90 by the control device 97 that controls the plurality of rotation driving devices 90 provided in the vehicle body transfer device C, and the driving motor 95 is driven based on the instruction, The car body 9 is turned over and put in and out. Instead of the limit switch 98 provided near the outlet side of the degreasing chemical treatment tank 101, the control device 97 is provided with a timer, and the timer starts timing when the limit switch 98 near the inlet side comes into contact. Then, when a predetermined time until the start of rotation for the discharge tank calculated from the transfer speed, the length of the dipping tank in the transfer direction, and the like is measured, the control device 97 issues a rotation start command to the rotation drive device 90. You may send it. By the control device 97, the plurality of rotation driving devices 90 provided on the conveyor 80 can be independently driven to rotate.
[0062]
As shown in FIG. 2, the skid 86 to which the automobile body 9 is fixed is moved to the vicinity of the entrance of the degreasing chemical treatment tank 101 by the conveyor 80 of the vehicle body transfer device C. When the limit switch pin 99 provided at the end of the rotating shaft 85 comes into contact with the limit switch 98 provided at a predetermined position near the entrance of the degreasing chemical treatment tank 101, the vehicle body 9 is moved to a predetermined position. It is detected that the position has been reached. Based on the detection, the control device 97 transmits a rotation start instruction to the corresponding rotation drive device 90. The driving motor 95 of the rotary drive device 90 starts driving based on the instruction, and stops driving when the front part of the vehicle body 9 in the transport direction is rotated downward by about 180 ° vertically (clockwise in FIG. 2). In this state, the vehicle body 9 is completely immersed in the degreasing chemical treatment tank 101.
[0063]
Then, the vehicle body 9 moves to the vicinity of the outlet portion of the degreasing chemical treatment tank 101 by the conveyor 80 in the degreasing chemical treatment tank 101 while maintaining the inverted state. In this way, by moving the inside of the degreasing chemical treatment tank in a vertically inverted state, air pockets are not generated in the roof portion, the hood portion, and the like where quality is important, and dust particles such as iron powder adhere. Can be prevented.
[0064]
Next, when the limit switch pin 99 provided at the end of the rotating shaft 85 comes into contact with a limit switch 98 provided at a predetermined position near the outlet of the degreasing chemical treatment tank 101, the vehicle body 9 is moved to a predetermined position. It is detected that the position has been reached. Based on the detection, the control device 97 transmits a rotation start instruction to the corresponding rotation drive device 90. The driving motor 95 of the rotary drive device 90 starts driving based on the instruction, and stops driving when the front part of the vehicle body 9 in the transport direction is rotated downward by about 180 ° vertically (clockwise in FIG. 2). In this state, the discharge of the automobile body 9 from the degreasing chemical treatment tank 101 is completed. Therefore, the rotation drive device 90 rotates the automobile body 9 by about 360 ° between the entry and the exit. The skid 86 is continuously moved by the conveyor 80 even during the rotation operation.
[0065]
As described above, by making the entry and exit tanks of the car body into and out of the dipping tank rotate, it is not necessary to provide an inclined surface at the entrance and exit of the dipping tank, that is, it is not necessary to make the shape of the dipping tank into a hull shape. In addition, the length of the dipping tank with respect to the transport direction can be reduced. Further, by rotating the automobile body in the degreasing chemical treatment tank, the processability of the air pocket generating portion in the bag structure or the like is improved.
[0066]
As shown in FIG. 1, a limit switch 98 is also provided at a predetermined position in the rinsing tank 201, similarly to the above-described degreasing chemical treatment tank 101, and the automobile body 9 is turned upside down into the rinsing tank 201. The tank is then moved while maintaining its state, and then inverted and discharged. Therefore, the same operation as in FIGS. 2 and 3 is performed also in the rinsing tank 201, so that the length of the dipping tank can be shortened and the cleaning property can be improved.
[0067]
In addition, while moving in the state of being inverted in the vertical direction, by applying a function of shaking the vehicle body by the rotation drive device, or by rotating the vehicle body a plurality of times in the dipping tank, the bag structure portion It is possible to further improve the processability. Alternatively, the vehicle body may be fixed to the skid with the side of the vehicle body facing the transport direction, or a rotation about an axis perpendicular to the transport direction or an axis parallel to the transport direction. It is possible to obtain the same effect by rotating around.
[0068]
Next, the operation will be described.
[0069]
The white body 9 that has been welded and assembled in the vehicle body process is transported by the coating transport device C while being fixed to the skid 86, and comes into contact with a limit switch 98 installed near the entry side of the degreasing chemical treatment tank 101. The wafer is rotated 180 ° in the vertical direction by the rotation driving device 90 and immersed in the processing tank 101. By being immersed in the processing tank 101, dust and oil such as iron powder adhered to the vehicle body 9 are removed into the processing tank 101 by the cleaning and degreasing effect of the degreasing and chemical conversion treatment liquid. Further, the steel plate parts of the automobile body 9 from which the oil has been removed react with the degreasing and chemical conversion treatment liquid and iron, and a zinc phosphate chemical conversion film is formed thereon.
[0070]
However, the aluminum parts of the automobile body 9 are only subjected to dust removal and degreasing, but do not react with the degreasing and chemical conversion treatment liquid, and no chemical conversion film is formed. That is, since the degreasing and chemical conversion treatment liquid of the present example does not contain a fluoride for etching aluminum, the chemical conversion sludge of aluminum is not accumulated in the processing tank 101, and the above-described conventional Japanese Patent Application Laid-Open No. 2001-515959 has been described. Compared with the pretreatment method disclosed in the gazette, it is possible to reduce the number of work steps and system cost required for removing and disposing of aluminum sludge. Further, since the aluminum sludge itself is not generated, the number of man-hours and system cost related to the concentration control of the fluoride can be reduced as compared with the conventional pretreatment method.
[0071]
The degreasing / chemical conversion treatment liquid in the treatment tank 101 is sucked into a pipe 105 by a pump 106 and passes through a dust removal device 102 to remove dust particles such as iron powder contained in the treatment solution. By passing through 103, iron conversion sludge contained in the processing liquid is removed, and further through passing through an oil removing device 104, oil such as press oil contained in the processing liquid is removed.
[0072]
The degreasing / chemical conversion treatment liquid from which the dust, the chemical sludge and the oil have been removed is sent to the treatment liquid supply tank 109, where a fresh degreasing / chemical conversion treatment liquid is replenished from the processing liquid tank 107 by the pump 108, and appropriately. After the adjustment, it is returned to the processing tank 101 by the pipe 111 and the pump 110. As described above, since the degreasing and chemical conversion treatment liquid in the treatment tank 101 is closed by the pipes 105 and 111, the cost can be reduced by reducing material costs and the burden on the wastewater treatment step can be reduced. Further, the use of the degreasing and chemical conversion treatment liquid can reduce the number of man-hours for controlling the pretreatment conditions. Furthermore, the use of this degreasing and chemical conversion treatment liquid can greatly reduce the number of washing steps, and the amount of the washing liquid used reduces the load on the wastewater treatment step.
[0073]
When it comes into contact with the limit switch 98 installed near the outlet side of the degreasing chemical treatment tank 101, it is further rotated by 180 ° in the vertical direction by the rotation driving device 90, and is discharged from the treatment tank 101. The automobile body 9 that has left the processing tank 101 is sent to the aluminum chemical conversion treatment zone 300, and a chemical conversion treatment liquid for aluminum is sprayed from the nozzle 304. The processing liquid in the aluminum chemical conversion liquid supply tank 301 is sucked by a pump 303 and sprayed from a nozzle 304 through a pipe 302 onto mainly aluminum parts of the automobile body 9. The chemical conversion solution for aluminum sprayed on the automobile body 9 is collected on the floor of the booth, collected in the collection tank 307, and is sucked by the pump 309 therefrom. After passing through the dust removing device 310, the chemical sludge removing device 311 and the oil removing device 312, the dust, the chemical sludge of aluminum or iron, and the oil contained in the aluminum processing liquid are removed, and then through the pipe 308. It is returned to the aluminum chemical conversion treatment liquid supply tank 301.
[0074]
By the treatment in the aluminum conversion treatment zone 300, a chemical conversion coating treatment can be performed on an aluminum component used as an outer plate component such as a hood, a trunk lid, and a door. In particular, when these aluminum parts are used for the outer panel parts of the automobile body 9, a sufficient chemical conversion coating can be formed only by the spray treatment as in this example, and as a result, the aluminum chemical conversion treatment step Length can be kept to a minimum.
[0075]
Finally, when the vehicle body 9 that has passed through the aluminum chemical conversion zone 300 comes into contact with a limit switch 98 installed near the inlet side of the rinsing tank 201, the rinsing tank 201 is rotated by 180 ° in the vertical direction by the rotation driving device 90. To remove the treatment liquid attached to the vehicle body 9. Then, when it comes into contact with the limit switch 98 installed near the exit side of the rinsing tank 201, the rotary driving device 90 further rotates the container 180 ° in the vertical direction and leaves the rinsing tank 201. Thereafter, the automobile body is transported to a drying oven to be dried, and is sent to an electrodeposition coating process as a base coating. At this time, the cleaning liquid in the rinsing tank 201 is guided by the pipe 202 and the pump 203 to the upstream of the dust remover 310 in the pipe 308, passes through the dust remover 310, the chemical sludge remover 311 and the oil remover 312, and then passes through the aluminum remover. It is supplied to the chemical conversion liquid supply tank 301. Thereby, the pure water in the rinsing tank 201 can be effectively used.
[0076]
Second Embodiment FIG. 5 is a system diagram showing a second embodiment of the coating pretreatment device of the present invention. As in the first embodiment, for example, an object to be coated such as an automobile body is used. The drawing shows a pre-coating treatment step of performing a degreasing treatment, a surface conditioning, and a chemical conversion treatment as a base treatment of the electrodeposition coating. The present embodiment is basically different from the above-described first embodiment in that a dipping tank 313 is employed in the aluminum chemical conversion treatment zone 300. Other configurations are the same as those of the first embodiment, and thus the same components are denoted by the same reference numerals.
[0077]
An aluminum chemical conversion treatment tank 313 filled with an aluminum chemical conversion treatment liquid is provided in the aluminum chemical conversion treatment zone 300 of this example, and the automobile body 9 conveyed by the conveyor C rotates and enters and exits.
[0078]
The aluminum chemical conversion liquid in the dipping tank 313 is returned to the aluminum chemical conversion liquid supply tank 301 by the pipe 308 and the pump 309. In addition, a pipe 308 connected to the dipping tank 313 includes a dust removing device 310 for removing dust contained in the chemical conversion treatment liquid for aluminum, aluminum and iron (produced in the processing of the preceding processing tank 101). A chemical sludge removing device 311 for removing the chemical sludge and an oil removing device 312 for removing the oil component are provided. As the dust removing device 310, the chemical sludge removing device 311 and the oil removing device 312, the specific examples exemplified as the dust removing device 102, the chemical sludge removing device 103 and the oil removing device 104, respectively, can be used.
[0079]
The chemical conversion treatment solution for aluminum used in this example is not particularly limited, and examples thereof include hexafluorotitanate and hexafluorozirconate. Such a new aluminum chemical conversion liquid is stored in an aluminum chemical conversion liquid tank 305, supplied to an aluminum chemical conversion liquid supply tank 301 by a pump 306, adjusted to an appropriate value here, and then supplied to a pipe 302 and a pump 303. Is supplied to the dipping tank 313.
[0080]
Since the dipping tank 313 is used as the aluminum conversion treatment means in the coating pretreatment apparatus of this example, the treatment is particularly excellent when the aluminum material is used for the inner plate portion.
[0081]
Incidentally, in the present example, similarly to the first embodiment described above, the vehicle body 9 is rotated by rotating the vehicle body 9 as shown in FIGS. 2 to 4 so as to enter and exit the three dipping tanks 101, 313, and 201. Rotation means is provided. At a predetermined position near the entrance of each of the dipping tanks 101, 313, 201, the rotation of the vehicle body 9 is started by the rotation drive device 90, and the vehicle body 9 is inverted and enters the tank, and is vertically inverted. And then turn over and leave the tank. Accordingly, it is not necessary to provide an inclined surface at the entrance / exit portion of the dipping tank, that is, it is not necessary to make the shape of the dipping tank into a hull shape, and it is possible to reduce the length of the dipping tank in the transport direction. In addition, by rotating the car body in the dipping tank, the occurrence of air pockets in the roof, hood, etc., where quality is important, is reduced, and it is possible to prevent dust particles such as iron powder from adhering. In addition, the processability in the bag structure is improved.
[0082]
Further, in the present embodiment, it is determined whether the automobile body 9 is a composite body of iron and aluminum or a steel plate body by, for example, ID collation. When it is determined that the vehicle body 9 transported by the vehicle body transport device C is a composite body, the rotation drive device 90 is brought into contact with the limit switch 98 installed near the inlet side of the aluminum chemical conversion treatment tank 313 to rotate the vehicle body 9. Is rotated in the vertical direction by 180 ° to be immersed in the dipping tank 313, and the rotation driving device 90 further moves the automobile body 9 in the vertical direction by contact with the limit switch 98 installed near the outlet side of the dipping tank 313. The container is rotated by 180 ° and discharged from the dipping tank 313.
[0083]
On the other hand, when it is determined that the vehicle body 9 conveyed by the vehicle body conveyance device C is a steel plate body that does not require chemical conversion treatment for aluminum, the limit switch installed near the entrance side of the aluminum chemical conversion treatment tank 313 is used. Even if there is a contact with 98, the control device 97 does not send a rotation start command to the rotation driving device 90, and there is a contact with the limit switch 98 installed near the exit side of the aluminum chemical conversion treatment tank 313. However, the control device 97 does not transmit a rotation start command to the rotation drive device 90. That is, when the vehicle body 9 is a steel plate body, the vehicle body 9 passes above the aluminum chemical conversion treatment tank 313 without immersion. This makes it possible to avoid unnecessary immersion in the aluminum chemical conversion treatment tank and to minimize the entry of impurities such as dust and oil in the chemical conversion treatment liquid for aluminum.
[0084]
In the present embodiment, when the vehicle body 9 is a steel plate body, the degreasing and chemical conversion liquid adhering to the vehicle body 9 is dried while the aluminum conversion tank 313 is passed over the aluminum conversion tank 313 without being immersed. Since there is a risk of drying, a spray device 71 for spraying pure water in a mist state is provided above the aluminum chemical conversion treatment tank 313 in order to prevent the drying. The spray device 71 is supplied by sucking pure water filled in the rinsing tank 201 by a pump 72. Note that, for example, in accordance with the above-described ID collation of the automobile body 9, the spraying by the spraying device 71 may be turned on / off by contact with a limit switch 98 installed near the entrance / exit of the aluminum chemical conversion treatment tank 313. That is, when the vehicle body 9 is determined to be a steel plate body, pure water is supplied from the rinsing tank 201 to the spraying device 71 via the pump 72 in accordance with a command from the control device 97. On the other hand, if it is determined that the body is a composite body, the control device 97 may not transmit a command to supply pure water to the spray device 71.
[0085]
The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
[0086]
Although parts such as the door, the trunk lid, and the door of the automobile body 9 of the above-described embodiment are made of aluminum, they may be made of an aluminum alloy.
[0087]
【Example】
Hereinafter, the effects of the present invention were confirmed by Examples and Comparative Examples that further embody the present invention. The following examples are for confirming the effects of the degreasing and chemical conversion treatment liquid used in the above-described embodiment.
The degreasing and chemical conversion treatment solution of Example <br/> Example, sodium nitrate as a diethylene glycol monoethyl ether (DEGMEE), sodium compound as a source of sodium ions as the polar organic solvent, lithium as a source of lithium Lithium nitrate as a compound, orthophosphoric acid as a source of phosphate ions, zinc nitrate as a zinc compound serving as a source of zinc ions, nickel nitrate and manganese ion as a source of nickel compounds serving as a source of nickel ions Using manganese nitrate as a manganese compound, the composition was adjusted as shown in Table 1.
[0088]
Hexafluorozirconate (Deoxylyte 54C manufactured by Henkel) was used as the chemical conversion treatment solution for aluminum in the examples.
[0089]
Three types of test pieces are prepared: cold-rolled steel sheet (CRS), galvanized steel sheet (ZE), and aluminum 6111 (AL). After degreasing with acetone, three kinds of rust-preventive oils (Lactclean manufactured by Cosmo Oil Co., Ltd.) K, manufactured by Idemitsu Kosan Idemitsu NR3, equal amounts mixed oil 0.5 g / ^{m 2} was applied in the Nippon oil Nonrasuto PN-1), was prepared a test piece having an oil surface for testing. The test piece was surface-treated with the above-described degreasing and chemical conversion treatment solution and a chemical conversion treatment solution for aluminum, and the properties and performance of the obtained zinc phosphate coating, that is, the coating weight, the density of the crystal coating, and the primary coating adhesion. And the secondary coating adhesion was evaluated. Table 1 shows the results.
[0090]
The treatment with the degreasing and chemical conversion treatment liquid was performed by dipping a test piece into the treatment liquid, the treatment time was 300 seconds, and the temperature of the treatment liquid was 40 ° C. The treatment with the chemical conversion treatment solution for aluminum was performed by spraying the treatment solution on the test piece, and the spray time was set to 20 seconds, 30 seconds, and 100 seconds. The pH of the chemical conversion treatment solution for aluminum was 4.0, and the solution temperature was 40 ° C.
[0091]
The evaluation results were carried out by classifying the coating weight, the density of the crystalline coating, the adhesion of the primary coating, and the adhesion of the secondary coating into four categories: 極 め て very good, 良好 good, △ slightly poor, and × bad.
[0092]
The film weight was measured after the test piece after the treatment was dried with a dryer. Here, the film weight is converted into the weight (g) per 1 m ^{2, and the} weight of the film is ² to 3.5 g / cm 2 in order for the zinc phosphate chemical conversion film to have excellent rust prevention and coating properties as a coating base. Since a uniform and dense crystal film of about m ² is required, the film weight is ² to 2.5 g / m ² (very good), 2.6 to 3.5 g / m ² ○ ( good), if 1.5~1.9g / ^{m 2} △ (slightly poor), was evaluated as × (poor) is less than 1.5 g / ^{m 2.}
[0093]
The density of the crystal film was determined by sampling a sample from the center of the test piece after the treatment, and observing the shape and size of the zinc phosphate crystal film with a scanning electron microscope (SEM).
[0094]
In this embodiment, A (extremely good) if the crystal size indicating the denseness is 5 μm or less, B (good) if it is more than 5 μm to 10 μm or less, and C (somewhat inferior) if it is more than 10 μm to 20 μm or less. If it is larger than 20 μm, it was evaluated based on the criterion D (defective).
[0095]
The primary coating adhesion was evaluated by coating the test piece after the treatment. Specifically, an electrodeposition paint (Shindo # 80V manufactured by Shinto Herberts Automotive Systems Co., Ltd.) was applied to the treated test piece by applying a voltage of 200V for 3 minutes, and then the test piece was heated at 170 ° C. Baking was performed for 20 minutes to form an electrodeposited film thickness of 15 to 20 μm. Using the test piece on which the electrodeposition coating film thus obtained was formed, the coated surface of the test piece was cut into 100 squares at 1 mm intervals with an NT cutter according to JIS K5400 grid test, and a cellophane tape was used. (Nichiban, width 18 mm) was applied, and after 2 minutes, the cellophane tape was peeled off, and the number of coating films remaining in 100 cells was evaluated by the number of cells.で あ れ ば (very good) when the number of remaining coating films is 100, （(good) when 95 to 99, △ (slightly poor) when 85 to 94, and × when 84 or less. (Poor).
[0096]
The secondary coating adhesion is determined by forming an electrodeposited coating similar to the primary coating adhesion test described above, and immersing it in warm water to deliberately degrade the adhesion of the coating and then adhere the coating. It evaluates sex. In hot water immersion, the test piece on which the electrodeposition coating film is formed is immersed in warm water at 40 ° C. ± 1 ° C. for 1000 hours. The adhesion was evaluated in accordance with the JIS K5400 grid test in the same manner as the primary coating adhesion.
[Table 1]

Comparative Example [0097]
A degreasing / chemical conversion liquid and an aluminum chemical conversion liquid were prepared under the same conditions as in the example except that the weight ratio of the polar organic solvent and water in the degreasing / chemical conversion liquid in the example was set to 1: 9, and the same evaluation was performed. went. Table 2 shows the results.
[Table 2]

Discussion [0098]
As is clear from the results of Tables 1 and 2, the coating pretreatment method of the comparative example is slightly inferior in any of the coating weight, the density of the crystalline coating, the primary coating adhesion, and the secondary coating adhesion. On the other hand, by adopting the coating pretreatment method of the example, the coating weight, the denseness of the crystalline coating, the primary coating adhesion, the secondary coating adhesion is also very good to slightly inferior, It was confirmed that there was no problem in quality.
[Brief description of the drawings]
FIG. 1 is a system diagram showing a first embodiment of a coating pretreatment device of the present invention.
FIG. 2 is a diagram schematically illustrating steps of entering, immersing, and exiting a processing tank in a processing tank according to the first embodiment of the present invention.
FIG. 3 is a schematic plan view of FIG. 2;
FIG. 4 is a cross-sectional view of a main part around a rotary drive device of the vehicle body transfer device shown in FIGS. 2 and 3;
FIG. 5 is a system diagram showing a second embodiment of the coating pretreatment device of the present invention.
[Explanation of symbols]
101: Treatment tank 201: Rinse tank (rinse means)
300 ... aluminum chemical conversion treatment zone (aluminum chemical conversion treatment means)
301: Chemical conversion liquid supply tank for aluminum 302 ... Piping 303 ... Pump 304 ... Nozzle 307 ... Recovery tank 308 ... Piping 309 ... Pump

Claims (48)

A mixed solvent of a polar organic solvent and water having a weight ratio of 2.8: 7.2 to 3.8: 6.2, sodium ion and / or lithium ion, phosphate ion, zinc ion, nickel ion, and manganese ion A treatment tank in which a degreasing and chemical conversion treatment solution containing at least nitrate ions and / or nitrite ions is filled, and an object to be coated is immersed;
Aluminum chemical conversion treatment means provided at the subsequent stage of the treatment tank and treating the object to be coated with a chemical conversion treatment solution for aluminum,
Rinsing means provided at a subsequent stage of the aluminum chemical conversion treatment means, for washing the article to be coated with a washing liquid,
The article to be coated, the treatment tank, the aluminum conversion treatment means, comprising an article transfer means to move to the rinsing means,
A pre-coating treatment apparatus, wherein the article transfer means has at least one of the treatment tank, the aluminum conversion treatment means, and the rinsing means, and has an article rotating means for rotating the article. The coating pretreatment apparatus according to claim 1, wherein at least a part of the object to be coated is a composite automobile body of iron and aluminum having at least a part of an outer plate portion made of aluminum or an aluminum alloy. The coating pretreatment apparatus according to claim 1, wherein the rinsing unit includes a rinsing tank filled with the cleaning liquid and immersed in the object to be coated. The article transporting means rotates the article by the article rotating means to enter the processing tank and / or the rinsing tank,
4. The pre-coating treatment apparatus according to claim 3, wherein the object to be coated is rotated by the object to be coated and discharged from the processing tank and / or the rinsing tank. The article transporting means, the article to be rotated by the article rotating means is vertically inverted and put into the treatment tank and / or the rinsing tank,
The coating pretreatment apparatus according to claim 4, wherein the object to be coated is further inverted in the vertical direction by the object to be coated and is discharged from the treatment tank and / or the rinsing tank. The coating pretreatment apparatus according to claim 5, wherein the object to be coated rotates about a vertical axis to a transport direction and parallel to a horizontal plane, and rotates a frontmost portion of the object to be coated vertically downward in the transport direction. . The coating pretreatment apparatus according to any one of claims 4 to 6, wherein the article transfer means moves the article to be coated in the treatment tank and / or the rinsing tank in a state of being vertically inverted. The coating pretreatment apparatus according to any one of claims 4 to 7, wherein the article transfer means further rotates the article in the processing tank and / or the rinsing tank. The aluminum chemical treatment means includes an aluminum chemical treatment liquid supply tank containing the adjusted aluminum chemical treatment liquid, and a spray device for spraying the aluminum chemical treatment liquid in the aluminum chemical treatment liquid supply tank onto the substrate. The coating pretreatment device according to claim 1, comprising: The aluminum chemical treatment unit is configured to collect a chemical conversion treatment liquid for aluminum sprayed on the object to be coated, and return the chemical conversion treatment liquid for aluminum collected in the collection tank to the chemical conversion treatment liquid supply tank for aluminum. The coating pretreatment device according to claim 9, comprising a first piping system. The first piping system includes a dust removing unit that removes dust contained in the chemical conversion liquid for aluminum collected in the collection tank, and a chemical sludge contained in the chemical conversion liquid for aluminum collected in the collection tank. The coating pretreatment apparatus according to claim 10, further comprising: chemical sludge removing means for removing oil; and oil removing means for removing oil contained in the chemical conversion treatment liquid for aluminum collected in the recovery tank. 12. The pre-coating treatment according to claim 11, further comprising a second piping system for leading the cleaning liquid of the rinsing means to the recovery tank and / or the most upstream means among the dust removing means, the chemical sludge removing means, and the oil removing means. apparatus. The coating pretreatment apparatus according to any one of claims 1 to 8, wherein the aluminum chemical treatment means includes an aluminum chemical treatment tank filled with the aluminum chemical treatment liquid and immersed in the article to be coated. The article-to-be-coated conveying means rotates the article to be coated by the article-to-be-coated rotating means to enter the aluminum chemical conversion treatment tank,
14. The pre-coating treatment apparatus according to claim 13, wherein the object to be coated is rotated by the object-to-be-coated rotating means to be discharged from the aluminum chemical conversion treatment tank. The object to be transported, the object to be coated is inverted by the object to be rotated in the vertical direction, and is put into the aluminum chemical conversion treatment tank,
The coating pretreatment apparatus according to claim 14, wherein the object to be coated is further vertically inverted by the object to be coated and is discharged from the aluminum chemical conversion treatment tank. 16. The pre-coating treatment according to claim 15, wherein the object to be coated rotates about an axis perpendicular to the transport direction and parallel to a horizontal plane, and vertically rotates the frontmost part of the object to be transported downward in the transport direction. apparatus. The coating pretreatment apparatus according to any one of claims 14 to 16, wherein the object-to-be-coated transporting means moves the object to be coated in the aluminum chemical conversion treatment tank in a state of being vertically inverted. The coating pretreatment apparatus according to any one of claims 14 to 17, wherein the object to be coated is further rotated in the aluminum chemical conversion treatment tank. Having a control means to control the start and stop of the rotation of the workpiece to the workpiece rotating means,
When the object to be coated has a part made of aluminum or an aluminum alloy on at least a part of an outer plate portion, when a composite automobile body of iron and aluminum is used,
The control means performs a command to rotate the object to be coated to the object rotating means, when the object to be coated is a steel plate automobile body having no aluminum or aluminum alloy parts in the outer plate portion,
The coating pretreatment apparatus according to any one of claims 14 to 18, wherein the control means issues a command not to rotate the work to the work rotating means. Spraying means for spraying pure water above the aluminum chemical conversion treatment tank,
20. The pretreatment apparatus according to claim 19, wherein when the control unit issues a command not to rotate the object to be rotated to the object rotating unit, the spraying unit sprays pure water on the steel plate-made automobile body. . 21. The pretreatment apparatus according to claim 20, wherein pure water sprayed from said spraying means is supplied to said spraying means from said rinsing means. The aluminum chemical conversion treatment means supplies an aluminum chemical conversion treatment liquid replenishment tank containing the adjusted aluminum chemical conversion treatment liquid, and supplies the aluminum chemical conversion treatment liquid in the aluminum chemical conversion treatment liquid supply tank to the aluminum chemical conversion treatment tank. The pre-coating according to any one of claims 13 to 21, comprising a third piping system and a fourth piping system for returning the chemical conversion treatment liquid for aluminum in the aluminum chemical conversion treatment tank to the chemical conversion treatment liquid supply tank for aluminum. Processing equipment. The fourth piping system includes dust removing means for removing dust contained in the aluminum chemical conversion treatment liquid in the aluminum chemical conversion treatment tank, and chemical conversion sludge contained in the aluminum chemical conversion treatment liquid in the aluminum chemical conversion treatment tank. 23. The pretreatment apparatus according to claim 22, further comprising: chemical sludge removing means for removing oil; and oil removing means for removing oil contained in the chemical conversion solution for aluminum in the aluminum chemical conversion tank. 24. The pretreatment apparatus according to claim 23, further comprising a fifth piping system for guiding the cleaning liquid of the rinsing means to the most upstream means among the dust removing means, the chemical sludge removing means, and the oil removing means. The coating pretreatment device according to any one of claims 1 to 24, wherein the polar organic solvent contains at least one of glycol ether and diethylene glycol ether. The coating pretreatment apparatus according to any one of claims 1 to 25, comprising 0.8 to 3.3 parts by weight of sodium ions and / or lithium ions with respect to 100 parts by weight of the mixed solvent of the polar organic solvent and water. . 27. The pretreatment apparatus according to claim 26, wherein the molar ratio of the sodium ions to the lithium ions is 50:50 to 2:98. 2 to 0.5 parts by weight of phosphate ions and 0.5 to 0.7 parts by weight of zinc ions with respect to 100 parts by weight of the mixed solvent of the polar organic solvent and water. 28. The coating pretreatment device according to any one of 27. The coating pretreatment apparatus according to any one of claims 1 to 28, comprising 0.09 to 0.23 parts by weight of nickel ions based on 100 parts by weight of the mixed solvent of the polar organic solvent and water. The coating pretreatment apparatus according to any one of claims 1 to 29, comprising 0.03 to 0.16 parts by weight of manganese ions based on 100 parts by weight of the mixed solvent of the polar organic solvent and water. The coating pretreatment according to any one of claims 1 to 30, wherein the polar organic solvent and water contain 3.5 to 10.8 parts by weight of nitrate ions and / or nitrite ions with respect to 100 parts by weight of the mixed solvent. apparatus. 32. The pre-coating treatment according to any one of claims 1 to 31, wherein the temperature of the treatment liquid filled in the treatment tank is 40C to 60C, and the immersion time of the object is 3 minutes to 10 minutes. apparatus. The coating pretreatment apparatus according to any one of claims 1 to 32, wherein the chemical conversion treatment liquid for aluminum includes at least one of hexafluorotitanate and hexafluorozirconate. The pH of the chemical conversion treatment liquid for aluminum sprayed on the article is 2.5 to 10, the temperature is 20 ° C to 70 ° C, and the time of spraying on the article is 20 seconds to 100 seconds. A coating pretreatment device according to any one of the above. A composite automobile body of iron and aluminum having an aluminum or aluminum alloy part in at least a part of the outer plate portion,
A mixed solvent of a polar organic solvent and water having a weight ratio of 2.8: 7.2 to 3.8: 6.2, sodium ion and / or lithium ion, phosphate ion, zinc ion, nickel ion, and manganese ion A first step of immersing in a degreasing and chemical conversion treatment solution containing at least nitrate ions and / or nitrite ions for treatment;
A second step of treating the automobile body with a chemical conversion treatment solution for aluminum;
A third step of cleaning the vehicle body with a cleaning liquid,
A coating pretreatment method for rotating the vehicle body in at least one of the steps. In the first step,
The vehicle body is inverted in the vertical direction and immersed in the degreasing and chemical conversion treatment solution,
36. The coating pretreatment method according to claim 35, wherein the automobile body is further inverted in a vertical direction and detaches from the degreasing and chemical conversion treatment liquid. In the second step,
The automobile body is immersed in the chemical conversion treatment solution for aluminum after being inverted in the vertical direction,
37. The coating pretreatment method according to claim 35, wherein the automobile body is further inverted in a vertical direction and detached from the chemical conversion treatment liquid for aluminum. In the third step,
The automobile body is inverted in the vertical direction and immersed in the cleaning liquid,
The coating pretreatment method according to any one of claims 35 to 37, wherein the vehicle body is further inverted in a vertical direction and detached from the cleaning liquid. The coating pretreatment method according to any one of claims 35 to 38, wherein the polar organic solvent contains at least one of glycol ether and diethylene glycol ether. The coating pretreatment method according to any one of claims 35 to 39, comprising 0.8 to 3.3 parts by weight of sodium ions and / or lithium ions with respect to 100 parts by weight of the mixed solvent of the polar organic solvent and water. . The coating pretreatment method according to any one of claims 35 to 40, wherein the molar ratio of the sodium ion to the lithium ion is 50:50 to 2:98. 35. The composition according to claim 35, comprising 0.2 to 0.5 parts by weight of phosphate ions and 0.5 to 0.7 parts by weight of zinc ions with respect to 100 parts by weight of the mixed solvent of the polar organic solvent and water. 41. The coating pretreatment method according to any one of 41. 43. The coating pretreatment method according to any one of claims 35 to 42, comprising 0.09 to 0.23 parts by weight of nickel ions based on 100 parts by weight of the mixed solvent of the polar organic solvent and water. The coating pretreatment method according to any one of claims 35 to 43, wherein manganese ion is contained in an amount of 0.03 to 0.16 parts by weight based on 100 parts by weight of the mixed solvent of the polar organic solvent and water. The pretreatment for coating according to any one of claims 35 to 44, comprising 3.5 to 10.8 parts by weight of nitrate ions and / or nitrite ions based on 100 parts by weight of the mixed solvent of the polar organic solvent and water. Method. The coating pretreatment method according to any one of claims 35 to 45, wherein the temperature of the degreasing / chemical conversion treatment solution is 40C to 60C, and the immersion time of the automobile body is 3 minutes to 10 minutes. The coating pretreatment method according to any one of claims 35 to 46, wherein the chemical conversion treatment liquid for aluminum contains at least one of hexafluorotitanate and hexafluorozirconate. 48. The chemical conversion treatment solution for aluminum sprayed on the vehicle body has a pH of 2.5 to 10, a temperature of 20C to 70C, and a time of spraying on the vehicle body of 20 seconds to 100 seconds. Pretreatment method for coating described in Crab.

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