CN103057198B - Aluminum alloy plate, and joint body and automobile member using same aluminum alloy plate - Google Patents

Aluminum alloy plate, and joint body and automobile member using same aluminum alloy plate Download PDF

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Publication number
CN103057198B
CN103057198B CN201210336967.8A CN201210336967A CN103057198B CN 103057198 B CN103057198 B CN 103057198B CN 201210336967 A CN201210336967 A CN 201210336967A CN 103057198 B CN103057198 B CN 103057198B
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aluminium alloy
alloy plate
surface oxidation
conjugant
adhesive
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CN103057198A (en
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巽明彦
高田悟
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2204/00—End product comprising different layers, coatings or parts of cermet

Abstract

The invention provides an aluminum alloy plate which has an adhesive strength difficult to reduce and excellent adhesive durability, and a joint body and an automobile member using the same aluminum alloy plate. The aluminum alloy plate is difficult to boundary disengagement with a joint boundary of an adhesive agent even though the aluminum alloy plate being exposed in high-temperature and moist environment and in salt water spray environment. The aluminum alloy plate is characterized in that: the aluminum alloy plate comprises an aluminum alloy substrate (1) and a surface scale film (2) formed on a surface of the aluminum alloy substrate (1). In the surface scale film (2), zirconium weight is 0.01-10 atoms %, magnesium weight is greater than or equal to 0.1 atom % and less than 10 atoms %. In the analysis of the surface scale film (2) with FT-IP (Fourier transform infrared spectrophotometer) at a 75-degree incident angle, absorbance is for indicating the light spectrum of a metal hydroxide, a reference line is from 400 cm-1 to 1800 cm-1, the height of a spectrum peak is less than or equal to 0.020 in a wave number part of 1060 cm-1.

Description

Aluminium alloy plate, the conjugant using this aluminium alloy plate and member for automobile
Technical field
The present invention relates to a kind of aluminium alloy plate, and the vehicle relating to a kind of automobile, boats and ships, aircraft etc. is used, particularly can be suitable for the aluminium alloy plate in car panel, the conjugant using this aluminium alloy plate and member for automobile.
Background technology
All the time, as the component of the conveyers such as automobile, boats and ships, aircraft, according to the various characteristic of each alloy and general various aluminium alloy plate.Particularly, CO is in recent years recognized 2the global environmental problems such as discharge, seek the saving of the light-weighted fuel consumption of Component-Based Development, increase proportion and are about 1/3 of iron and have the use of the aluminium alloy plate of excellent energy absorption.
Such as, as the aluminium alloy plate being used as member for automobile, enumerate the aluminium alloy plate containing Mg such as the Al-Mg system alloy sheets of JIS5000 system, the Al-Mg-Si system alloy sheets of JIS6000 system.As the joint method of above-mentioned aluminium alloy plate, use and be somebody's turn to do both based on welding, the joint of adhesive or dual-purpose.Utilize point, line and engaging relative to welding, because binding agent based bonding utilizes face entirety to engage, therefore bond strength becomes higher, thus the aspects such as security are hit in the sight being conducive to automobile, and therefore binding agent based bonding is in recent years in increasing tendency.
On the other hand, utilize the aluminum alloy member for automobile of adhesive bond, in use have moisture, oxygen, chloride ion etc. to immerse its junction surface, the interface thus between adhesive phase and aluminium alloy plate runs down, produce interface peel, there is the problem that bonding strength reduces.The salinity particularly comprised because of the antifreezing agent from evaporation of seawater salinity, road etc. soaks into and causes promoting the deterioration of stick portion.
As improving the method with the adhesion durability of the aluminum alloy member for automobile of adhesive phase, generally as we all know there are between those skilled in the art: before coating adhesive, utilize pickling and the method that removes the near surface that is present in aluminium alloy plate in advance and become the weak oxide scale film of the mechanical property of interface peel reason (such as, with reference to patent document 1), by the near surface anodic oxidation of aluminium alloy plate, oxidizing epithelium brings the method for the imparting configuration of surface of fixed effect, and warm water process is carried out to the surface of aluminium alloy plate and adjust oxide scale film Mg amount and OH amount method (such as, with reference to patent document 2, 3).
In addition, when aluminium alloy is used as car panel, require formability, weldability, cohesive, chemical combination treatability, smear after corrosion resistance and attractive in appearance etc.The method using aluminium alloy to manufacture car panel is: 1) being shaped (cuts into given size, and stamping be regulation shape), 2) engage (welding and/or bonding), 3) chemical combination process (degreasing → based on the surface adjustment → trbasic zinc phosphate process of colloid titanate process etc. based on cleaning agent), 4) smear (the lower painting → middle painting → upper painting based on plating), substantially identical with the situation of existing use steel plate.
On the other hand, along with the modular processes of automobile component develops, after aluminium alloy plate self is manufactured, during entering Auto-body manufacturing operation, elongated tendency is had from above-mentioned car panel than ever.The modularization of automobile component refers to, all parts being directly installed on vehicle body is installed in components company the method for vehicle body in automobile factory in advance after partial assembled.Its main purpose is to simplify the difficult operation in automobile factory, thus enhances productivity.Also there is shortening production process, reduce half-finished effect.Although the burden of components company increases, the cost for motor corporation and components company's entirety reduces and has effect, consequently contributes to the cost cutting of automobile.
In addition, the transport path of aluminium alloys for automobile plate up to now main flow be directly pay mode from Ruan Ya manufactory to automobile factory.But, along with modular progress, have to via components company, in any case aluminium alloy plate self manufactured after to entering above-mentioned manufacturing process during elongated than ever.
But, under these circumstances, in any case the situation of surface characteristic along with time variations of aluminium alloy plate also can be there is, there is the problem to cohesive, chemical combination treatability, smear generation baneful influence.As everyone knows, wherein make degreasing during chemical combination process worsen along with time variations, chemical combination process epithelium becomes and is difficult to attachment, consequently has an impact to corrosion resistance.Therefore, according to the magnesium (following, also magnesium to be called Mg) in the past by the aluminum alloy surface of removing containing magnesium, strength (with reference to patent document 1,4 ~ 6) is poured into raising chemical combination treatability etc.
In addition, in order to obtain the moistening after particularly degreasing and the excellent aluminium alloy plate of cohesive, also proposing to have measure the Mg amount of the surperficial epithelium of aluminium alloy plate and OH and adjust and within surface adjusts latter 14 days, apply the scheme (reference patent document 2) of the motor-car body sheet aluminium alloy plate of antirust oil.In addition, in order to Formation and characteristics is along with the little aluminium alloy plate of time variations, propose the scheme having following Aluminum alloy for automotive body plate, it possesses: the metallic aluminium matrix of the aluminium alloy plate of the Mg containing 2 ~ 10 % by weight, the phosphate coating being formed at the aluminium on this matrix and the pellumina (with reference to patent document 7) be formed on phosphate coating.
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-256881 publication
Patent document 2: Japanese Unexamined Patent Publication 2006-200007 publication
Patent document 3: Japanese Unexamined Patent Publication 2007-217750 publication
Patent document 4: Japanese Unexamined Patent Publication 06-256980 publication
Patent document 5: Japanese Unexamined Patent Publication 04-214835 publication
Patent document 6: Japanese Unexamined Patent Publication 02-115385 publication
Patent document 7: Japan Patent No. 2744697 publication
In the above prior art, there is following problem about adhesion durability.
Carrying out in the method for pickling described in patent document 1, due to containing the more Mg as alloying component, oxide scale film that mechanical property is weak is removed, therefore prevent the interface peel at initial stage, thus improve bonding strength.But, when being exposed in the adverse condition such as high temperature moist environment, salt spray environment that moisture, oxygen, chloride ion etc. soak into gradually, Cu as alloying component is concentrated on oxide scale film removing face, produces the phenomenon being referred to as copper evil causing adhesive phase deterioration to be accelerated because of this Cu.Consequently, moisture etc. soak into the quality (substrate) of aluminium alloy plate sometimes, interface degradation, so cause interface peel and exist bonding strength reduce problem.Further, when Cu is in Al surface densification, due to the potential difference between itself and Al, thus under saltwater environment, the corrosion of Al is promoted.
In addition, carrying out in anodised method, in order to prevent deterioration, the stripping at interface, need to be formed as thicker by being endowed the oxide scale film being used for the configuration of surface improving adhesion durability fully, therefore, epithelium is formed needs the long period, there is the problem of production efficiency step-down.
In addition, carry out in the method for warm water process described in patent document 2,3, although the bonding strength at initial stage, moistening after secondary adhesion be enhanced, but when being exposed in high temperature moist environment, salt spray environment, because of the aquation at interface, the dissolving of base material and cause the deterioration at interface to be in progress, thus generation interface peel, there is the problem that bonding strength reduces.
In addition, in the above prior art, there is following problem about the stability (surface stability) of surface characteristic, i.e. water profit stability.
In above-mentioned patent document 1,4 ~ 6, incessantly needing the removing of the magnesium of aluminum alloy surface after cold rolling, is only that the removing of such magnesium just can not obtain surface characteristic along with the excellent aluminium alloy plate of the surface stability that time variations is little.Further, as described in Patent Document 2, be only that adjustment only applies antirust oil and protects surface within latter 14 days on surface, surface characteristic can not be obtained along with the excellent aluminium alloy plate of the surface stability that time variations is little.
In addition, in above-mentioned patent document 7, in embodiment, make the rear placement material of a week with sample and compare evaluation for benchmark.But the change in time of the surface characteristic of above-mentioned aluminium alloy, maximum from the variable quantity by about a week after sample has just been made, change is afterwards smaller.Therefore, the evaluation result according to above-mentioned patent document 7, can not ensure the stability of the surface characteristic of target.
Like this, require a kind of surface stability, be namely coated with unction and long-term keeping and the excellent aluminium alloy plate of moistening (after the degreasing after long-term moistening keeping moistening (following, to be suitably called water profit stability)) after having carried out degreasing afterwards.
Summary of the invention
The present invention is used for solving the problem, even if its problem be to provide a kind of be exposed to high temperature moist environment, salt spray environment under be also difficult to produce the interface peel at the joint interface of adhesive, therefore bonding strength be difficult to decline, the aluminium alloy plate that adhesion durability is excellent, the conjugant using this aluminium alloy plate and member for automobile.In addition, its problem is also the aluminium alloy plate providing a kind of water to moisten excellent in stability, the conjugant using this aluminium alloy plate and member for automobile.
Problem of the present invention more preferably, provides a kind of above-mentioned adhesion durability and water to moisten stability all excellent aluminium alloy plate, the conjugant using this aluminium alloy plate and member for automobile.
In order to solve the problem, aluminium alloy plate involved in the present invention possesses: aluminium alloy base plate; And the surface of above-mentioned aluminium alloy base plate formed surface oxidation epithelium, in above-mentioned surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %, at the FT-IR (Fourier transform infrared spectrophotometer) being 75 degree by use incidence angle, above-mentioned surface oxidation epithelium is analyzed, and when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights be less than or equal to 0.020.
According to said structure, owing to possessing the surface oxidation epithelium of zirconium containing ormal weight and magnesium, therefore when utilizing adhesive member joining aluminum alloy plate, even if under being exposed to high temperature moist environment, salt spray environment, also can suppress the aquation on the interface between adhesive member and surface oxidation epithelium, and the liquate of aluminium alloy base plate can be suppressed.Consequently, can interface peel be suppressed, thus suppress the reduction of bonding strength.And, owing to controlling the content of zirconium and magnesium, therefore by the impact of kind of adhesive forming adhesive member, in all adhesives used when joining aluminum alloy plate all the time, can interface peel be suppressed, thus the reduction of bonding strength can be suppressed.In addition, due to (following by the spectrum peak heights to metal hydroxides, suitably, be called metal hydroxides peak height) control, crisp and metal hydroxides that is that be easy to dissolve tails off compared with oxide, therefore can suppress the generation of interface peel between aluminium alloy plate surface under salt spray environment and adhesive.
In addition, the feature of aluminium alloy plate involved in the present invention is, above-mentioned aluminium alloy plate possesses: aluminium alloy base plate; And the surface of above-mentioned aluminium alloy base plate formed surface oxidation epithelium, in above-mentioned surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %, at the FT-IR (Fourier transform infrared spectrophotometer) being 75 degree by use incidence angle, above-mentioned surface oxidation epithelium is analyzed, and when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1when as datum line, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights be less than or equal to 0.040.
According to said structure, owing to possessing the surface oxidation epithelium of zirconium containing ormal weight and magnesium, the oxidation of aluminium alloy base plate for a long time under moist environment therefore can be suppressed.In addition, be difficult to the ester composition in surface oxidation epithelium forms easy absorption punching oil or organic pore, oil component is difficult to be taken in by pore.Thus, obtain long-term surface stability, even if the moistening also degreasing can be maintained after long-term keeping after.And then controlled by the spectrum peak heights (following, to be suitably called metal oxide peak height) to metal oxide, the ester composition easily in absorption punching oil or organic pore reduce, thus manifest good water profit stability.
In addition, the feature of aluminium alloy plate involved in the present invention is, above-mentioned aluminium alloy plate possesses: aluminium alloy base plate; And the surface of above-mentioned aluminium alloy base plate formed surface oxidation epithelium, in above-mentioned surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %, at the FT-IR (Fourier transform infrared spectrophotometer) being 75 degree by use incidence angle, above-mentioned surface oxidation epithelium is analyzed, and when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights be less than or equal to 0.020, and at the FT-IR (Fourier transform infrared spectrophotometer) being 75 degree by use incidence angle, above-mentioned surface oxidation epithelium is analyzed, and when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1when as datum line, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights be less than or equal to 0.040.
According to said structure, utilize above-mentioned effect, can interface peel be suppressed, thus the reduction of bonding strength can be suppressed, and manifest good water profit stability.
Aluminium alloy plate involved in the present invention is preferably, and also possesses on the surface of above-mentioned surface oxidation epithelium the adhesive phase be made up of adhesive.
According to said structure, because aluminium alloy plate possesses adhesive phase in advance, therefore when using aluminium alloy plate to make conjugant or member for automobile, the formation operation of adhesive member on the surface of aluminium alloy plate can be omitted.
Aluminium alloy plate involved in the present invention is preferably, and the ratio of the zirconium amount (Zr amount) of above-mentioned surface oxidation epithelium and magnesium amount (Mg measures) (Zr measure/Mg measure) is 0.0025 ~ 10.
According to said structure, because the zirconium amount of surface oxidation epithelium and the ratio of magnesium amount are in prescribed limit, therefore, it is possible to suppress the aquation on the interface between adhesive member (adhesive phase) and surface oxidation epithelium further, thus the liquate of aluminium alloy base plate can be suppressed further.Consequently, interface peel can be suppressed further, thus suppress the reduction of bonding strength further.In addition, water profit stability improves.
Aluminium alloy plate involved in the present invention is preferably, and above-mentioned aluminium alloy base plate is made up of Al-Mg system alloy, Al-Cu-Mg alloy, Al-Mg-Si system alloy or Al-Zn-Mg system alloy.
According to said structure, when the alloy kind many by content of magnesium forms aluminium alloy base plate, although have magnesium in substrate surface multiviscosisty and easily produce weak boundary layer at adhesive interface, but due to the magnesium amount of the surface oxidation formed at substrate surface epithelium is controlled in prescribed limit, specifically remove the magnesium of multiviscosisty and control in prescribed limit, even if therefore form substrate by the alloy kind that content of magnesium is many, also can suppress interface peel, thus the reduction of bonding strength can be suppressed.In addition, because the magnesium amount of surface oxidation epithelium is controlled in prescribed limit, even if therefore form substrate by the alloy kind that content of magnesium is many, water profit stability also can be improved.
Conjugant involved in the present invention be do not possess adhesive phase above-mentioned aluminium alloy each other across the conjugant that the adhesive member be made up of adhesive is engaged, it is characterized in that, the surface oxidation epithelium side engagement of above-mentioned adhesive member and two above-mentioned aluminium alloy plates, the surface oxidation epithelium of two above-mentioned aluminium alloy plates configures in the mode relative across above-mentioned adhesive member respectively.
In addition, conjugant involved in the present invention is the conjugant being bonded to the second aluminium alloy plate be made up of aluminium alloy on the first aluminium alloy plate be made up of the above-mentioned aluminium alloy plate not possessing adhesive phase across the adhesive member be made up of adhesive, it is characterized in that, the surface oxidation epithelium side engagement of above-mentioned adhesive member and above-mentioned first aluminium alloy plate.
In addition, conjugant involved in the present invention is the conjugant having the above-mentioned aluminium alloy plate not possessing adhesive phase in the adhesive phase side engagement of the above-mentioned aluminium alloy plate having possessed adhesive phase, it is characterized in that, the surface oxidation epithelium of two above-mentioned aluminium alloy plates configures in the mode relative across above-mentioned adhesive phase respectively.
And then, conjugant involved in the present invention is the conjugant being bonded to the second aluminium alloy plate be made up of aluminium alloy on the first aluminium alloy plate be made up of the above-mentioned aluminium alloy plate having possessed adhesive phase, it is characterized in that, the adhesive phase side engagement of above-mentioned second aluminium alloy plate and above-mentioned first aluminium alloy plate.
According to said structure, because the aluminium alloy plate of conjugant by the surface oxidation epithelium of the zirconium possessed containing ormal weight and magnesium is formed, and have adhesive member or adhesive phase in the surface oxidation epithelium side engagement of this aluminium alloy plate (the first aluminium alloy plate), therefore when conjugant is used in member for automobile, even if under being exposed to high temperature moist environment, salt spray environment, also can suppress the aquation on adhesive member or the interface between adhesive phase and surface oxidation epithelium, and the liquate of aluminium alloy base plate can be suppressed.Consequently, can interface peel be suppressed, thus the reduction of bonding strength can be suppressed.In addition, owing to controlling the content of zirconium amount and magnesium amount, therefore the impact of the kind of the adhesive forming adhesive member or adhesive phase is not subject to, in all adhesives all the time used when joining aluminum alloy plate, can interface peel be suppressed, thus the reduction of bonding strength can be suppressed.And then, by controlling metal hydroxides peak height, because metal hydroxides that is crisp compared with oxide and that be easy to dissolve tails off, the generation of interface peel between aluminium alloy plate surface under salt spray environment and adhesive therefore can be suppressed.
In addition, by using the aluminium alloy plate of water profit excellent in stability to form conjugant, easily improving aluminium alloy plate cohesive each other, thus easily improving adhesion durability.
The feature of member for automobile involved in the present invention is, above-mentioned member for automobile is manufactured by above-mentioned conjugant.
According to said structure, because member for automobile is manufactured by conjugant as described above, even if under being therefore exposed to high temperature moist environment, salt spray environment, also can suppress to form the aquation on the adhesive member in the conjugant of member for automobile or the interface between adhesive phase and surface oxidation epithelium, and the liquate of aluminium alloy base plate can be suppressed.Consequently, can interface peel be suppressed, thus the reduction of bonding strength can be suppressed.In addition, by using the aluminium alloy plate of water profit excellent in stability to form conjugant, easily improving aluminium alloy plate cohesive each other, thus easily improving adhesion durability.
Invention effect
According to the present invention, even if a kind of joint interface be also difficult at adhesive that is exposed in high temperature moist environment, salt spray environment can be provided to produce interface peel, thus bonding strength be difficult to reduce, excellent and its adhesion durability of adhesion durability by the species influence of adhesive aluminium alloy plate and use the conjugant of this aluminium alloy plate.In addition, the member for automobile that adhesion durability is excellent can be provided.
According to the present invention, aluminium alloy plate, the conjugant using this aluminium alloy plate and member for automobile that water moistens excellent in stability can be provided.
According to the present invention, above-mentioned adhesion durability and water can be provided to moisten stability all excellent aluminium alloy plate, the conjugant using this aluminium alloy plate and member for automobile.
Accompanying drawing explanation
Fig. 1 (a), (b) are the sectional views of the structure schematically showing aluminium alloy plate involved in the present invention.
Fig. 2 is the process flow of manufacture method of aluminium alloy plate that Fig. 1 (a), (b) are shown.
Fig. 3 (a) ~ (d) is the sectional view of the structure schematically showing conjugant involved in the present invention.
Fig. 4 illustrates the shape of the adhesive test body made in an embodiment, and (a) is side view, and (b) is top view.
Description of reference numerals is as follows:
1 aluminium alloy base plate (substrate)
2 surface oxidation epitheliums
3 adhesive phases
10,10A aluminium alloy plate
10a, 10Aa first aluminium alloy plate
11 adhesive members
12 second aluminium alloy plates
20,20A, 20B, 20C conjugant
Detailed description of the invention
" aluminium alloy plate "
Below, with reference to Fig. 1 (a), aluminium alloy plate involved in the present invention is specifically described.As shown in Fig. 1 (a), the surface oxidation epithelium 2 that aluminium alloy plate 10 possesses aluminium alloy base plate 1 (hereinafter referred to as substrate) and formed on the surface of this substrate 1.In addition, as described later, in a manufacturing method, initial formation oxide scale film, then zirconium saline solution is utilized to carry out surface treatment to the oxide scale film formed, zirconium dioxide is attached to or enters oxide scale film thus, and obtains as the magnesium amount of oxide scale film the epithelium that controls and form surface oxidation epithelium 2.
In addition, the surface of substrate 1 represents at least one side on the surface of substrate 1 herein, comprises so-called one side, two-sided.
Below, each formation of aluminium alloy plate 10 is described.
< substrate >
Substrate 1 is made up of aluminium alloy, and according to the purposes of aluminium alloy plate 10 suitably from JIS regulation or select the various nonheat-treatable aluminum alloy that is similar to JIS or heat treatment type aluminium alloy.In addition, nonheat-treatable aluminum alloy is fine aluminium (1000 are), Al-Mn system alloy (3000 are), Al-Si system alloy (4000 are) and Al-Mg system alloy (5000 are), and heat treatment type aluminium alloy is Al-Cu-Mg alloy (2000 are), Al-Mg-Si system alloy (6000 are) and Al-Zn-Mg system alloy (7000 are).
When enumerating concrete example, when aluminium alloy plate 10 is used for automobile, be preferably the substrate that 0.2% endurance is more than or equal to the high strength of 100MPa.Meeting the aluminium alloy of the substrate of above-mentioned characteristic as forming, usually using aptly: general in this type of structure component purposes, 2000 be, 5000 be, 6000 be and 7000 be etc. containing many magnesium, general-purpose alloy that endurance is higher and be as required and by modified aluminium alloy.From excellent age-hardening energy, alloying element amount is fewer and aspect that the recycling of waste material or formability are also excellent, preferably uses 6000 line aluminium alloys.
< surface oxidation epithelium >
Even if realize the raising of water profit stability in order to the raising that also can realize adhesion durability when being exposed in high temperature moist environment, salt spray environment, surface oxidation epithelium 2 contains the zirconium of ormal weight and the surface oxidation epithelium of magnesium.
And then, with metal hydroxides peak height for specifying that following mode forms the epithelium that inhibit metal hydroxides amount.Or, with metal oxide peak height for specifying that following mode forms the epithelium that inhibit metal oxide amount.About above-mentioned epithelium, when paying attention to adhesion durability, suppress metal hydroxides amount; When paying attention to water profit stability, suppress metal oxide amount.Thus, as long as at least one party of regulation metal hydroxides amount and metal oxide amount.But, from the view point of meeting adhesion durability and water profit both stability, preferably specify metal hydroxides amount and metal oxide amount simultaneously.
In addition, about the formation of surface oxidation epithelium 2, this is in surface oxidation epithelium formation process S2 described later (with reference to Fig. 2), heating after the surface of substrate 1 forms oxide scale film in utilization, by utilizing zirconium saline solution, surface-treated oxide scale film entirety having been carried out to form surface oxidation epithelium 2 to the surface of oxide scale film.
(zirconium amount)
The zirconium amount that surface oxidation epithelium 2 has is in the scope of 0.01 ~ 10 atom %.
By being that the mode of 0.01 ~ 10 atom % contains zirconium with the zirconium amount of surface oxidation epithelium 2, surface oxidation epithelium 2 increases relative to the stability of the degradation factors such as water, oxygen, chloride ion thus, the aquation on the interface of adhesive and surface oxidation epithelium 2 can be suppressed, and suppress the liquate of substrate 1.Consequently, the adhesion durability of aluminium alloy plate 10 improves.In addition, due to the existence of zirconium, even if also can surface stabilization be made under high temperature moist environment, salt spray environment, prevent the deterioration at interface, thus improve adhesion durability.And then, contain zirconium in the mode that the zirconium amount of surface oxidation epithelium 2 is 0.01 ~ 10 atom %, suppress the oxidation of aluminium alloy base plate for a long time under moist environment thus.Thus, obtain long-term surface stability, even if the moistening also degreasing can be maintained after long-term keeping after.
When the zirconium amount of surface oxidation epithelium 2 is less than 0.01 atom %, not there is effect; When more than 10 atom %, effect is saturated.Zirconium amount is preferably 0.02 ~ 8 atom %, more preferably 0.04 ~ 6 atom %.Method in surface oxidation epithelium 2 is contained in as making zirconium, such as, the aqueous solution effects on surface oxide scale film 2 enumerating the zirconates utilizing zirconium nitrate (formal name: dinitric acid zirconia, trivial name: zirconyl nitrate, zirconyl nitrate, nitric acid zircon etc.), zirconium sulfate, zirconium acetate such carries out surface treatment.In addition, in order to the zirconium amount of effects on surface oxide scale film 2 adjusts, can be undertaken adjusting by the concentration of the processing time of effects on surface process, temperature, surface treatment liquid and pH and form desired zirconium amount.
(magnesium amount)
The magnesium amount that surface oxidation epithelium 2 has is being more than or equal to 0.1 atom % and being less than in the scope of 10 atom %.
The aluminium alloy forming substrate 1 contains magnesium usually as alloying component.And in the surface oxidation epithelium 2 that the surface of substrate 1 is formed, magnesium exists with the state of multiviscosisty in its surface, and this magnesium becomes the weak boundary layer of adhesive interface and makes the adhesion durability at initial stage reduce.In addition, under the high temperature moist environment soaked into gradually at moisture, oxygen, chloride ion etc., salt spray environment, and the aquation at interface between adhesive becomes the reason of the dissolving of substrate 1, thus the adhesion durability of aluminium alloy plate 10 is reduced.In addition, magnesium is the element of the volume contraction because of oxidation, and in aluminium alloy containing magnesium, the oxide on the surface of substrate 1 forms the composite oxides of aluminium and magnesium.When the magnesium component amount in oxide is many, easily form pore at surface oxidation epithelium 2.And oil component is ingested pore, in degreasing process, be difficult to removing, thus the moistening after degreasing reduces.Therefore, in order to ensure the moistening after the degreasing after long-term keeping, need to make magnesium within the limits prescribed.
Therefore, by the surface treatment of surface oxidation epithelium 2, magnesium amount is adjusted to and is less than 10 atom % and makes adhesion durability, water moisten stability raising.Magnesium amount is preferably less than 8 atom %, is more preferably less than 6 atom %.From the view point of economy, the lower limit of magnesium amount is for being more than or equal to 0.1 atom %.Magnesium amount as effects on surface oxide scale film 2 carries out the method for adjustment adjusted, such as, utilize the acid such as nitric acid, sulfuric acid or the aqueous solution effects on surface oxide scale film 2 such as zirconates to carry out surface treatment, undertaken adjusting by the concentration of processing time of effects on surface process, temperature and surface treatment liquid or pH and desired magnesium amount can be formed.That is, the magnesium of surface oxidation epithelium 2 is dissolved in acid or zirconium saline solution, thus the magnesium amount of adjustment form surface oxidized skin film 2.
In addition, even if separately the zirconium amount of control surface oxide scale film 2 and magnesium amount, compared with the raising effect also finding out adhesion durability when not controlling.But, when carrying out the control of either party of the zirconium amount of surface oxidation epithelium 2 and magnesium amount, sometimes also causing because of the kind of adhesive can't see improving effect, not finding stable adhesion durability.According to the kind of adhesive, also there is the adhesive that adhesion durability affects by magnesium amount magnesium amount sensitivity, and also there is the adhesive that zirconium amount sensitivity is affected by zirconium amount, therefore in order to improve the adhesion durability of the adhesive of overall heat cure system, zirconium amount and magnesium amount are controlled particularly important.
In addition, surface oxidation epithelium 2 is preferably the ratio (Zr measure/Mg measure) of zirconium amount (Zr amount) and magnesium amount (Mg measures) is 0.0025 ~ 10.By making ratio (Zr amount/Mg measures) in prescribed limit, the aquation at the interface between adhesive and surface oxidation epithelium 2 can be suppressed thus further, and the liquate of substrate 1 can be suppressed further.Consequently, interface peel can be suppressed further, the reduction of the bonding strength of aluminium alloy plate 10 can be suppressed further, thus improve adhesion durability further.Preferred higher limit is 5 further.
In addition, about water profit stability, by controlling zirconium amount and magnesium amount and the ratio of zirconium amount and magnesium amount controlled in above-mentioned scope simultaneously, even if carry out the keeping of longer-term thus, good water profit stability also can be manifested.
In addition, surface oxidation epithelium 2 is preferably containing the zirconium of afore mentioned rules amount and the magnesium of afore mentioned rules amount, simultaneously in fact not containing halogen and phosphorus.In fact what is called does not refer to containing halogen and phosphorus, such as when measuring halogen and phosphorus, fluorine: be less than 0.1 atom %, chlorine: be less than 0.1 atom %, bromine: be less than 0.1 atom %, iodine: be less than 0.1 atom %, astatine: be less than 0.1 atom %, phosphorus: be less than 0.1 atom %.And, when surface oxidation epithelium 2 is containing halogen, the manufacturing equipment corresponding with halogen is increased burden.In addition, when surface oxidation epithelium 2 is containing phosphorus, easily precipitation is produced when discharging surface treatment liquid, easy contaminated environment.
And then surface oxidation epithelium 2 is except containing except above-mentioned element (zirconium, magnesium, halogen and phosphorus), and surplus comprises oxygen, aluminium and impurity.The preferred content of oxygen, aluminium is respectively 15 ~ 80 atom %.C, N, Si, Ca, Fe, Cu, Mn, Ti, Zn, Ni etc. are exemplified out, if C is then less than 10 atom % if N is then less than 15 atom % if the content that other impurity is then less than 7 atom % is allowed to as impurity.
Then, the spectrum peak heights of metal hydroxides and the spectrum peak heights of metal oxide are described.
(the spectrum peak heights of metal hydroxides: be less than or equal to 0.020)
As the Al (OH) of metal hydroxides 3, Mg (OH) 2carry out reacting being formed although to be contacted with water by the oxide in surface oxidation epithelium 2, metal hydroxides is more crisp compared with oxide, more easily dissolve.Therefore, under the adverse condition that there is the salinity becoming problem in adhesion durability especially, easily produce the interface peel between aluminium alloy plate surface and adhesive.By suppressing metal hydroxides peak height for being less than or equal to 0.020, stably show adhesion durability.Metal hydroxides peak height is preferably less than or equal to 0.017, is more preferably less than or equal to 0.015.
In addition, metal hydroxides peak height is the smaller the better, although be 0 also can, the lower limit that can suppress in reality is 0.001.
In order to metal hydroxides peak height being suppressed for being less than or equal to 0.020, after being less than the liquid comes into contact of 5 with pH, washing within 5 minutes, carrying out drying in washing within latter 5 minutes.Thereby, it is possible to suppress the metal hydroxides amount on surface.When the time to washing or time to drying more than 5 minutes time, the quantitative change of metal hydroxides is many and do not meet regulation.
At this, " after being less than the liquid comes into contact of 5 with pH; washed within 5 minutes; carry out drying in washing within latter 5 minutes " refers to, after the terminating with the contact of liquid of stipulated time, washed within 5 minutes, after carrying out this washing stipulated time, within 5 minutes, carry out drying.Now, after the contact with liquid terminates, even if liquid is attached to aluminium alloy, as long as carried out washing within 5 minutes, after water washing, even if be attached with water droplet, as long as carried out drying within 5 minutes.
(quantitative approach at the spectrum peak of metal hydroxides)
As the quantitative approach at the spectrum peak of metal hydroxides, can make with the following method: such as, analyze at the FT-IR (Fourier transform formula infrared spectrophotometer: Nicolet Magna-750spectrometer) by use incidence angle 75 degree, according to when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights (maximum height) and carry out quantification.
That is, by carrying out FT-IR analysis, the spectrum of the metal hydroxides in surface oxidation epithelium 2 is shown in Fourier transform formula infrared spectrophotometer by absorbance.In the spectrum that this is shown by absorbance from 400cm -1to 1800cm -1as datum line, at 1060cm -1wave number part produce spectrum peak heights measure.
(the spectrum peak heights of metal oxide: be less than or equal to 0.040)
The composite oxides of Al and Mg are formed on aluminium alloy plate surface.The composite oxides of Al and Mg be considered to have the moistening after reducing degreasing, ester composition easily in absorption punching oil or organic pore.And because the pore that the ratio of Mg is more, it easily adsorbs more increases, therefore oxide amount is more few better.By suppressing metal oxide peak height for being less than or equal to 0.040, show good water profit stability.Metal oxide peak height is preferably less than or equal to 0.037, is more preferably less than or equal to 0.035.
In addition, metal oxide peak height is the smaller the better, although be 0 also can, the lower limit that can suppress in reality is 0.001.
In order to metal oxide peak height being suppressed for being less than or equal to 0.040, washing after being less than more than liquid comes into contact 2 second of 5 with pH, carrying out drying within 5 minutes after water washing.Thereby, it is possible to suppress the metal oxide amount on surface.When the time of contact being less than the liquid of 5 with pH be less than 2 seconds or time to drying more than 5 minutes time, the quantitative change of metal oxide is many and do not meet regulation.
At this, " wash after being less than more than liquid comes into contact 2 second of 5 with pH, carry out drying within 5 minutes after water washing " and refer to, wash after terminating with the contact of liquid more than 2 seconds, after carrying out this washing stipulated time, within 5 minutes, carry out drying.Now, although be not particularly limited in the time after the contact with liquid terminates to washing, as long as carried out washing within such as 5 minutes.In addition, after water washing, even if be attached with water droplet, as long as carried out drying within 5 minutes.
(quantitative approach at the spectrum peak of metal oxide)
As the quantitative approach at the spectrum peak of metal oxide, can make with the following method: such as, analyze at the FT-IR (Fourier transform formula infrared spectrophotometer: Nicolet Magna-750spectrometer) by use incidence angle 75 degree, according to when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1when as datum line, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights (maximum height) and carry out quantification.
That is, by carrying out FT-IR analysis, the spectrum of the metal oxide in surface oxidation epithelium 2 is shown in Fourier transform formula infrared spectrophotometer by absorbance.In the spectrum that this is shown by absorbance from 400cm -1to 1800cm -1as datum line, to from 800cm -1to 1000cm -1wave number part produce spectrum peak heights measure.
In addition, if due to the metal hydroxides in surface oxidation epithelium 2 or metal oxide not with above-mentioned spectrum peak heights for index; be difficult to specify, therefore in the present invention, use the spectrum peak heights of the quantitative approach at the spectrum peak based on above-mentioned metal hydroxides or metal oxide, metal hydroxides amount or metal oxide amount are specified.
(thickness)
The thickness of this surface oxidation epithelium 2 is preferably 1 ~ 30nm.When thickness is less than 1nm, the absorption of the ester composition the punching oil of the antirust oil used when making substrate 1 and use when making conjugant (with reference to Fig. 3 (a) ~ (d)) and member for automobile (not shown) from aluminium alloy plate 10.Therefore, even if do not have surface oxidation epithelium 2, also can guarantee the degreasing of aluminium alloy plate 10, chemical combination treatability and adhesion durability, but be less than 1nm to need excessive acid cleaning etc. by the film thickness monitoring of surface oxidation epithelium 2, productivity ratio is low, and practicality easily reduces.On the other hand, when the thickness of surface oxidation epithelium 2 is more than 30nm, easily occur concavo-convex on surface due to epithelium amount surplus, it is uneven that result easily produces chemical combination, thus cause chemical combination easily to reduce.In addition, the further preferred scope of thickness is 10 ~ 20nm.
In addition, the thickness of surface oxidation epithelium 2 is large by the essential factor of the oxide scale film formed by the heating decision in surface oxidation epithelium formation process S2 described later (with reference to Fig. 2).And in the surface treatment based on zirconium saline solution described later, zirconium dioxide is attached to or enters oxide scale film, and the magnesium amount that oxide scale film contains is controlled, and therefore major part is determined by the thickness heating the oxide scale film formed.In addition, the thickness of oxide scale film is by heating and temperature control.In addition, by heating the Porous epithelium that the oxide scale film that formed is the convex-concave shape formed on the surface of substrate 1, be take magnesia as the epithelium of main component.
(amount of element in surface oxidation epithelium and film thickness measuring)
Amount of element (zirconium amount, magnesium amount, halogen quantity, phosphorus amount etc.) in the surface oxidation epithelium 2 that the surface of substrate 1 is formed is measured by GD-OES (glow discharge apparatus for analyzing luminosity (Glow Discharge OpticalEmission Spectroscopy)), in the depth direction distribution map (profile) of surface oxidation epithelium 2, using until the mensuration maximum of regulation element when the degree of depth that the measured value of oxygen amount is less than or equal to 15 atom % measures is as amount of element.In addition, GD-OES also can the thickness of effects on surface oxide scale film 2 measure.That is, can using measured by GD-OES, in depth direction distribution map, the measured value of oxygen amount is less than or equal to the thickness of the degree of depth as surface oxidation epithelium 2 of 15 atom %.In addition, amount of element and thickness can adopt the mean value of the measurement result of the multiple positions in the surface of surface oxidation epithelium 2 certainly.In addition, zirconium amount also can be tried to achieve according to the zirconium dioxide amount of surface oxidation epithelium 2.In other words, obtain zirconium dioxide amount, calculate zirconium amount according to this zirconium dioxide amount obtained by the calculating of regulation.
In addition, as long as the determination method of amount of element and thickness has the determination method with GD-OES same precision, just not being defined in GD-OES especially, also can be AES (auger electrons optical spectroscopy) and XPS (x-ray photoelectron optical spectroscopy) etc.
As shown in Fig. 1 (b), aluminium alloy plate 10A involved in the present invention preferably also possesses the adhesive phase 3 be made up of adhesive on the surface of surface oxidation epithelium 2.
< adhesive phase >
As forming the adhesive of this adhesive phase 3, not limiting especially, the adhesive used during joining aluminum alloy plate all the time can be used.Such as, the epoxy resin of thermohardening type, acrylic resin and polyurethane resin etc. are enumerated.The thickness of adhesive phase 3 does not limit especially, is preferably 10 ~ 500 μm, more preferably 50 ~ 400 μm.When the thickness of adhesive phase 3 is less than 10 μm, sometimes with high adhesion durability, aluminium alloy plate 10A can not be engaged across adhesive phase 3 with the aluminium alloy plate 10 (with reference to Fig. 1 (a)) not possessing other adhesive phases.That is, the adhesion durability of the conjugant 20B of Fig. 3 (c) described later reduces sometimes.When the thickness of adhesive phase 3 is more than 500 μm, bonding strength diminishes sometimes.
" manufacture method of aluminium alloy plate "
Then, be described with reference to the manufacture method of Fig. 2 to above-mentioned aluminium alloy plate.In addition, the structure of aluminium alloy plate is with reference to Fig. 1 (a), (b).
The manufacture method of aluminium alloy plate 10 comprise substrate make operation S1, with surface oxidation epithelium formation process S2.Below, each operation is described.
Operation > made by < substrate
Operation S1 made by substrate is the operation being made substrate 1 by calendering.Specifically, preferably substrate 1 is made according to following order like that.
The aluminium alloy of the composition with regulation is melted by continuous casting, casts and manufacture ingot bar (melting casting process), and the ingot bar of above-mentioned manufacture is implemented to homogenize heat treatment (homogenize heat treatment step).Then, hot rolling implemented to the above-mentioned heat treated ingot bar that homogenized and manufacture hot rolled plate (hot-rolled process).Then, under the condition of 300 ~ 580 DEG C, black annealing or intermediate annealing are carried out to hot rolled plate, at least implement once final cold rolling rate be more than or equal to 5% cold rolling, thus manufacture the cold-reduced sheet (substrate 1) (cold rolling process) of thickness of slab of regulation.By the temperature of black annealing or intermediate annealing being formed as being more than or equal to 300 DEG C, the effect that formability improves is played further, by being less than or equal to 580 DEG C, and the reduction of the formability easily suppressing the generation of burning to cause.By final cold rolling rate being formed as being more than or equal to 5%, the effect that formability improves is played further.In addition, the condition of the heat treatment that homogenizes, hot rolling does not limit especially, usually obtains the condition of the situation of hot rolled plate.In addition, also intermediate annealing can not be carried out.
< surface oxidation epithelium formation process >
Surface oxidation epithelium formation process S2 is the operation that the surface of the substrate 1 made at last operation S1 forms surface oxidation epithelium 2.And, be such as by heating substrate 1 and then carrying out surface treatment, thus the zirconium amount of surface oxidation epithelium 2 and magnesium amount are adjusted the operation in prescribed limit.Or the operation in prescribed limit by metal hydroxides peak height or the adjustment of metal oxide peak height.
(heating)
Heating is that substrate 1 is heated to 400 ~ 580 DEG C, forms the operation of the oxide scale film forming surface oxidation epithelium 2 on the surface of substrate 1.In addition, heating also adjusts the intensity of aluminium alloy plate 10.In addition, heating preferably firing rate is the instant heating of more than 100 DEG C/minute.
And heating when substrate 1 is made up of heat treatment type aluminium alloy is solution treatment, be the heating in annealing (final annealing) when substrate 1 is made up of nonheat-treatable aluminum alloy.
Be more than or equal to 400 DEG C by being heated to rapidly heating-up temperature, the intensity thus after the intensity of aluminium alloy plate 10 and the application of this aluminium alloy plate 10 after heating (baking) becomes larger.580 DEG C are less than or equal to, the reduction of the formability suppressing the generation of burning to cause thus by being heated to rapidly heating-up temperature.In addition, heat by being 400 ~ 580 DEG C with heating-up temperature, forming on the surface of substrate 1 thickness forming surface oxidation epithelium 2 is the oxide scale film of 1 ~ 30nm.In addition, from the view point of raising intensity, the retention time is preferably 3 ~ 30 seconds.
(surface treatment)
Surface treatment carries out surface treatment to the surface of the substrate 1 defining oxide scale film, by this surface treatment, zirconium amount and the magnesium amount of the surface oxidation epithelium 2 that the oxide scale film formed by above-mentioned heating, i.e. oxide scale film have been surface treated are adjusted in prescribed limit.In addition, metal hydroxides peak height or metal oxide peak height are adjusted in prescribed limit.
In surface treatment, as surface treatment liquid, working concentration is the zirconium saline solution that 0.01 ~ 15 quality %, pH are less than 5.In addition, in surface treatment, in order to adjust pH, also the acid such as nitric acid, sulfuric acid can be added.And then in surface treatment, treatment temperature is 10 ~ 90 DEG C, the processing time is 1 ~ 200 second or 2 ~ 200 seconds.
In addition, in order to metal hydroxides peak height being suppressed for being less than or equal to 0.020, after contacting 1 ~ 200 second with the zirconium saline solution that pH is less than 5, washing within 5 minutes, after terminating from washing, carrying out drying within 5 minutes.Thereby, it is possible to suppress the metal hydroxides amount on surface.Or, in order to metal oxide peak height being suppressed for being less than or equal to 0.040, washing after contacting 2 seconds more than (less than 200 seconds) with the zirconium saline solution that pH is less than 5, after terminating from washing, carrying out drying within 5 minutes.Thereby, it is possible to suppress the metal oxide amount on surface.In addition, by meeting above-mentioned two conditions, metal hydroxides peak height can be suppressed for being less than or equal to 0.020, and metal oxide peak height is suppressed for being less than or equal to 0.040.
In this surface treatment, such as, by carrying out shower or spraying to the substrate 1 being formed with oxide scale film and spraying zirconium saline solution, or make it by zirconium saline solution, or impregnated in zirconium saline solution, carry out the surface treatment of substrate 1 thus.In addition, as surface treatment liquid, preferably use the surface treatment liquid not containing halogen and phosphorus.
By using the zirconium saline solution of 0.01 ~ 15 quality % as surface treatment liquid, the zirconium amount of surface oxidation epithelium 2 is formed as 0.01 ~ 10 atom %, and magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %.When the concentration of zirconium saline solution is less than 0.01 quality %, the zirconium quantitative change of surface oxidation epithelium 2 is few (being less than 0.01 atom %), and magnesium amount becomes many (being more than or equal to 10 atom %), and adhesion durability and the water profit stability of aluminium alloy plate 10 can not be guaranteed.On the other hand, when the concentration of zirconium saline solution is more than 15 quality %, the zirconium quantitative change of surface oxidation epithelium 2 is many (more than 10 atom %), or magnesium amount tails off (being less than 0.1 atom %), and the raising effect of adhesion durability and water profit stability is saturated.Therefore, the concentration of zirconium saline solution is set to 0.01 ~ 15 quality %.
When the pH of the zirconium saline solution as surface treatment liquid is more than or equal to 5, the stability of surface treatment liquid reduces, and easily in surface treatment liquid, produces precipitation.When producing precipitation in surface treatment liquid, precipitate the plate surface being pressed into aluminium alloy plate 10 as impurity, cause outward appearance defective, therefore this is not preferred.Therefore, the pH as the zirconium saline solution of surface treatment liquid is formed as being less than 5.
When the treatment temperature of the zirconium saline solution as surface treatment liquid is less than 10 DEG C or the processing time is less than 1 second, the zirconium amount of surface oxidation epithelium 2 is less than 0.01 atom %, and magnesium amount is more than or equal to 10 atom %, and adhesion durability and the water profit stability of aluminium alloy plate 10 can not be guaranteed.On the other hand, when the treatment temperature of zirconium saline solution is more than 90 DEG C or the processing time more than 200 seconds time, the zirconium amount of surface oxidation epithelium 2 is less than 0.1 atom % more than 10 atom % or magnesium amount, and the raising effect of adhesion durability and water profit stability is saturated.Therefore, the treatment temperature of zirconium saline solution is set to 10 ~ 90 DEG C, the processing time is set to 1 ~ 200 second.In addition, when suppressing metal oxide peak height for being less than or equal to 0.040, the processing time is set to 2 ~ 200 seconds.
In addition, when carrying out washing within latter 5 minutes from process and then when not carrying out drying from washing within latter 5 minutes, metal hydroxides increases, because metal hydroxides peak height is more than 0.020, therefore when metal hydroxides peak height is suppressed for being less than or equal to 0.020, washing within latter 5 minutes from process, and then carrying out drying from washing within latter 5 minutes.In addition, after having carried out after treatment washing, when not carrying out drying within 5 minutes after terminating from washing, metal oxide increases, because metal oxide peak height is more than 0.040, therefore, when suppressing metal oxide peak height for being less than or equal to 0.040, drying is being carried out from washing within latter 5 minutes.
In addition, what can be used in washing comprises water for industrial use, running water, ion exchange water, distilled water and pure water etc.
As mentioned above, the zirconium saline solution as surface treatment liquid does not refer to containing halogen and phosphorus, when utilizing GD-OES etc. to measure halogen and phosphorus, can not carry out measuring, being namely less than determination limit.And, when surface treatment liquid contains halogen, burden is caused to manufacturing equipment.In addition, when surface treatment liquid contains phosphorus, easily produce precipitation, easy contaminated environment when discharging surface treatment liquid.In addition, simultaneously the control of the halogen quantity in surface treatment liquid and phosphorus amount carry out with when according to concentration or treatment conditions, the zirconium amount of effects on surface treatment fluid and magnesium amount control.
In addition, before the above-mentioned surface treatment utilizing zirconium saline solution to carry out, to remove for the purpose of magnesium from surface oxidation epithelium 2, namely in order to make the magnesium amount of surface oxidation epithelium 2 for being more than or equal to 0.1 atom % and being less than 10 atom %, the acid such as nitric acid, sulfuric acid also can be used to carry out surface treatment, i.e. so-called acid cleaning as surface treatment liquid.And as the condition of acid cleaning, preferred acid concentration is that 0.5 ~ 6N, pH are less than 1, cleaning temperature is 20 ~ 80 DEG C, scavenging period is 1 ~ 100 second.
Then, the manufacture method of the aluminium alloy plate 10A possessing adhesive phase 3 is described.The manufacture method of aluminium alloy plate 10A comprises substrate and makes operation S1, surface oxidation epithelium formation process S2 and adhesive phase formation process S3.Because substrate makes operation S1 and surface oxidation epithelium formation process S2 as described above, therefore the description thereof will be omitted.
< adhesive phase formation process >
Adhesive phase formation process S3 is the operation forming the adhesive phase 3 be made up of adhesive on the surface of the surface oxidation epithelium 2 formed by above-mentioned operation S2.The formation method of adhesive phase 3 does not limit especially, such as, enumerate following method: when adhesive is solid, after being formed as solution adhesive is dissolved in solvent, the surface of effects on surface oxide scale film 2 carries out spraying or applying, and the surface of effects on surface oxide scale film 2 of keeping intact when adhesive is aqueous in addition carries out spraying or applying.
Although the manufacture method of aluminium alloy plate 10,10A as described above, but also can carry out at every turn aluminium alloy plate 10,10A manufacture time, in the scope above-mentioned each operation not had a negative impact, between above-mentioned each operation or front and back comprise other operations.Such as, the preliminary aging treatment operation implementing preliminary aging treatment also can be set after above-mentioned surface oxidation epithelium formation process S2 or adhesive phase formation process S3.Preliminary aging treatment is carried out preferably by carrying out the low-temperature heat of 8 ~ 36 hours in 72 hours under the condition of 40 ~ 120 DEG C.By carrying out preliminary aging treatment under this condition, the raising of the intensity after formability and baking can be realized.
In addition, the foreign matter removal step such as removed by the foreign matter on the plate surface of aluminium alloy plate 10,10A or the defective product removal step etc. removed by the defective product produced in each operation can also be comprised.
And, manufactured aluminium alloy plate 10,10A before the making of conjugant or before being configured as member for automobile, at its surface application punching oil.Punching oil mainly uses the punching oil containing ester composition.
Then, the method at aluminium alloy plate 10 involved in the present invention, 10A coating punching oil is described.
As the method for the coating of punching oil, such as, only make aluminium alloy plate 10,10A impregnated in containing in the punching oil of ethyl oleate as ester composition.The method of punching oil of coating containing ester composition or condition do not limit especially, extensive use can apply method or the condition of common punching oil.In addition, ester composition is also not limited to ethyl oleate, can utilize the various ester composition such as butyl stearate or sorbitan monostearate.
" conjugant "
Then, conjugant involved in the present invention is described.In addition, below, the situation (with reference to Fig. 1 (a), (b)) possessing surface oxidation epithelium 2 with aluminium alloy plate 10,10A at one side is described.
As shown in Fig. 3 (a), conjugant 20 possesses two aluminium alloy plates 10,10; And adhesive member 11.Specifically, the aluminium alloy plate of conjugant 20 10,10 is engaged across adhesive member 11 each other.And, surface oxidation epithelium 2 side engagement of the one side of adhesive member 11 and the aluminium alloy plate 10 of a side, surface oxidation epithelium 2 side engagement of the aluminium alloy plate 10 of another side and the opposing party.Consequently, the surface oxidation epithelium 2,2 of two aluminium alloy plates 10,10 configures in the mode relative across adhesive member 11 respectively.
< aluminium alloy plate >
Due to aluminium alloy plate 10 as described above, therefore the description thereof will be omitted.
< adhesive member >
Adhesive member 11 is made up of adhesive, identical with above-mentioned adhesive phase 3.Specifically, adhesive member 11 is made up of the adhesive such as epoxy resin, acrylic resin, polyurethane resin of thermohardening type.In addition, the thickness of adhesive member 11 does not limit especially, is preferably 10 ~ 500 μm, more preferably 50 ~ 400 μm.
As mentioned above, two-sided zirconium and the magnesium containing ormal weight of the adhesive member 11 of conjugant 20, and then when defining metal hydroxides peak height, the surface oxidation epithelium 2 be adjusted in prescribed limit with metal hydroxides peak height engages.Therefore, when conjugant 20 is used for member for automobile, even if under being exposed to high temperature moist environment, salt spray environment, also can suppress the reduction of the bonding strength at the interface between adhesive member 11 and surface oxidation epithelium 2, thus improve adhesion durability.In addition, not by the species influence of the adhesive of formation adhesive member 11, and the adhesion durability at interface is improved at all adhesives all the time for the joint of aluminium alloy plate.In addition, when defining metal oxide peak height, owing to engaging with the surface oxidation epithelium 2 that metal oxide peak height is adjusted in prescribed limit, therefore water profit stability improves, and easily improves adhesion durability thus.
As shown in Fig. 3 (b), conjugant 20A uses the second aluminium alloy plate 12 a side of two aluminium alloy plates 10,10 (with reference to Fig. 3 (a)) of above-mentioned conjugant 20.Specifically, the first aluminium alloy plate 10a be made up of aluminium alloy plate 10 engages the second aluminium alloy plate 12 be made up of aluminium alloy, surface oxidation epithelium 2 side engagement of adhesive member 11 and the first aluminium alloy plate 10a across adhesive member 11.In addition, the first aluminium alloy plate 10a is made up of aluminium alloy plate 10, due to aluminium alloy plate 10 as described above, therefore the description thereof will be omitted.
< second aluminium alloy plate >
Second aluminium alloy plate 12 is same with aforesaid substrate 1, specifically, by JIS defined or the various nonheat-treatable aluminum alloy that is similar to JIS or heat treatment type aluminium alloy form.
Due to one side and surface oxidation epithelium 2 side engagement of the adhesive member 11 in conjugant 20A, therefore same with above-mentioned conjugant 20, when defining metal hydroxides peak height, when conjugant 20A is used for member for automobile, even if under being exposed to high temperature moist environment, salt spray environment, also can improve the adhesion durability at interface, in addition, adhesion durability is not by the impact of the kind of adhesive.In addition, when defining metal oxide peak height, owing to engaging with the surface oxidation epithelium 2 that metal oxide peak height is adjusted in prescribed limit, therefore water profit stability improves, and easily improves adhesion durability thus.
As shown in Fig. 3 (c), conjugant 20B possesses: aluminium alloy plate 10A, and this aluminium alloy plate 10A possesses adhesive phase 3 (with reference to Fig. 1 (b)); And aluminium alloy plate 10, this aluminium alloy plate 10 does not possess adhesive phase 3.Specifically, the surface oxidation epithelium 2 of aluminium alloy plate 10 is had in adhesive phase 3 side engagement of aluminium alloy plate 10A.Consequently, two aluminium alloy plate 10A, 10 surface oxidation epithelium 2,2 configure in the mode that the adhesive phase 3 across aluminium alloy plate 10A is relative respectively.In addition, due to two aluminium alloy plate 10A, 10 as described above, therefore the description thereof will be omitted.
Due to the two-sided of the adhesive phase 3 in conjugant 20B and surface oxidation epithelium 2 side engagement, therefore same with above-mentioned conjugant 20, when defining metal hydroxides peak height, when conjugant 20B is used for member for automobile, even if under being exposed to high temperature moist environment, salt spray environment, also can improve the adhesion durability at interface, in addition, adhesion durability is not by the impact of the kind of adhesive.In addition, when defining metal oxide peak height, owing to engaging with the surface oxidation epithelium 2 that metal oxide peak height is adjusted in prescribed limit, therefore water profit stability improves, and easily improves adhesion durability thus.
As shown in Fig. 3 (d), conjugant 20C uses the second aluminium alloy plate 12 to replace the aluminium alloy plate 10 (with reference to Fig. 3 (c)) not possessing adhesive phase 3 of above-mentioned conjugant 20B.Specifically, the first aluminium alloy plate 10Aa be made up of the aluminium alloy plate 10A possessing adhesive phase 3 engages adhesive phase 3 side engagement of the second aluminium alloy plate 12, second aluminium alloy plate 12 and the first aluminium alloy plate 10Aa be made up of aluminium alloy.In addition, the first aluminium alloy plate 10Aa is made up of aluminium alloy plate 10A, due to aluminium alloy plate 10A as described above, therefore the description thereof will be omitted.In addition, due to the second aluminium alloy plate 12 as described above, therefore the description thereof will be omitted.
Due to one side and surface oxidation epithelium 2 side engagement of the adhesive phase 3 in conjugant 20C, therefore same with above-mentioned conjugant 20, when defining metal hydroxides peak height, when conjugant 20C is used for member for automobile, even if under being exposed to high temperature moist environment, salt spray environment, also can improve the adhesion durability at interface, in addition, adhesion durability is not by the impact of the kind of adhesive.In addition, when defining metal oxide peak height, owing to engaging with the surface oxidation epithelium 2 that metal oxide peak height is adjusted in prescribed limit, therefore water profit stability improves, and easily improves adhesion durability thus.
The manufacture method of conjugant 20,20A ~ 20C, specifically joint method use existing known joint method.And the formation method of adhesive member 11 does not limit especially, such as, the adhesive member 11 be made up of adhesive in advance can be used, also can by adhesive being sprayed or being coated on the surface of surface oxidation epithelium 2 and being formed.In addition, conjugant 20,20A ~ 20C and aluminium alloy plate 10,10A are same, also before being configured as member for automobile, punching oil can be coated on its surface.
In conjugant 20,20A ~ 20C, although not shown, but when being used in the two-sided aluminium alloy plate possessing surface oxidation epithelium 2 as aluminium alloy plate 10,10A (first aluminium alloy plate 10a, 10Aa), can further aluminium alloy plate 10,10A (first aluminium alloy plate 10a, 10Aa) or the second aluminium alloy plate 12 be engaged across adhesive member 11 or adhesive phase 3.
" member for automobile "
Then, member for automobile involved in the present invention is described.
Although not shown, member for automobile is manufactured by above-mentioned conjugant 20,20A ~ 20C.And member for automobile is such as automobile panel etc.In addition, the manufacture method of member for automobile does not limit especially, uses existing known manufacture method.Such as, to the member for automobile that above-mentioned conjugant 20,20A ~ 20C implement to cut off processing, punch process etc. and manufacture regulation shape.
In addition, because member for automobile is manufactured by above-mentioned conjugant 20,20A ~ 20C, therefore when surface oxidation epithelium 2 defines metal hydroxides peak height, even if under being exposed to high temperature moist environment, salt spray environment, the adhesion durability at interface can also be improved.In addition, when surface oxidation epithelium 2 defines metal oxide peak height, water profit stability improves, and easily improves adhesion durability thus.
Embodiment
Then, contrast meets the embodiment of necessary condition of the present invention and does not meet the comparative example of necessary condition of the present invention, is specifically described aluminium alloy plate of the present invention.
Use 6000 line aluminium alloys of 6022 specifications (Mg:0.55 quality %, Si:0.95 quality %) of JIS regulation, utilize above-mentioned manufacture method to make cold-rolled aluminum alloy sheet (thickness of slab 1mm).0.2% endurance of this cold-reduced sheet is 230MPa.And, using the evaluation plate of this cold-reduced sheet as adhesion durability, be cut to length 100mm × width 25mm and form substrate.In addition, as the evaluation plate of water profit stability, be cut to length 70mm × width 150mm and form substrate.Alkali degreasing is carried out to aforesaid substrate, substrate is heated until entity arrives temperature 550 DEG C, after cooling, adding nitric acid, pH is adjusted to and is less than in the aqueous solution of the zirconyl nitrate containing 0.01 ~ 15 quality % of 4, flood 2 ~ 20 seconds under the condition of 10 ~ 80 DEG C.Then, washed within 5 minutes, and carry out drying in washing within latter 5 minutes, thus be formed in substrate be two-sidedly formed with the aluminium alloy plate that zirconium amount, magnesium amount and metal hydroxides peak height (metal hydroxides amount) and metal oxide peak height (metal oxide amount) obtain the surface oxidation epithelium controlled, be formed as sample (No.6 ~ 15).Sample (No.1) does not carry out the dipping to zirconyl nitrate solution, sample (No.2 ~ 5) by the temperature of the pH of zirconyl nitrate concentration, the aqueous solution, the aqueous solution, the processing time until the time of washing until make under the time of drying is located at outside control range condition.
For above-mentioned sample (No.1 ~ 15), the content utilizing high frequency glow discharge ICP Atomic Emission Spectrophotometer (GD-OES (Horiba Jobin Yvon Inc., model JY-5000RF)) to come the zirconium (Zr) of effects on surface oxide scale film, magnesium (Mg), halogen and phosphorus measures.Table 1 illustrates this result.
In addition, in whole sample (No.1 ~ 15), do not detect halogen, phosphorus, and when the total of the content of Mg, Zr is not 100 atom %, comprise O or Al, trace impurity.
In addition, for above-mentioned sample (No.1 ~ 15), utilize FT-IR (Fourier transform formula infrared spectrophotometer: Nicolet Magna-750spectrometer) to analyze and metal hydroxides peak height and metal oxide peak height are carried out quantitatively.Specifically, for metal hydroxides, by using the FT-IR of incidence angle 75 degree to analyze, according to when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights and carry out quantification.For metal oxide, by using the FT-IR of incidence angle 75 degree to analyze, according to when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1as during datum line when, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights and carry out quantification.
Then, use sample (No.1 ~ 15) and carry out following evaluation.Table 1 illustrates its result.
< condenses destructive rate (adhesion durability) >
As shown in Fig. 4 (a), (b), pasting as overlapping length by the end thermosetting epoxy resin system adhesive overlap of identical for structure two samples (25mm width) is 13mm (bond area: 25mm × 13mm).Adhesive is thermosetting epoxy resin system adhesive (bisphenol A type epoxy resin amount 40 ~ 50%) as used herein.And the bead (particle diameter 150 μm) of trace makes an addition in adhesive and regulates by the mode becoming 150 μm with the thickness of adhesive phase.After overlap, within 30 minutes, carry out drying at ambient temperature, then heat 20 minutes under the condition of 170 DEG C, thus implement heat cure process.Then leave standstill 24 hours at ambient temperature and make adhesive test body.
By the adhesive test body made in the early stage, 50 DEG C and to keep under the high temperature moist environment of relative humidity 95% after 10 days and after utilizing salt spray tester to be sprayed 3000 hours under the condition of 35 DEG C by 5%NaCl water under these three experimental conditions, the speed utilizing cupping machine to divide with 50mm/ stretches, thus evaluates the cohesion destructive rate of the adhesive of stick portion.Cohesion destructive rate formula described as follows (1) is tried to achieve like that.In formula (1), one-sided as test film A, another is one-sided as test film B using after the stretching of adhesive test body.
Cohesion destructive rate (%)=100-{ (bond area of the interface peel area/test film A of test film A) × 100}+{ (bond area of the interface peel area/test film B of test film B) × 100} ... (1)
In addition, make three samples under each experimental condition respectively, cohesion destructive rate is the mean value of three samples.In addition, metewand is, cohesion destructive rate is less than 60% and is be evaluated as defective "×", is more than or equal to 60% and is less than 80% to be evaluated as slightly defective " Δ ", be more than or equal to 80% and be less than 90% and be evaluated as good "○", be more than or equal to 90% and be evaluated as excellent " ◎ ".
< water profit stability (after the degreasing after long-term moistening keeping moistening) >
The sample (No.1 ~ 15) of length 70mm × width 150mm be impregnated in punching oil.Then, in order to investigate the ageing stability on surface of the test film being coated with punching oil, following test is like that carried out.In the environmental chamber being positioned over 50 ~ 90%RH by keeping the sample being coated with above-mentioned punching oil state under the condition of 15 ~ 35 DEG C 6 months.Then, after 6 months, for by during dipping in its commercially available weak base degreaser at automobile (temperature 40 DEG C) 2 minutes, measure (better, numerical value is higher) relative to water profit area occupation ratio (only one-sided) of the area of test film.Thereby, it is possible to evaluate the moistening (stable chemical combination treatability) during chemical combination process.
Metewand is, water profit area occupation ratio is less than 40% and is be evaluated as quite defective " ×× ", 40% ~ be less than 60% to be evaluated as defective "×", 60% ~ be less than 80% to be evaluated as slightly defective " Δ ", 80% ~ be less than 90% to be evaluated as good "○", be more than or equal to 90% and be evaluated as excellent " ◎ ".
Table 1
< condenses the evaluation > of destructive rate (adhesion durability)
As shown in table 1, as comparative example sample (No.1) from not carrying out to the dipping of zirconyl nitrate solution in the early stage, high temperature moistening after and in whole after 3000 hours of brine spray, cohesion destructive rate is all defective.In addition, compared with unsteered sample (No.1), although to Mg measure control sample (No.2), to Zr measure control sample (No.3), the sample (No.4) controlled is measured to Zr, Mg, the sample (No.5) utilizing manufacture method to control metal hydroxides peak height sees a little improvement, the improvement effect under moist environment, salt spray environment is insufficient.
On the other hand, as embodiment sample (No.6 ~ 15) by suitably to Zr amount, Mg amount and metal hydroxides peak height control, thus in the early stage, high temperature moistening after and in whole after 3000 hours of brine spray, cohesion destructive rate is the evaluation of more than good "○".In addition, by by Zr measure, Mg amount and metal hydroxides peak height control in preferred scope (sample (No.8 ~ 11)), thus high temperature moistening after and brine spray also demonstrate excellent cohesion destructive rate (" ◎ ") after 3000 hours.
The evaluation > of < water profit stability (after the degreasing after long-term moistening keeping moistening)
As shown in table 1, as comparative example water from not carrying out to the sample (No.1) of the dipping of zirconyl nitrate solution profit stability be quite defective.In addition, compared with unsteered sample (No.1), although to Mg measure control sample (No.2), to Zr measure control sample (No.3,5), the sample (No.4) controlled measured to Zr, Mg see a little improvement, after the degreasing after long-term moistening exposure, the improvement effect of moistening is insufficient.
On the other hand, as embodiment sample (No.6 ~ 15) by suitably to Zr amount, Mg amount and metal oxide peak height control and obtain the evaluation of more than "○".In addition, by metal oxide peak height being controlled in preferred scope (sample (No.8 ~ 11,13)), even if also show excellent water profit stability (" ◎ ") after long-term moistening exposure.
Above, although illustrate that embodiment and embodiment have been described in detail aluminium alloy plate involved in the present invention, purport of the present invention is not limited to foregoing, and its interest field must be explained based on the record of the scope of Patent request.In addition, content of the present invention certainly can carry out based on above-mentioned record changing, change etc.

Claims (14)

1. an aluminium alloy plate, is characterized in that,
Described aluminium alloy plate is the aluminium alloy plate for automobile, and this aluminium alloy plate possesses: aluminium alloy base plate; And the surface of described aluminium alloy base plate formed surface oxidation epithelium, in described surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, and magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %,
By using incidence angle to be that the FT-IR of 75 degree and Fourier transform infrared spectrophotometer are analyzed described surface oxidation epithelium, and when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights be less than or equal to 0.020.
2. an aluminium alloy plate, is characterized in that,
Described aluminium alloy plate is the aluminium alloy plate for automobile, and this aluminium alloy plate possesses: aluminium alloy base plate; And the surface of described aluminium alloy base plate formed surface oxidation epithelium, in described surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, and magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %,
By using incidence angle to be that the FT-IR of 75 degree and Fourier transform infrared spectrophotometer are analyzed described surface oxidation epithelium, and when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1when as datum line, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights be less than or equal to 0.040.
3. an aluminium alloy plate, is characterized in that,
Described aluminium alloy plate is the aluminium alloy plate for automobile, and this aluminium alloy plate possesses: aluminium alloy base plate; And the surface of described aluminium alloy base plate formed surface oxidation epithelium, in described surface oxidation epithelium, zirconium amount is 0.01 ~ 10 atom %, and magnesium amount is more than or equal to 0.1 atom % and is less than 10 atom %,
By using incidence angle to be that the FT-IR of 75 degree and Fourier transform infrared spectrophotometer are analyzed described surface oxidation epithelium, and when representing the spectrum of metal hydroxides with absorbance, will from 400cm -1to 1800cm -1when as datum line, at 1060cm -1wave number part produce spectrum peak heights be less than or equal to 0.020,
By using incidence angle to be that the FT-IR of 75 degree and Fourier transform infrared spectrophotometer are analyzed described surface oxidation epithelium, and when representing the spectrum of metal oxide with absorbance, will from 400cm -1to 1800cm -1when as datum line, from 800cm -1to 1000cm -1wave number part produce spectrum peak heights be less than or equal to 0.040.
4. aluminium alloy plate according to any one of claim 1 to 3, is characterized in that,
Described aluminium alloy plate also possesses on the surface of described surface oxidation epithelium the adhesive phase be made up of adhesive.
5. aluminium alloy plate according to any one of claim 1 to 3, is characterized in that,
The ratio that the zirconium amount of described surface oxidation epithelium and Zr amount and magnesium amount and Mg measure and Zr measure/and it is 0.0025 ~ 10 that Mg measures.
6. aluminium alloy plate according to any one of claim 1 to 3, is characterized in that,
Described aluminium alloy base plate is made up of Al-Mg system alloy, Al-Cu-Mg alloy, Al-Mg-Si system alloy or Al-Zn-Mg system alloy.
7. a conjugant, this conjugant be aluminium alloy plate according to any one of claims 1 to 3 each other across the conjugant that the adhesive member be made up of adhesive is engaged, it is characterized in that,
The surface oxidation epithelium side engagement of described adhesive member and two described aluminium alloy plates, the surface oxidation epithelium of two described aluminium alloy plates configures in the mode relative across described adhesive member respectively.
8. a conjugant, this conjugant is the conjugant the first aluminium alloy plate of forming at the aluminium alloy plate according to any one of claims 1 to 3 being bonded to the second aluminium alloy plate be made up of aluminium alloy across the adhesive member be made up of adhesive, it is characterized in that
The surface oxidation epithelium side engagement of described adhesive member and described first aluminium alloy plate.
9. a conjugant, this conjugant is the conjugant of the aluminium alloy plate according to any one of requirement 1 to 3 of having the right in the adhesive phase side engagement of aluminium alloy plate according to claim 4, it is characterized in that,
The surface oxidation epithelium of two described aluminium alloy plates configures in the mode relative across described adhesive phase respectively.
10. a conjugant, this conjugant is the conjugant being bonded to the second aluminium alloy plate be made up of aluminium alloy on the first aluminium alloy plate be made up of aluminium alloy plate according to claim 4, it is characterized in that,
The adhesive phase side engagement of described second aluminium alloy plate and described first aluminium alloy plate.
11. 1 kinds of member for automobile, is characterized in that,
Described member for automobile is manufactured by conjugant according to claim 7.
12. 1 kinds of member for automobile, is characterized in that,
Described member for automobile is manufactured by conjugant according to claim 8.
13. 1 kinds of member for automobile, is characterized in that,
Described member for automobile is manufactured by conjugant according to claim 9.
14. 1 kinds of member for automobile, is characterized in that,
Described member for automobile is manufactured by conjugant according to claim 10.
CN201210336967.8A 2011-10-05 2012-09-12 Aluminum alloy plate, and joint body and automobile member using same aluminum alloy plate Expired - Fee Related CN103057198B (en)

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JP2004018992A (en) * 2002-06-20 2004-01-22 Furukawa Sky Kk Nonchromium type aluminum underlayer treatment material having excellent coating film adhesion and acid elution resistance
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* Cited by examiner, † Cited by third party
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