WO2016031937A1 - Aluminum alloy sheet for forming - Google Patents

Aluminum alloy sheet for forming Download PDF

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Publication number
WO2016031937A1
WO2016031937A1 PCT/JP2015/074297 JP2015074297W WO2016031937A1 WO 2016031937 A1 WO2016031937 A1 WO 2016031937A1 JP 2015074297 W JP2015074297 W JP 2015074297W WO 2016031937 A1 WO2016031937 A1 WO 2016031937A1
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WO
WIPO (PCT)
Prior art keywords
aluminum alloy
less
compound
compounds
plate
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PCT/JP2015/074297
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French (fr)
Japanese (ja)
Inventor
有賀 康博
久郎 宍戸
松本 克史
Original Assignee
株式会社神戸製鋼所
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Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to KR1020187023408A priority Critical patent/KR20180095117A/en
Priority to US15/502,838 priority patent/US20170233853A1/en
Priority to KR1020177005027A priority patent/KR20170029633A/en
Priority to CN201580043418.3A priority patent/CN106574327A/en
Publication of WO2016031937A1 publication Critical patent/WO2016031937A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08Alloys based on aluminium with magnesium as the next major constituent with silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/043Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions

Definitions

  • the present invention relates to an Al—Mg—Si based aluminum alloy sheet for forming.
  • the aluminum alloy sheet referred to in the present invention is a rolled sheet such as a hot-rolled sheet or a cold-rolled sheet, and is subjected to tempering such as solution treatment and quenching process, and is baked and coated and cured. Says aluminum alloy plate before being done.
  • aluminum is also referred to as aluminum or Al.
  • panels such as outer panels (outer plates) and inner panels (inner plates) of panel structures such as automobile hoods, fenders, doors, roofs and trunk lids are thin and high-strength aluminum alloy plates.
  • Al—Mg—Si based AA to JISJ6000 (hereinafter also simply referred to as 6000) aluminum alloy plates is being studied.
  • This 6000 series aluminum alloy plate contains Si and Mg as essential components.
  • the 6000 series aluminum alloy plate has a relatively small amount of alloy elements as compared with other 5000 series aluminum alloys having a large amount of alloy such as Mg. For this reason, when the scraps of these aluminum alloy plates are reused as an aluminum alloy melting material (melting raw material), the original 6000 series aluminum alloy ingot is easily obtained and the recyclability is excellent.
  • an outer panel of an automobile is manufactured by combining an aluminum alloy plate with a forming process such as press forming and bending forming.
  • a forming process such as press forming and bending forming.
  • a large outer panel such as a hood or a door
  • it is formed into a molded product shape as an outer panel by press molding such as overhanging, and then the inner panel is formed by hem (hemming) processing such as flat hem on the outer peripheral edge of the outer panel.
  • hem hem
  • the 6000 series aluminum alloy has an advantage of having excellent BH property, but has aging property at room temperature, and after the solution quenching treatment, it is age-hardened by holding at room temperature for several months to increase the strength. As a result, there is a problem that the formability to the panel, particularly the bending workability, is lowered.
  • a 6000 series aluminum alloy plate when used for an automotive panel, it usually takes about 1 to 4 months after it is solution-quenched by an aluminum maker (after manufacture) and then molded into a panel by an automotive maker. It is left at room temperature (and left at room temperature), and during this time, it is considerably age-hardened (room temperature aging).
  • Patent Document 1 proposes a method for improving formability, baking paintability, and corrosion resistance by adding Sn having a temporal change suppressing effect and Cu for improving formability.
  • an object of the present invention is to form Sn-containing Al—Mg, which can exhibit high BH properties and good workability even in a car body paint baking process after long-term aging at room temperature. -To provide a Si-based aluminum alloy sheet.
  • the gist of the forming aluminum alloy plate of the present invention is, in mass%, Mg: 0.2 to 2.0%, Si: 0.3 to 2.0%, and Sn: 0.00.
  • Al—Mg—Si-based aluminum alloy plate containing 005 to 0.3% and the balance being Al and inevitable impurities is measured using a 500-fold SEM as the structure of the aluminum alloy plate.
  • the average number density of the compound having an equivalent circle diameter of 0.3 to 20 ⁇ m is 0 / mm 2 and 5000 / mm 2 or less, and among the compounds measured by the SEM,
  • the average number ratio of the compound containing 0.5 mass% or more of Sn to be identified is 0% or more and less than 50%.
  • the manufacturing conditions such as intermediate annealing are devised, and the presence state of the contained Sn is controlled to precipitate Sn as a compound. It suppresses and promotes the solid solution of Sn in the matrix, and ensures the solid solution amount of Sn.
  • the effect of improving heme workability and BH property is sufficiently exhibited by the trapping of Sn atomic vacancies and the suppression of aging by the release effect.
  • the conventional Sn-containing Al—Mg—Si based aluminum alloy plate could not sufficiently exhibit such effects of Sn.
  • the solid solution and precipitation of Sn which was only one of the selective additive elements, while always paying attention to the solid solution and precipitation of the main elements Mg and Si. This is probably due to the fact that they did not pay much attention.
  • the Sn present form of the plate produced by a conventional method is crystallization or precipitation (hereinafter, also simply referred to as precipitation) as a compound. In contrast to this, it is difficult to solidify Sn itself, and since the solid solution state of Sn is a very rare form, it is difficult to know the effects exhibited by the solid solution of Sn. Inferred.
  • the 6000 series aluminum alloy plate targeted by the present invention is required to have excellent properties such as formability, BH property, strength, weldability, and corrosion resistance as a plate for an automobile panel. That is, even for a plate that has been aged at room temperature for a long period of 100 days after the tempering treatment, the As proof stress is 110 MPa or less, the BH (bake hard) property is proof stress difference of 100 MPa or more, and the hem workability is described later in the examples. It is required that it is excellent in press formability and hem workability to automobile panels, etc., and BH properties are excellent, such as 2 or more on the basis.
  • the composition of the aluminum alloy sheet as a premise is Mg: 0.2-2.0%, Si: 0.3-2.0%, and Sn: 0.0. 005 to 0.3% is included, and the balance is made of Al and inevitable impurities.
  • % display of content of each element means the mass% altogether.
  • the percentage (mass%) based on mass is the same as the percentage (wt%) based on weight.
  • the content of each chemical component may be expressed as “X% or less (excluding 0%)” as “over 0% and X% or less”.
  • the 6000 series aluminum alloy plate targeted by the present invention is an excess Si type 6000 series aluminum alloy plate having a better BH property and a Si / Mg mass ratio of Si / Mg of 1 or more. Is preferred.
  • the 6000 series aluminum alloy sheet secures formability by reducing the yield strength during press molding and bending, and is age-hardened by heating during relatively low temperature artificial aging treatment such as paint baking treatment of the panel after molding. Yield strength is improved, and it has excellent age-hardening ability (BH property) that can secure the required strength.
  • the excess Si type 6000 series aluminum alloy plate is more excellent in this BH property than the 6000 series aluminum alloy plate having a mass ratio Si / Mg of less than 1.
  • these other elements other than Mg and Si are impurities or elements that may be contained, and the content (allowable amount) at each element level in accordance with AA or JIS standards.
  • the following elements are allowed to be contained in the range below the upper limit amount in accordance with the AA to JIS standards specified below.
  • Mn 1.0% or less (excluding 0%), Cu: 1.0% or less (excluding 0%), Fe: 1.0% or less (excluding 0%) %), Cr: 0.3% or less (excluding 0%), Zr: 0.3% or less (excluding 0%), V: 0.3% or less (provided that 0%), Ti: 0.05% or less (excluding 0%), Zn: 1.0% or less (excluding 0%), and Ag: 0.2% or less (provided that
  • it may further include one or more selected from the group consisting of:
  • the Cu content is preferably 0.7% or less, more preferably 0.3% or less.
  • Mn, Fe, Cr, Zr, and V are contained in a large amount, a relatively coarse compound is likely to be generated, and the hem workability (hem bendability) that is a subject of the present invention is likely to be deteriorated. Therefore, the Mn content is preferably 0.6% or less, more preferably 0.3% or less, and the Cr, Zr, and V contents are each preferably 0.2% or less, more preferably 0.1%. % Or less.
  • Si 0.3-2.0%
  • Si is a major element, and forms Mg-Si-based precipitates that contribute to strength improvement during solid solution strengthening and artificial aging treatment such as paint baking treatment, and exhibits age-hardening ability, which is necessary for automobile outer panels It is an indispensable element for obtaining a sufficient strength (yield strength).
  • Si / Mg is set to 1.0 or more in mass ratio, and Si is further Mg than the excessive Si type generally called. It is preferable to make the composition of 6000 series aluminum alloy excessively contained. If the Si content is too small, the amount of Mg—Si based precipitates is insufficient, and the BH property is significantly reduced.
  • Si is set in the range of 0.3 to 2.0%.
  • a more preferred lower limit is 0.6%, and a more preferred upper limit is 1.4%.
  • Mg 0.2-2.0%
  • Mg is also a major element, forming solid solution strengthening and forming an Mg-Si-based precipitate that contributes to strength improvement during artificial aging treatment such as paint baking treatment, and exhibits age-hardening ability and the required proof strength as a panel It is an essential element for obtaining. If the Mg content is too small, the amount of Mg—Si-based precipitates is insufficient, and the BH property is significantly reduced. For this reason, the proof stress required as a panel cannot be obtained. On the other hand, when there is too much Mg content, a coarse crystallized substance and a precipitate will be formed and bending workability will fall remarkably. Therefore, the Mg content is in the range of 0.2 to 2.0%. A more preferred lower limit is 0.3%, and a more preferred upper limit is 1.0%.
  • Sn 0.005 to 0.3%
  • Sn is an essential element.
  • the diffusion of Mg and Si at room temperature is suppressed, and the increase in strength at room temperature (room temperature aging) is suppressed over a long period of time.
  • the trapped pores are released during the artificial aging treatment such as the paint baking treatment of the molded panel.
  • the diffusion of Mg and Si can be promoted and the BH property can be increased. .
  • the Sn content is in the range of 0.005 to 0.3%.
  • a more preferred lower limit is 0.01%, and a more preferred upper limit is 0.2%.
  • the Sn—Al—Mg—Si based aluminum alloy sheet of the present invention is an Al—Mg—Si based aluminum alloy sheet that does not contain Sn in terms of its solid solution in terms of structure and characteristics. It is very different compared to Similarly, even in the case of Al—Mg—Si-based aluminum alloy plates containing Sn (the same amount), if the production conditions such as intermediate annealing are different, the solid solution amount of Sn is different, Under manufacturing conditions (ordinary method), Sn is likely to precipitate as a compound, and the amount of solid solution is remarkably reduced (decreased). For this reason, even if it contains Sn (the same amount) in the same manner, it is possible to obtain a structure having an effect of suppressing room temperature aging at a high level as in the present invention and improving BH properties and hemmability. Not necessarily.
  • the average number density of a compound having a circle equivalent diameter in the range of 0.3 to 20 ⁇ m when measured using a 500-fold SEM as the structure of the plate is 5000 pieces / mm 2 or less (including 0 pieces / mm 2) .
  • the number density of the compound having an equivalent circle diameter of 0.3 ⁇ m or more is reduced to 5000 / mm 2 or less, the starting point of breakage in the structure of the plate at the time of molding is reduced, and hem workability is improved. Furthermore, since the amount of solid solution Mg and the amount of solid solution Si are increased and the amount of Mg—Si based precipitates generated during the BH treatment and contributing to the increase in strength is increased, the BH property is also improved. On the other hand, if the number density of the compound having an equivalent circle diameter of 0.3 ⁇ m or more exceeds 5000 / mm 2 , the starting point of breakage in the structure of the plate at the time of molding increases, and hemming workability, drawing and tensioning are increased.
  • the press formability such as protrusion decreases. Furthermore, the amount of solid solution Mg and the amount of solid solution Si decrease, and the amount of Mg—Si-based precipitates that are generated during the BH treatment and contribute to increasing the strength is insufficient, and the BH property is also lowered.
  • the equivalent circle diameter of the compound defined in the present invention is in the range of 0.3 to 20 ⁇ m, and the composition of the compound is not limited.
  • the equivalent circle diameter of the compound defined in the present invention is the diameter of a circle having the same area as the compound that is indefinite, and as a method for measuring or defining the size of the compound accurately and with good reproducibility, It has been widely used.
  • the average number density of compounds having an equivalent circle diameter in the range of 0.3 to 20 ⁇ m is preferably as small as possible from the viewpoint of reducing the starting point of fracture during heme processing and securing the solid solution amount of Sn. From the production limit of the efficient production method of the plate, it cannot be completely 0 pieces / mm 2 . Therefore, the lower limit in the present invention of the average number density of compounds having an equivalent circle diameter in the range of 0.3 to 20 ⁇ m does not include 0 pieces / mm 2. The lower limit is about 100 pieces / mm 2 .
  • the compounds observed in the plate structure by SEM of 500 times are observed as white particles scattered in the structure when observed in a black and white image. It is a variety of compounds (precipitates, crystallization products) containing Sn such as Mn, Al—Fe—Mn—Si, Al—Si—Sn, and the like. In addition, Mg—Si compounds may also be found in small numbers as black particles scattered in the structure. As described above, the composition of the compound varies widely depending on the composition of the aluminum alloy plate, and it is difficult to limit the composition to a specific composition.
  • Standard of Sn solid solution amount The present invention is characterized by securing the solid solution amount of Sn necessary for exhibiting the effect of Sn.
  • a guideline (standard) for securing the solid solution amount of Sn 0.5 mass, which is identified by an X-ray spectrometer among compounds having a circle equivalent diameter measured by the SEM in the range of 0.3 to 20 ⁇ m. % Or more of the compounds containing Sn in an amount of less than 50% (including 0%), that is, not less than 0% but less than 50%, preferably less than 40% (including 0%), more preferably less than 30% (0 % Included).
  • a compound having a Sn content of less than 0.5% is not a measurement target of a compound containing Sn as a measure of the Sn solid solution amount.
  • a compound containing Sn with a very small amount of Sn having a Sn content of less than 0.5% by mass is also measured, a compound containing Sn smaller than the measurement error of the X-ray spectrometer is detected, and the size described above. There is a possibility that all the compounds in the range will be measured. In this case, it cannot be said that the solid solution amount of Sn is accurately reflected. Therefore, from the viewpoint of correlation and reproducibility, a lower limit value of 0.5% by mass or more is provided for the Sn content of the compound.
  • the ratio of the number of compounds containing 0.5 mass% or more of Sn (average number) out of the total number of compounds measured by SEM having an equivalent circle diameter of 0.3 to 20 ⁇ m is less than 50%. Indicates that the amount of Sn that precipitates is small and the solid solution amount of Sn is sufficient to exhibit the effect of the added Sn. On the other hand, when the ratio of the number of compounds containing 0.5 mass% or more of Sn (average number) is 50% or more, the amount of precipitated Sn increases, and the solid solution amount of Sn contributes to the effect of the added Sn. The amount is so small that it does not show.
  • the evaluation of the Sn solid solution amount by the number ratio of the Sn-containing compound is an indirect measurement method, but includes 0.5 mass% or more of Sn having an equivalent circle diameter in the range of 0.3 to 20 ⁇ m. If the compound is the object of measurement, it correlates well with the effect exhibited by solid solution Sn. That is, the effect exhibited by solid solution Sn correlates well with the ratio of the number of compounds containing Sn (average number), which is identified by the X-ray spectrometer whether or not Sn is contained by 0.5 mass% or more. To do. This point is supported by the examples described later.
  • the ratio of the average number of compounds containing Sn of 0.5% by mass or more is less than 50%, and only after securing the solid solution amount of Sn, the capture of atomic vacancies at room temperature is not possible.
  • the effect of suppressing the diffusion of Mg and Si and the increase in strength at room temperature (room temperature aging) are exhibited over a long period of time.
  • the press formability, particularly the hem workability is improved at the time of press forming the panel after aging at room temperature onto the panel.
  • the effect of releasing the trapped holes is also exhibited, and the diffusion of Mg and Si can be promoted to increase the BH property. .
  • the lower limit of the ratio (average number) of compounds containing 0.5 mass% or more of Sn is theoretically 0% when the number of compounds containing Sn is 0 when all Sn is dissolved. This is the case.
  • Sn is likely to precipitate in the conventional method, and it is difficult to re-dissolve Sn once precipitated. Therefore, if the production efficiency is ignored, the number ratio of compounds containing Sn can be reduced to 0%, but the number of compounds containing Sn (average number) coming from an efficient (industrial) production limit.
  • the lower limit of the ratio is about 0.1%.
  • Compound measurement Measurement by SEM, which is 500 times the number density of the compound having an equivalent circle diameter of 0.3 to 20 ⁇ m, is performed at 10 points at an arbitrary point of 1/4 part in the plate thickness direction from the surface of the test plate (samples Ten samples are collected), and the number density of each sample is averaged to obtain an average number density (pieces / mm 2 ).
  • the measurement of the number ratio of the compound containing 0.5 mass% or more of Sn, which will be described later, is also performed along with this SEM, and similarly, the average number ratio (%) is obtained by averaging the number ratio of each sample. .
  • an SEM of 500 times the surface parallel to the plate surface passes through an arbitrary point from the surface in a 1/4 part of the plate thickness direction.
  • a sample is prepared by mechanically polishing a plate cross-section sample surface sampled 10 pieces from the above-mentioned site, cutting off about 0.25 mm from the plate surface by mechanical polishing, and further performing buffing to adjust the surface.
  • the number of compounds in the equivalent circle diameter range is measured by an automatic analyzer to calculate the number density.
  • the measurement site is the sample polishing surface, and the measurement area per sample is 240 ⁇ m ⁇ 180 ⁇ m.
  • an X-ray spectrometer used for measuring the number ratio of compounds containing Sn is well known as an analyzer using energy dispersive X-ray spectroscopy (Energy Dispersive X-ray Spectroscopy), and is usually called EDX.
  • This X-ray spectrometer is generally attached to the SEM used in the present invention and is widely used for quantitative analysis of the composition of the observed compound.
  • the number of compounds identified as containing Sn out of the total number of compounds having an equivalent circle diameter of 0.3 to 20 ⁇ m measured by the SEM was measured. The sample measurement results are averaged and calculated as an average number ratio.
  • the aluminum alloy sheet of the present invention is a conventional process or a known process, and the aluminum alloy ingot having the above-mentioned 6000 series component composition is subjected to homogenization heat treatment after casting, and then subjected to hot rolling and cold rolling to obtain a predetermined process. It is manufactured by being subjected to a tempering treatment such as solution hardening and quenching.
  • an ordinary molten casting method such as a continuous casting method and a semi-continuous casting method (DC casting method) is appropriately selected for the molten aluminum alloy adjusted to be dissolved within the above-mentioned 6000 series component composition range.
  • the average cooling rate during casting is as follows: It is preferable that the liquidus temperature to the solidus temperature be as large (fast) as possible at 30 ° C./min or more.
  • homogenization heat treatment Next, the cast aluminum alloy ingot is subjected to a homogenization heat treatment prior to hot rolling.
  • the purpose of this homogenization heat treatment (soaking) is to homogenize the structure, that is, eliminate segregation in crystal grains in the ingot structure.
  • the conditions are not particularly limited as long as the object is achieved, and normal one-stage or one-stage processing may be performed.
  • the homogenization heat treatment temperature is appropriately selected from the range of 500 ° C. or more and less than the melting point, and the homogenization time is 4 hours or more.
  • this homogenization temperature is low, segregation within the crystal grains cannot be sufficiently eliminated, and this acts as a starting point of fracture, so that stretch flangeability and bending workability are deteriorated.
  • the hot rolling may be started immediately, or the hot rolling may be started after cooling to an appropriate temperature.
  • Hot rolling is composed of an ingot (slab) rough rolling process and a finish rolling process according to the thickness of the rolled sheet.
  • a reverse or tandem rolling mill is appropriately used.
  • the hot rolling start temperature is preferably 350 ° C. to the solidus temperature, more preferably 400 ° C. to the solidus temperature.
  • Hot rolled sheet annealing Annealing (roughening) before cold rolling of this hot-rolled sheet is not always necessary, but it can be performed to further improve properties such as formability by refining crystal grains and optimizing the texture. good.
  • Cold rolling In cold rolling, the hot-rolled sheet is rolled to produce a cold-rolled sheet (including a coil) having a desired final thickness. However, in order to further refine the crystal grains, the total cold rolling rate is desirably 60% or more regardless of the number of passes.
  • the plate Before this cold rolling (after hot rolling) or in the middle of cold rolling (between passes), the plate is held at a high temperature of 480 ° C or higher and below the melting point for 0.1 to 10 seconds, and then 3 ° C / second or higher It is preferable to repeat the intermediate annealing forcibly cooling (rapid cooling) to room temperature at an average cooling rate of 2 times or more, so that Sn produced as a compound in the hot rolling step or the like is dissolved.
  • Sn is likely to precipitate, and it is difficult to re-dissolve once precipitated Sn, and the ratio of the average number of compounds containing Sn is less than 50% of the number of compounds of the specific size described above.
  • the holding time may be a short time including momentary such as 0.1 seconds, but if it exceeds 10 seconds, the mechanical properties of the plate are remarkably deteriorated.
  • the cooling after annealing is not the forced cooling (rapid cooling) to room temperature by air cooling, mist, water cooling or the like with an average cooling rate of 3 ° C./second or more, that is, the average cooling rate is less than 3 ° C./second. Then, Sn once dissolved is reprecipitated and compounded.
  • Annealing under such conditions is impossible in a batch furnace, including rapid cooling, and requires a continuous heat treatment furnace that winds the sheet through the furnace while unwinding it.
  • the solid solution amount of Sn is inevitably insufficient by only one continuous annealing.
  • the intermediate annealing by continuous annealing shall be repeated twice or more.
  • the number of repetitions of continuous annealing is preferably about 2 because the efficiency of the manufacturing process is greatly reduced as the number of repetitions increases.
  • the solution treatment and quenching treatment may be heating and cooling using a normal continuous heat treatment line, and is not particularly limited. However, since it is desirable to obtain a sufficient solid solution amount of each element and that the crystal grains of the plate structure are finer, the solution treatment temperature is 520 ° C. or higher and the melting temperature or lower. It is preferable that the heating be performed for at least 2 seconds, and the conditions are maintained for 0 to 10 seconds.
  • the average cooling rate from the solution temperature to the quenching stop temperature is preferably 3 ° C./second or more.
  • the quenching treatment is performed by selecting water cooling means and conditions such as air cooling such as a fan, mist, spray, and immersion, respectively.
  • reheating treatment a pre-aging treatment (reheating treatment) is performed after the solution quenching treatment in order to form an aggregate (cluster) of atoms serving as nuclei of the Mg—Si-based compound generated during the BH treatment.
  • the ultimate temperature (substance temperature) of the plate is preferably in the temperature range of 80 to 150 ° C., and the holding time is preferably in the range of 3 to 50 hours.
  • the cooling to room temperature after the reheating treatment may be allowed to cool or may be forcibly quenched using the cooling means at the time of quenching in order to increase production efficiency.
  • Embodiments of the present invention will be described. 6000 series aluminum alloy plates having different Sn solid solution amounts defined in the present invention were prepared according to the intermediate annealing conditions, and the number density of the compounds and the Sn solid solution amount based thereon were investigated. And BH property (coating bake hardenability) after holding this board at room temperature for 100 days and hem workability were also evaluated. The results are shown in Table 2.
  • the specific production conditions for these aluminum alloy plates were as follows.
  • Aluminum alloy ingots having respective compositions shown in Table 1 were commonly melted by DC casting.
  • the average cooling rate during casting was set to 50 ° C./min from the liquidus temperature to the solidus temperature.
  • the display in which the numerical value in each element is blank the content is below the detection limit and includes these elements No 0%.
  • the ingot was subjected to soaking treatment at 540 ° C. for 4 hours in common with each example, and then hot rough rolling was started. And in each example, it was hot rolled to a thickness of 2.5 mm in the subsequent finish rolling to obtain a hot rolled sheet.
  • Table 2 the aluminum alloy plate after hot rolling was subjected to rough annealing at 500 ° C. for 1 minute in common with each example, and then during the cold rolling pass (between passes) as shown in Table 2.
  • Intermediate annealing with an annealing furnace was performed under various conditions with different numbers, temperatures, average cooling rates, and the like, and finally a cold-rolled sheet (product sheet) having a thickness of 1.0 mm was obtained.
  • these cold-rolled sheets were subjected to a solution treatment in a 560 ° C. glass stone furnace in common with each example, held for 10 seconds after reaching the target temperature, and quenched by water cooling. Immediately after this quenching, a preliminary aging treatment was carried out by holding at 100 ° C. for 5 hours (after holding, slow cooling at a cooling rate of 0.6 ° C./hour).
  • test plate (blank) was cut out from each plate immediately after the tempering treatment, and the structure (number density of compounds, number ratio of compounds containing Sn) of each test plate was measured. Moreover, the test plate (blank) was cut out from each plate after being left at room temperature for 100 days after the tempering treatment, and the strength (AS proof stress) and BH property of each test plate were examined. These results are shown in Table 2.
  • Test plate structure As the structure of each test plate immediately after the tempering treatment, the average number density (pieces / mm 2 ) of the compound having a circle equivalent diameter in the range of 0.3 to 20 ⁇ m was measured with the SEM of 500 times by the measurement method described above. The average number ratio (%) of compounds containing 0.5% or more of Sn identified by the X-ray spectroscopic apparatus among the measured compounds was investigated.
  • Test test In the tensile test, JISZ2201 No. 5 test pieces (25 mm ⁇ 50 mmGL ⁇ plate thickness) were sampled from each test plate after being left at room temperature for 100 days after the tempering treatment, and a tensile test was performed at room temperature. It was. The tensile direction of the test piece at this time was the direction perpendicular to the rolling direction. The tensile speed was 5 mm / min up to 0.2% proof stress and 20 mm / min after proof stress. The N number for the measurement of mechanical properties was 5, and each was calculated as an average value. The test piece for measuring the yield strength after the BH was subjected to the BH treatment after giving a pre-strain of 2% simulating press forming of the plate to the test piece by the tensile tester.
  • BH property Each test plate was commonly aged at room temperature for 100 days and then subjected to an artificial age-hardening treatment at 185 ° C. for 20 minutes (after BH). Yield strength) was determined by the tensile test. And the BH property of each test plate was evaluated from the difference between these 0.2% proof stresses (increased proof stress), and the case where the increased amount of 0.2% proof stress was 100 MPa or more was regarded as acceptable.
  • Hem workability Hem workability was measured for each test plate after standing at room temperature for 100 days.
  • a strip-shaped test piece with a width of 30 mm was used, and after bending 90 ° with an internal bend R of 1.0 mm by a down flange, a 1.0 mm thick inner was sandwiched, and the bent portion was further bent inwardly to about 130 degrees.
  • Pre-hem processing was performed, and flat hem processing was performed in which the end was closely attached to the inner by bending 180 degrees.
  • the flat hem bend (edge bend) is visually observed for surface conditions such as rough skin, minute cracks, and large cracks, and visually evaluated according to the following criteria. . 0: No cracking, rough skin, 1: Mild rough skin, 2; Deep rough skin, 3: Small surface crack, 4; Continuous surface crack, 5: Break
  • each of the inventive examples shown in the numbers 1 to 4 and 12 to 23 in Table 2 is within the composition range of the present invention (alloy numbers 1 to 13 in Table 1) and within the above-mentioned preferable condition range including the intermediate annealing. Manufacture. For this reason, as shown in Table 2, each of these inventive examples satisfies the average number density of the compound defined in the present invention and the average number ratio of the compound containing 0.5 mass% or more of Sn, and precipitates Sn contained. Is suppressed, and the solid solution amount of Sn is high.
  • each of the above-mentioned invention examples has a BH (baked hard) even after the long-term room temperature aging for 100 days after the tempering treatment, or even when the As proof strength is 90 to 110 MPa.
  • the yield strength is 190 MPa and the difference in yield strength is 100 MPa or more.
  • the As yield strength is relatively low, so that it is excellent in press formability to automobile panels and the like, and is excellent in hem workability.
  • Comparative Examples 5 to 11 in Table 2 using the same alloy number 1 in Table 1 as those of the invention examples are examples in which the intermediate annealing conditions deviate from the preferred range. For this reason, these comparative examples have too many compounds prescribed
  • Comparative Example 5 is not subjected to intermediate annealing. Although the comparative example 6 satisfy
  • the second intermediate annealing satisfies the conditions of temperature, holding time, and average cooling rate, but the temperature of the first intermediate annealing is too low at 480 ° C.
  • the first intermediate annealing satisfies the conditions of temperature, holding time, and average cooling rate, but the temperature of the second intermediate annealing is too low at 480 ° C.
  • the temperatures of the first and second intermediate annealings are both less than 480 ° C. and too low.
  • the temperature and holding time of the first and second intermediate annealing satisfy the conditions, but the average cooling rate of the first or second time is too slow.
  • Comparative Examples 24 to 29 in Table 2 are manufactured within a preferable range including intermediate annealing conditions, Alloy Nos. 14 to 19 in Table 1 are used, and inclusion of essential elements Mg, Si, and Sn Each amount is outside the scope of the present invention. For this reason, as shown in Table 2, these Comparative Examples 24 to 29 have a relatively high As yield strength after holding at room temperature for 100 days, as compared with each invention example. It is inferior in workability or BH property. In Comparative Example 27, Sn was too much, and cracking occurred during hot rolling, so that the hot rolled sheet itself could not be manufactured.
  • the comparative example 24 is the alloy 14 of Table 1, and there is too little Si.
  • the comparative example 25 is the alloy 15 of Table 1, and there is too much Si.
  • the comparative example 26 is the alloy 16 of Table 1, and there is too little Sn.
  • the comparative example 27 is the alloy 17 of Table 1, and there is too much Sn.
  • the comparative example 28 is the alloy 18 of Table 1, and there is too little Mg.
  • the comparative example 29 is the alloy 19 of Table 1, and there is too much Mg.
  • composition and compound structure defined in the present invention and intermediate annealing conditions for the improvement of heme workability and BH property after long-term aging of a 6000 series aluminum alloy plate containing Sn The critical significance or effect of preferable manufacturing conditions such as the above is supported.
  • the present invention it is possible to provide a 6000 series aluminum alloy plate having both BH properties and formability after long-term room temperature aging.
  • the application of the 6000 series aluminum alloy plate can be expanded as a member for a transport device such as an automobile, a ship or a vehicle, a home appliance, a building or a structure, and particularly as a member for a transport device such as an automobile.

Abstract

 The present invention pertains to an Al-Mg-Si based aluminum alloy sheet for forming, that contains 0.2-2.0% of Mg, 0.3-2.0% of Si, and 0.005-0.3% of Si (all amounts given with respect to mass), the balance comprising Al and unavoidable impurities, wherein the aluminum alloy sheet for forming is characterized in that the structure of the aluminum alloy sheet is such that the average number density of compounds having a circle-equivalent diameter within a range of 0.3-20 μm as measured by SEM at 500 times magnification is more than 0/mm2 but not more than 5,000/mm2, and of the compounds measured by SEM, the average count ratio of compounds that contain 0.5% by mass or more of Sn as identified using an X-ray spectrograph, is 0% or more but less than 50%. This aluminum alloy sheet for forming exhibits high BH properties and good workability.

Description

成形用アルミニウム合金板Aluminum alloy sheet for forming
 本発明は成形用Al-Mg-Si系アルミニウム合金板に関するものである。本発明で言うアルミニウム合金板とは、熱間圧延板や冷間圧延板などの圧延板であって、溶体化処理および焼入れ処理などの調質が施された後であって、焼付け塗装硬化処理される前のアルミニウム合金板を言う。また、以下の記載ではアルミニウムをアルミやAlとも言う。 The present invention relates to an Al—Mg—Si based aluminum alloy sheet for forming. The aluminum alloy sheet referred to in the present invention is a rolled sheet such as a hot-rolled sheet or a cold-rolled sheet, and is subjected to tempering such as solution treatment and quenching process, and is baked and coated and cured. Says aluminum alloy plate before being done. In the following description, aluminum is also referred to as aluminum or Al.
 近年、地球環境などへの配慮から、自動車等の車両の軽量化の社会的要求はますます高まってきている。かかる要求に答えるべく、自動車パネル、特にフード、ドア、ルーフなどの大型ボディパネル(アウタパネル、インナパネル)の材料として、鋼板等の鉄鋼材料に代えて、成形性や焼付け塗装硬化性に優れた、より軽量なアルミニウム合金材の適用が増加しつつある。 In recent years, due to consideration for the global environment, social demands for weight reduction of vehicles such as automobiles are increasing. In order to meet such demands, as a material for large-sized body panels (outer panels, inner panels) such as automobile panels, especially hoods, doors, roofs, etc., instead of steel materials such as steel plates, it was excellent in formability and bake coating curability. The application of lighter aluminum alloy materials is increasing.
 この内、自動車のフード、フェンダー、ドア、ルーフ、トランクリッドなどのパネル構造体の、アウタパネル(外板)やインナパネル(内板)等のパネルには、薄肉でかつ高強度アルミニウム合金板として、Al-Mg-Si系のAA乃至JIS 6000系(以下、単に6000系とも言う)アルミニウム合金板の使用が検討されている。 Among these, panels such as outer panels (outer plates) and inner panels (inner plates) of panel structures such as automobile hoods, fenders, doors, roofs and trunk lids are thin and high-strength aluminum alloy plates. The use of Al—Mg—Si based AA to JISJ6000 (hereinafter also simply referred to as 6000) aluminum alloy plates is being studied.
 この6000系アルミニウム合金板は、Si、Mgを必須として含み、特に過剰Si型の6000系アルミニウム合金は、これらSi/Mgが質量比で1以上である組成を有し、優れた時効硬化能を有している。このため、プレス成形や曲げ加工時には低耐力化により成形性を確保するとともに、成形後のパネルの塗装焼付処理などの、比較的低温の人工時効(硬化)処理時の加熱により時効硬化して耐力が向上し、パネルとしての必要な強度を確保できる焼付け塗装硬化性(以下、ベークハード性=BH性、焼付硬化性とも言う)がある。 This 6000 series aluminum alloy plate contains Si and Mg as essential components. Particularly, the excess Si type 6000 series aluminum alloy has a composition in which these Si / Mg is 1 or more in mass ratio, and has excellent age hardening ability. Have. For this reason, formability is ensured by reducing the yield strength during press molding and bending, and age-hardening is achieved by heating during relatively low-temperature artificial aging (curing) treatment such as paint baking treatment of panels after molding. And has a baking coating curability (hereinafter also referred to as bake hard property = BH property, bake curability) that can secure the required strength as a panel.
 また、6000系アルミニウム合金板は、Mg量などの合金量が多い他の5000系アルミニウム合金などに比して、合金元素量が比較的少ない。このため、これらアルミニウム合金板のスクラップを、アルミニウム合金溶解材(溶解原料)として再利用する際に、元の6000系アルミニウム合金鋳塊が得やすく、リサイクル性にも優れている。 In addition, the 6000 series aluminum alloy plate has a relatively small amount of alloy elements as compared with other 5000 series aluminum alloys having a large amount of alloy such as Mg. For this reason, when the scraps of these aluminum alloy plates are reused as an aluminum alloy melting material (melting raw material), the original 6000 series aluminum alloy ingot is easily obtained and the recyclability is excellent.
 一方、自動車のアウタパネルは、周知の通り、アルミニウム合金板に対し、プレス成形における張出成形時や曲げ成形などの成形加工が複合して行われて製作される。例えば、フードやドアなどの大型のアウタパネルでは、張出などのプレス成形によって、アウタパネルとしての成形品形状となされ、次いで、このアウタパネル周縁部のフラットヘムなどのヘム(ヘミング)加工によって、インナパネルとの接合が行われ、パネル構造体とされる。 On the other hand, as is well known, an outer panel of an automobile is manufactured by combining an aluminum alloy plate with a forming process such as press forming and bending forming. For example, in a large outer panel such as a hood or a door, it is formed into a molded product shape as an outer panel by press molding such as overhanging, and then the inner panel is formed by hem (hemming) processing such as flat hem on the outer peripheral edge of the outer panel. Are joined to form a panel structure.
 ここで、6000系アルミニウム合金は、優れたBH性を有するという利点がある反面で、室温時効性を有し、溶体化焼入れ処理後、数ヶ月間の室温保持で時効硬化して強度が増加することにより、パネルへの成形性、特に曲げ加工性が低下する課題があった。例えば、6000系アルミニウム合金板を自動車パネル用途に用いる場合、アルミメーカーで溶体化焼入れ処理された後(製造後)、自動車メーカーでパネルに成形加工されるまでに、通常は1~4ヶ月間程度室温におかれ(室温放置され)、この間で、かなり時効硬化(室温時効)することとなる。特に、厳しい曲げ加工が入るアウタパネルにおいては、製造後1ヵ月経過後では、問題無く成形可能であっても、3ヶ月経過後では、ヘム加工時に割れが生じるなどの問題が有った。したがって、自動車パネル用、特にアウタパネル用の6000系アルミニウム合金板では、1~4ヶ月間程度の比較的長期に亙る室温時効を抑制する必要がある。 Here, the 6000 series aluminum alloy has an advantage of having excellent BH property, but has aging property at room temperature, and after the solution quenching treatment, it is age-hardened by holding at room temperature for several months to increase the strength. As a result, there is a problem that the formability to the panel, particularly the bending workability, is lowered. For example, when a 6000 series aluminum alloy plate is used for an automotive panel, it usually takes about 1 to 4 months after it is solution-quenched by an aluminum maker (after manufacture) and then molded into a panel by an automotive maker. It is left at room temperature (and left at room temperature), and during this time, it is considerably age-hardened (room temperature aging). In particular, in the outer panel that undergoes severe bending, there was a problem that cracking occurred at the time of hem processing after three months even though it could be molded without any problem after one month after manufacture. Therefore, it is necessary to suppress room temperature aging over a relatively long period of about 1 to 4 months in a 6000 series aluminum alloy plate for automobile panels, particularly for outer panels.
 更に、このような室温時効が大きい場合には、BH性が低下して、成形後のパネルの塗装焼付処理などの、比較的低温の人工時効(硬化)処理時の加熱によっては、パネルとしての必要な強度までに、耐力が向上しなくなるという問題も生じる。 Further, when such room temperature aging is large, the BH property is lowered, and depending on the heating at the relatively low temperature artificial aging (curing) treatment such as paint baking treatment of the panel after molding, There is also a problem that the yield strength is not improved to the required strength.
 従来から、6000系アルミニウム合金板の組織、特に含有元素が形成する化合物(晶出物、析出物)の観点から、成形性やBH性の向上、あるいは室温時効の抑制を図るなどの特性向上について、種々の提案がなされている。最近では、特に、6000系アルミニウム合金板のBH性や室温時効性に影響するクラスタ(原子の集合体)を直接測定して制御する試みなども提案されている。 Conventionally, from the viewpoint of the structure of a 6000 series aluminum alloy sheet, particularly the compound (crystallized product, precipitate) formed by the contained elements, improvement of properties such as improvement of formability and BH property, or suppression of room temperature aging Various proposals have been made. Recently, in particular, attempts have been made to directly measure and control clusters (aggregates of atoms) that affect the BH properties and room temperature aging properties of 6000 series aluminum alloy plates.
 また、本発明におけるSnの添加に関係する先行特許としても、6000系アルミニウム合金板にSnを積極的に添加し、室温時効を抑制と焼付け塗装硬化を向上させる方法も多数提案されている。例えば、特許文献1では、経時変化抑制効果を有するSnを適量添加し、また溶体化処理後に予備時効を施すことで、室温時効抑制と焼付け塗装硬化を兼備する方法が兼備されている。また、特許文献2では、経時変化抑制効果を有するSnと成形性を向上させるCuを添加して、成形性、焼付け塗装性、耐食性を向上させる方法が提案されている。 Also, as a prior patent related to the addition of Sn in the present invention, a number of methods have been proposed in which Sn is positively added to a 6000 series aluminum alloy plate to suppress room temperature aging and improve baking coating hardening. For example, in Patent Document 1, there is a method that combines room temperature aging suppression and baking coating curing by adding an appropriate amount of Sn having a temporal change suppressing effect and applying pre-aging after solution treatment. Patent Document 2 proposes a method for improving formability, baking paintability, and corrosion resistance by adding Sn having a temporal change suppressing effect and Cu for improving formability.
日本国特開平09-249950号公報Japanese Unexamined Patent Publication No. 09-249950 日本国特開平10-226894号公報Japanese Unexamined Patent Publication No. 10-226894
 ただし、従来のSnを積極的に添加したAl-Mg-Si系アルミニウム合金板でも、長時間の室温時効後の良好な成形性と高いBH性とを兼備するのには、未だ改善の余地があった。 However, even Al-Mg-Si based aluminum alloy sheets to which Sn is positively added still have room for improvement in order to have both good formability after long-term aging at room temperature and high BH properties. there were.
 このような課題に鑑み、本発明の目的は、長時間の室温時効後の車体塗装焼付け処理であっても、高いBH性と良好な加工性とが発揮できる、Snを含む成形用Al-Mg-Si系アルミニウム合金板を提供することである。 In view of such problems, an object of the present invention is to form Sn-containing Al—Mg, which can exhibit high BH properties and good workability even in a car body paint baking process after long-term aging at room temperature. -To provide a Si-based aluminum alloy sheet.
 この目的を達成するために、本発明の成形用アルミニウム合金板の要旨は、質量%で、Mg:0.2~2.0%、Si:0.3~2.0%およびSn:0.005~0.3%を各々含み、残部がAlおよび不可避的不純物からなるAl-Mg-Si系アルミニウム合金板であって、前記アルミニウム合金板の組織として、500倍のSEMを用いて測定した際の円相当直径が0.3~20μmの範囲の化合物の平均数密度が0個/mm超5000個/mm以下であり、前記SEMにて測定された化合物のうち、X線分光装置により識別される、0.5質量%以上のSnを含む化合物の平均個数割合が0%以上50%未満であることとする。 In order to achieve this object, the gist of the forming aluminum alloy plate of the present invention is, in mass%, Mg: 0.2 to 2.0%, Si: 0.3 to 2.0%, and Sn: 0.00. When an Al—Mg—Si-based aluminum alloy plate containing 005 to 0.3% and the balance being Al and inevitable impurities is measured using a 500-fold SEM as the structure of the aluminum alloy plate The average number density of the compound having an equivalent circle diameter of 0.3 to 20 μm is 0 / mm 2 and 5000 / mm 2 or less, and among the compounds measured by the SEM, The average number ratio of the compound containing 0.5 mass% or more of Sn to be identified is 0% or more and less than 50%.
 Snは、Al-Mg-Si系アルミニウム合金板の組織において、室温においては、原子空孔を捕獲(捕捉、トラップ)することで、室温でのMgやSiの拡散を抑制し、室温における強度増加を抑制し、板のパネルへの成形時に、ヘム加工性や絞り加工や張出加工などのプレス成形性(以下、このプレス成形性を代表してヘム加工性とも言う)を向上させる効果がある。そして、パネルの塗装焼き付け処理などの人工時効処理時には捕獲していた空孔を放出するため、逆にMgやSiの拡散を促進し、BH性を高くすることができる。 Sn, in the structure of Al-Mg-Si aluminum alloy plate, traps atomic vacancies at room temperature, thereby suppressing the diffusion of Mg and Si at room temperature and increasing the strength at room temperature. Has the effect of improving press formability such as hem workability, drawing and overhanging (hereinafter also referred to as hem workability as a representative of this press formability) when forming plates into panels. . And since the vacancies captured during the artificial aging treatment such as the paint baking treatment of the panel are released, the diffusion of Mg and Si can be promoted and the BH property can be increased.
 ただ、本発明者らの知見によれば、このようなSnの添加には、Sn特有の特性からくる大きな制約が存在する。Snの原子空孔の捕獲や放出効果は、Snがマトリックスに固溶して初めて発揮される。しかしながら、Snのマトリックスへの固溶量はごく少なく(低く)、通常の板の製造方法では、Snの添加量を理論固溶量以下に抑えたとしても、その多くが固溶せずに、化合物として晶出あるいは析出してしまう。このように化合物として晶出あるいは析出したSnには原子空孔の捕獲や放出効果が無い。 However, according to the knowledge of the present inventors, such addition of Sn has a great restriction due to the characteristics peculiar to Sn. The effect of capturing and releasing Sn atomic vacancies is exhibited only when Sn is dissolved in the matrix. However, the amount of Sn dissolved in the matrix is very small (low), and in the ordinary plate manufacturing method, even if the addition amount of Sn is kept below the theoretical solid solution amount, most of it does not dissolve, Crystallized or precipitated as a compound. Thus, Sn crystallized or precipitated as a compound has no effect of trapping or releasing atomic vacancies.
 このため、本発明では、板の製造方法も敢えて見直した上で、後述する通り、中間焼鈍などの製造条件を工夫し、含有するSnの存在状態を制御して、Snの化合物としての析出を抑制し、Snのマトリックスへの固溶を促進して、Snの固溶量を確保する。これによって、Snの原子空孔の捕獲や放出効果による時効抑制によって、ヘム加工性やBH性の向上効果を十分に発揮させる。 For this reason, in this invention, after deliberately reviewing the manufacturing method of the plate, as described later, the manufacturing conditions such as intermediate annealing are devised, and the presence state of the contained Sn is controlled to precipitate Sn as a compound. It suppresses and promotes the solid solution of Sn in the matrix, and ensures the solid solution amount of Sn. As a result, the effect of improving heme workability and BH property is sufficiently exhibited by the trapping of Sn atomic vacancies and the suppression of aging by the release effect.
 これによって、板製造後に例えば100日間の長時間室温時効した場合であっても、より高い成形性やBH性が発揮できる、Sn入りAl-Mg-Si系アルミニウム合金板を提供できる。 As a result, it is possible to provide an Sn-containing Al—Mg—Si based aluminum alloy plate that can exhibit higher formability and BH properties even when it is aged at room temperature for a long time, for example, for 100 days after the plate is manufactured.
 ちなみに、従来のSn入りAl-Mg-Si系アルミニウム合金板では、このようなSnの効果を充分に発揮できてはいなかった。 Incidentally, the conventional Sn-containing Al—Mg—Si based aluminum alloy plate could not sufficiently exhibit such effects of Sn.
 その理由は、従来は、主要元素であるMgやSiの固溶や析出には常に注目しながらも、選択的な添加元素の一つでしかなかった、Snの固溶や析出の存在形態には、あまり注目していなかったためであると推考される。また、常法により製造された板のSnの存在形態は、化合物としての晶出あるいは析出(以下、単に析出とも言う)である。これとは異なり、しかも、Snを固溶させること自体が難しく、Snの固溶状態がごく稀な存在形態であるため、Snの固溶により発揮される効果について、知見しにくかったためであると推考される。 The reason for this is that in the past, the solid solution and precipitation of Sn, which was only one of the selective additive elements, while always paying attention to the solid solution and precipitation of the main elements Mg and Si. This is probably due to the fact that they did not pay much attention. Further, the Sn present form of the plate produced by a conventional method is crystallization or precipitation (hereinafter, also simply referred to as precipitation) as a compound. In contrast to this, it is difficult to solidify Sn itself, and since the solid solution state of Sn is a very rare form, it is difficult to know the effects exhibited by the solid solution of Sn. Inferred.
 以下に、本発明の実施の形態につき、要件ごとに具体的に説明する。 Hereinafter, the embodiment of the present invention will be specifically described for each requirement.
(化学成分組成)
 先ず、本発明のAl-Mg-Si系(以下、6000系とも言う)アルミニウム合金板の化学成分組成について、以下に説明する。本発明が対象とする6000系アルミニウム合金板は、自動車のパネル用の板などとして、優れた成形性やBH性、強度、溶接性、耐食性などの諸特性が要求される。すなわち、前記調質処理後に100日の長期室温時効された板であっても、As耐力が110MPa以下、BH(ベークハード)性が耐力差で100MPa以上、ヘム加工性が実施例で後述する評価基準で2以上など、自動車パネルなどへのプレス成形性やヘム加工性にも優れ、BH性も優れていることが要求される。
(Chemical composition)
First, the chemical composition of the Al—Mg—Si (hereinafter also referred to as 6000) aluminum alloy sheet of the present invention will be described below. The 6000 series aluminum alloy plate targeted by the present invention is required to have excellent properties such as formability, BH property, strength, weldability, and corrosion resistance as a plate for an automobile panel. That is, even for a plate that has been aged at room temperature for a long period of 100 days after the tempering treatment, the As proof stress is 110 MPa or less, the BH (bake hard) property is proof stress difference of 100 MPa or more, and the hem workability is described later in the examples. It is required that it is excellent in press formability and hem workability to automobile panels, etc., and BH properties are excellent, such as 2 or more on the basis.
 このような要求を満足するために、前提となるアルミニウム合金板の組成は、質量%で、Mg:0.2~2.0%、Si:0.3~2.0%およびSn:0.005~0.3%を各々含み、残部がAlおよび不可避的不純物からなるものとする。なお、各元素の含有量の%表示は全て質量%の意味である。また、本明細書においては、質量を基準とした百分率(質量%)は、重量を基準とした百分率(重量%)と同じである。また、各化学成分の含有量について、「X%以下(但し、0%を含まず)」であることを、「0%超X%以下」と表すことがある。 In order to satisfy such a requirement, the composition of the aluminum alloy sheet as a premise is Mg: 0.2-2.0%, Si: 0.3-2.0%, and Sn: 0.0. 005 to 0.3% is included, and the balance is made of Al and inevitable impurities. In addition,% display of content of each element means the mass% altogether. Moreover, in this specification, the percentage (mass%) based on mass is the same as the percentage (wt%) based on weight. In addition, the content of each chemical component may be expressed as “X% or less (excluding 0%)” as “over 0% and X% or less”.
 本発明が対象とする6000系アルミニウム合金板は、BH性がより優れた、SiとMgとの質量比Si/Mgが1以上であるような過剰Si型の6000系アルミニウム合金板とされるのが好ましい。6000系アルミニウム合金板は、プレス成形や曲げ加工時には低耐力化により成形性を確保するとともに、成形後のパネルの塗装焼付処理などの、比較的低温の人工時効処理時の加熱により時効硬化して耐力が向上し、必要な強度を確保できる優れた時効硬化能(BH性)を有している。この中でも、過剰Si型の6000系アルミニウム合金板は、質量比Si/Mgが1未満の6000系アルミニウム合金板に比して、このBH性がより優れている。 The 6000 series aluminum alloy plate targeted by the present invention is an excess Si type 6000 series aluminum alloy plate having a better BH property and a Si / Mg mass ratio of Si / Mg of 1 or more. Is preferred. The 6000 series aluminum alloy sheet secures formability by reducing the yield strength during press molding and bending, and is age-hardened by heating during relatively low temperature artificial aging treatment such as paint baking treatment of the panel after molding. Yield strength is improved, and it has excellent age-hardening ability (BH property) that can secure the required strength. Among these, the excess Si type 6000 series aluminum alloy plate is more excellent in this BH property than the 6000 series aluminum alloy plate having a mass ratio Si / Mg of less than 1.
 本発明では、これらMg、Si以外のその他の元素は不純物あるいは含まれても良い元素であり、AA乃至JIS規格などに沿った各元素レベルの含有量(許容量)とする。 In the present invention, these other elements other than Mg and Si are impurities or elements that may be contained, and the content (allowable amount) at each element level in accordance with AA or JIS standards.
 すなわち、資源リサイクルの観点から、本発明でも、合金の溶解原料として、高純度Al地金だけではなく、Mg、Si以外のその他の元素を添加元素(合金元素)として多く含む6000系合金やその他のアルミニウム合金スクラップ材、低純度Al地金などを多量に使用した場合には、下記のような他の元素が必然的に実質量混入される。そして、これらの元素を敢えて低減する精錬自体がコストアップとなり、ある程度の含有を許容することが必要となる。また、これらの元素を実質量含有しても、本発明目的や効果を阻害しない有用な含有範囲がある。 That is, from the viewpoint of resource recycling, in the present invention, not only high-purity Al ingots but also 6000 series alloys containing many other elements other than Mg and Si as additive elements (alloy elements) are used as melting raw materials for alloys. When a large amount of aluminum alloy scrap material, low-purity Al metal, etc. is used, the following other elements are necessarily mixed in substantial amounts. And refining itself that dares to reduce these elements increases the cost, and it is necessary to allow a certain amount of inclusion. Moreover, even if these elements are contained in substantial amounts, there is a useful content range that does not impair the object and effects of the present invention.
 したがって、本発明では、このような下記元素を各々以下に規定するAA乃至JIS 規格などに沿った上限量以下の範囲での含有を許容する。 Therefore, in the present invention, the following elements are allowed to be contained in the range below the upper limit amount in accordance with the AA to JIS standards specified below.
 具体的には、Mn:1.0%以下(但し、0%を含まず)、Cu:1.0%以下(但し、0%を含まず)、Fe:1.0%以下(但し、0%を含まず)、Cr:0.3%以下(但し、0%を含まず)、Zr:0.3%以下(但し、0%を含まず)、V:0.3%以下(但し、0%を含まず)、Ti:0.05%以下(但し、0%を含まず)、Zn:1.0%以下(但し、0%を含まず)およびAg:0.2%以下(但し、0%を含まず)からなる群から選択される1種または2種以上を、この範囲で、上記した基本組成に加えて、更に含んでも良い。 Specifically, Mn: 1.0% or less (excluding 0%), Cu: 1.0% or less (excluding 0%), Fe: 1.0% or less (excluding 0%) %), Cr: 0.3% or less (excluding 0%), Zr: 0.3% or less (excluding 0%), V: 0.3% or less (provided that 0%), Ti: 0.05% or less (excluding 0%), Zn: 1.0% or less (excluding 0%), and Ag: 0.2% or less (provided that In addition to the basic composition described above, it may further include one or more selected from the group consisting of:
 なお、これらの元素を含有する場合、Cuは含有量が多いと耐食性を劣化させやすいので、好ましくはCuの含有量を0.7%以下、より好ましくは0.3%以下とする。また、Mn、Fe、Cr、Zr、Vは、含有量が多いと比較的粗大な化合物を生成しやすく、本発明で課題とするヘム加工性(ヘム曲げ性)を劣化させやすい。このため、Mn含有量は、好ましくは0.6%以下、より好ましくは0.3%以下とし、Cr、Zr、V含有量は、それぞれ好ましくは0.2%以下、より好ましくは0.1%以下とする。 In addition, when these elements are contained, since Cu tends to deteriorate the corrosion resistance when the content is large, the Cu content is preferably 0.7% or less, more preferably 0.3% or less. Further, when Mn, Fe, Cr, Zr, and V are contained in a large amount, a relatively coarse compound is likely to be generated, and the hem workability (hem bendability) that is a subject of the present invention is likely to be deteriorated. Therefore, the Mn content is preferably 0.6% or less, more preferably 0.3% or less, and the Cr, Zr, and V contents are each preferably 0.2% or less, more preferably 0.1%. % Or less.
 上記6000系アルミニウム合金における、各元素の含有範囲と意義、あるいは許容量について以下に順に説明する。 The content range and significance of each element in the 6000 series aluminum alloy, or the allowable amount will be described in order below.
Si:0.3~2.0%
 Siは、主要元素として、固溶強化と、塗装焼き付け処理などの人工時効処理時に、強度向上に寄与するMg-Si系析出物を形成して、時効硬化能を発揮し、自動車のアウタパネルとして必要な強度(耐力)を得るための必須の元素である。また、パネルへの成形後の塗装焼き付け処理での優れた時効硬化能を発揮させるためには、Si/Mgを質量比で1.0以上とし、一般に言われる過剰Si型よりも更にSiをMgに対し過剰に含有させた6000系アルミニウム合金組成とすることが好ましい。Si含有量が少なすぎると、Mg-Si系析出物の生成量が不足するため、BH性が著しく低下する。一方、Si含有量が多すぎると、粗大な晶出物および析出物が形成されて、曲げ加工性が著しく低下する。したがって、Siは0.3~2.0%の範囲とする。さらに好ましい下限値は0.6%であり、さらに好ましい上限値は1.4%である。
Si: 0.3-2.0%
Si is a major element, and forms Mg-Si-based precipitates that contribute to strength improvement during solid solution strengthening and artificial aging treatment such as paint baking treatment, and exhibits age-hardening ability, which is necessary for automobile outer panels It is an indispensable element for obtaining a sufficient strength (yield strength). In addition, in order to exhibit the excellent age-hardening ability in the paint baking process after forming on the panel, Si / Mg is set to 1.0 or more in mass ratio, and Si is further Mg than the excessive Si type generally called. It is preferable to make the composition of 6000 series aluminum alloy excessively contained. If the Si content is too small, the amount of Mg—Si based precipitates is insufficient, and the BH property is significantly reduced. On the other hand, when there is too much Si content, a coarse crystallized substance and a precipitate will be formed and bending workability will fall remarkably. Therefore, Si is set in the range of 0.3 to 2.0%. A more preferred lower limit is 0.6%, and a more preferred upper limit is 1.4%.
Mg:0.2~2.0%
 Mgも、主要元素として、固溶強化と、塗装焼き付け処理などの人工時効処理時に、強度向上に寄与するMg-Si系析出物を形成して、時効硬化能を発揮し、パネルとしての必要耐力を得るための必須の元素である。Mg含有量が少なすぎると、Mg-Si系析出物の生成量が不足するため、BH性が著しく低下する。このためパネルとして必要な耐力が得られない。一方、Mg含有量が多すぎると、粗大な晶出物および析出物が形成されて、曲げ加工性が著しく低下する。したがって、Mgの含有量は0.2~2.0%の範囲とする。さらに好ましい下限値は0.3%であり、さらに好ましい上限値は1.0%である。
Mg: 0.2-2.0%
Mg is also a major element, forming solid solution strengthening and forming an Mg-Si-based precipitate that contributes to strength improvement during artificial aging treatment such as paint baking treatment, and exhibits age-hardening ability and the required proof strength as a panel It is an essential element for obtaining. If the Mg content is too small, the amount of Mg—Si-based precipitates is insufficient, and the BH property is significantly reduced. For this reason, the proof stress required as a panel cannot be obtained. On the other hand, when there is too much Mg content, a coarse crystallized substance and a precipitate will be formed and bending workability will fall remarkably. Therefore, the Mg content is in the range of 0.2 to 2.0%. A more preferred lower limit is 0.3%, and a more preferred upper limit is 1.0%.
Sn:0.005~0.3%
 Snは必須の元素であり、室温において原子空孔を捕獲することで、室温でのMgやSiの拡散を抑制し、室温における強度増加(室温時効)を長期に亘って抑制し、この室温時効後の板の、パネルへのプレス成形時に、プレス成形性や、特にヘム加工性を向上させる効果がある。そして、一方では、成形されたパネルの塗装焼き付け処理などの人工時効処理時に、捕獲していた空孔を放出するため、逆にMgやSiの拡散を促進し、BH性を高くすることができる。
Sn: 0.005 to 0.3%
Sn is an essential element. By capturing atomic vacancies at room temperature, the diffusion of Mg and Si at room temperature is suppressed, and the increase in strength at room temperature (room temperature aging) is suppressed over a long period of time. There is an effect of improving press formability, particularly hemmability, at the time of press-molding a subsequent plate to a panel. And on the other hand, the trapped pores are released during the artificial aging treatment such as the paint baking treatment of the molded panel. On the contrary, the diffusion of Mg and Si can be promoted and the BH property can be increased. .
 Snの含有量が少なすぎると、室温における強度増加を抑制できず、耐力が高くなって、ヘム加工性が劣化するだけでなく、BH処理時のMg-Si系析出物の生成量も減少して、BH性が低くなりやすい。したがって、Snの含有量は0.005~0.3%の範囲とする。さらに好ましい下限値は0.01%であり、さらに好ましい上限値は0.2%である。 If the Sn content is too small, the increase in strength at room temperature cannot be suppressed, the yield strength becomes high, the hemmability deteriorates, and the amount of Mg-Si precipitates produced during BH treatment also decreases. Therefore, the BH property tends to be low. Therefore, the Sn content is in the range of 0.005 to 0.3%. A more preferred lower limit is 0.01%, and a more preferred upper limit is 0.2%.
 但し、これらのSnの効果は、Snが固溶して初めて発揮される。このために、本発明では、後述する通り、特定の範囲のサイズの化合物のうち、一定量以上のSnを含む化合物の個数割合を規定して、Snの必要固溶量を確保する。 However, these effects of Sn are exhibited only after Sn is dissolved. Therefore, in the present invention, as will be described later, among the compounds having a specific range of sizes, the ratio of the number of compounds containing a certain amount or more of Sn is specified to ensure the necessary solid solution amount of Sn.
 したがって、本発明のSnを含有したAl-Mg-Si系アルミニウム合金板は、Snの固溶という点で、組織的にも特性的にも、Snを含有しないAl-Mg-Si系アルミニウム合金板と比較して大きく異なる。また、同じように(同じ量の)Snを含有したAl-Mg-Si系アルミニウム合金板であっても、中間焼鈍などの製造条件が違えば、Snの固溶量が異なり、通常の板の製造条件(常法)では、Snが化合物として析出しやすく、固溶量が著しく低くなる(少なくなる)ために、その組織は互いに大きく異なる。このため、同じように(同じ量の)Snを含有していても、本発明のような高いレベルで室温時効を抑制するとともに、BH性やヘム加工性を向上させる効果のある組織が得られるとは限らない。 Therefore, the Sn—Al—Mg—Si based aluminum alloy sheet of the present invention is an Al—Mg—Si based aluminum alloy sheet that does not contain Sn in terms of its solid solution in terms of structure and characteristics. It is very different compared to Similarly, even in the case of Al—Mg—Si-based aluminum alloy plates containing Sn (the same amount), if the production conditions such as intermediate annealing are different, the solid solution amount of Sn is different, Under manufacturing conditions (ordinary method), Sn is likely to precipitate as a compound, and the amount of solid solution is remarkably reduced (decreased). For this reason, even if it contains Sn (the same amount) in the same manner, it is possible to obtain a structure having an effect of suppressing room temperature aging at a high level as in the present invention and improving BH properties and hemmability. Not necessarily.
(組織)
 本発明の6000系アルミニウム合金板の組織について、以下に説明する。
(Organization)
The structure of the 6000 series aluminum alloy plate of the present invention will be described below.
化合物の平均数密度:
 先ず、板の組織として、500倍のSEMを用いて測定した際の円相当直径が0.3~20μmの範囲の化合物の平均数密度を5000個/mm以下(0個/mmを含まず)、すなわち0個/mm超5000個/mm以下、好ましくは4500個/mm以下(0個/mmを含まず)、より好ましくは4000個/mm以下(0個/mmを含まず)とする。
Average number density of compounds:
First, the average number density of a compound having a circle equivalent diameter in the range of 0.3 to 20 μm when measured using a 500-fold SEM as the structure of the plate is 5000 pieces / mm 2 or less (including 0 pieces / mm 2) . In other words, more than 0 pieces / mm 2 and 5000 pieces / mm 2 or less, preferably 4500 pieces / mm 2 or less (excluding 0 pieces / mm 2 ), more preferably 4000 pieces / mm 2 or less (0 pieces / mm). 2 is not included).
 円相当直径が0.3μm以上の化合物の数密度を5000個/mm以下まで低減させると、成形の際の、板の組織中の破断の起点が減少して、ヘム加工性が向上する。さらに、固溶Mg量と固溶Si量が増加して、BH処理時に生成して高強度化に寄与するMg-Si系析出物の生成量が増加するため、BH性も向上する。一方、円相当直径が0.3μm以上の化合物の数密度が5000個/mmを超えると、成形の際の、板の組織中の破断の起点が増して、ヘム加工性や、絞りや張出などのプレス成形性が低下する。さらに、固溶Mg量と固溶Si量が減少して、BH処理時に生成して高強度化に寄与するMg-Si系析出物の生成量が不足して、BH性も低下する。 When the number density of the compound having an equivalent circle diameter of 0.3 μm or more is reduced to 5000 / mm 2 or less, the starting point of breakage in the structure of the plate at the time of molding is reduced, and hem workability is improved. Furthermore, since the amount of solid solution Mg and the amount of solid solution Si are increased and the amount of Mg—Si based precipitates generated during the BH treatment and contributing to the increase in strength is increased, the BH property is also improved. On the other hand, if the number density of the compound having an equivalent circle diameter of 0.3 μm or more exceeds 5000 / mm 2 , the starting point of breakage in the structure of the plate at the time of molding increases, and hemming workability, drawing and tensioning are increased. The press formability such as protrusion decreases. Furthermore, the amount of solid solution Mg and the amount of solid solution Si decrease, and the amount of Mg—Si-based precipitates that are generated during the BH treatment and contribute to increasing the strength is insufficient, and the BH property is also lowered.
 ヘム加工の際の破断の起点となりうるか否かは、化合物の大きさ(サイズ)に依存しており、円相当直径が0.3μmより大きいほど、破断の起点となりやすく、その組成には依存しない。ただし、円相当直径が、規定する上限値である20μmを超えるような粗大な化合物は、板の基本的な機械的特性や品質を著しく阻害する。このため、通常の板の製法や品質管理では、極力、このように粗大な化合物を存在させないように製造しており、SEMによる測定範囲として意味が無い。したがって、本発明で規定する化合物の円相当直径は0.3~20μmの範囲として、化合物の組成は問わない。ちなみに、本発明で規定する化合物の円相当直径とは、不定形である化合物と同じ面積を有する円の直径であり、化合物の大きさを正確に、かつ再現性良く測定あるいは規定する方法として、従来から汎用されている。 Whether or not it can be the starting point of breakage during hemming depends on the size (size) of the compound, and the larger the equivalent circle diameter is, the more likely it is to be the starting point of breakage and not depending on the composition. . However, a coarse compound having a circle-equivalent diameter exceeding 20 μm, which is the upper limit to be defined, remarkably hinders the basic mechanical properties and quality of the plate. For this reason, in the manufacturing method and quality control of a normal board, it manufactures so that such a coarse compound may not exist as much as possible, and it is meaningless as a measurement range by SEM. Therefore, the equivalent circle diameter of the compound defined in the present invention is in the range of 0.3 to 20 μm, and the composition of the compound is not limited. Incidentally, the equivalent circle diameter of the compound defined in the present invention is the diameter of a circle having the same area as the compound that is indefinite, and as a method for measuring or defining the size of the compound accurately and with good reproducibility, It has been widely used.
 円相当直径が0.3~20μmの範囲の化合物の平均数密度は、ヘム加工の際の破断の起点の減少や、Snの固溶量の確保からすると、少ないほど好ましいが、実際の製造において、板の効率的な製造方法の製造限界からして、完全に0個/mmとすることはできない。したがって、円相当直径が0.3~20μmの範囲の化合物の平均数密度の本発明規定での下限は、0個/mmを含まず、板の効率的な製造での限界からすると、その下限は100個/mm程度である。 The average number density of compounds having an equivalent circle diameter in the range of 0.3 to 20 μm is preferably as small as possible from the viewpoint of reducing the starting point of fracture during heme processing and securing the solid solution amount of Sn. From the production limit of the efficient production method of the plate, it cannot be completely 0 pieces / mm 2 . Therefore, the lower limit in the present invention of the average number density of compounds having an equivalent circle diameter in the range of 0.3 to 20 μm does not include 0 pieces / mm 2. The lower limit is about 100 pieces / mm 2 .
 なお、500倍のSEMにより板組織中に観察される化合物は、白黒の画像にて観察した際に、組織中に点在する白色の粒子として観察される、Al-Fe系、Al-Fe-Mn系、Al-Fe-Mn-Si系などや、Al-Si-Sn系などのSnを含む、多様な化合物(析出物、晶出物)である。また、Mg-Si系の化合物も、組織中に点在する黒色の粒子として、少数ではあるが散見される場合もある。このように、アルミニウム合金板の組成によって、化合物の組成が多種多様で、特定の組成に限定しにくい点も、本発明で規定する化合物の組成を問わない理由である。 The compounds observed in the plate structure by SEM of 500 times are observed as white particles scattered in the structure when observed in a black and white image. It is a variety of compounds (precipitates, crystallization products) containing Sn such as Mn, Al—Fe—Mn—Si, Al—Si—Sn, and the like. In addition, Mg—Si compounds may also be found in small numbers as black particles scattered in the structure. As described above, the composition of the compound varies widely depending on the composition of the aluminum alloy plate, and it is difficult to limit the composition to a specific composition.
Sn固溶量の目安:
 本発明では、Snの効果を発揮させるために必要な、Snの固溶量を確保することを特徴とする。このSnの固溶量確保の目安(基準)として、前記SEMにて測定された円相当直径が0.3~20μmの範囲の化合物のうち、X線分光装置により識別される、0.5質量%以上のSnを含む化合物の平均個数割合を50%未満(0%を含む)、すなわち0%以上50%未満、好ましくは40%未満(0%を含む)、より好ましくは30%未満(0%を含む)とする。なお、Snの含有量が0.5%未満である化合物は、Sn固溶量の目安としてのSnを含む化合物の測定対象とはしない。ちなみに、Snの含有量が0.5質量%未満の、ごく微量のSnを含む化合物も測定対象とすると、X線分光装置の測定誤差よりも小さいSnを含む化合物まで検出され、前記した大きさの範囲の化合物全てが測定対象となってしまう可能性がある。これでは、Snの固溶量を正確に反映しているとは言えないので、相関性や再現性の点から、化合物のSnの含有量に0.5質量%以上という下限値を設けた。
Standard of Sn solid solution amount:
The present invention is characterized by securing the solid solution amount of Sn necessary for exhibiting the effect of Sn. As a guideline (standard) for securing the solid solution amount of Sn, 0.5 mass, which is identified by an X-ray spectrometer among compounds having a circle equivalent diameter measured by the SEM in the range of 0.3 to 20 μm. % Or more of the compounds containing Sn in an amount of less than 50% (including 0%), that is, not less than 0% but less than 50%, preferably less than 40% (including 0%), more preferably less than 30% (0 % Included). In addition, a compound having a Sn content of less than 0.5% is not a measurement target of a compound containing Sn as a measure of the Sn solid solution amount. By the way, when a compound containing Sn with a very small amount of Sn having a Sn content of less than 0.5% by mass is also measured, a compound containing Sn smaller than the measurement error of the X-ray spectrometer is detected, and the size described above. There is a possibility that all the compounds in the range will be measured. In this case, it cannot be said that the solid solution amount of Sn is accurately reflected. Therefore, from the viewpoint of correlation and reproducibility, a lower limit value of 0.5% by mass or more is provided for the Sn content of the compound.
 円相当直径が0.3~20μmの範囲の、SEMにより測定された全部の化合物の個数のうち、0.5質量%以上のSnを含む化合物の個数(平均個数)の割合が50%未満とは、析出するSnが少なく、Snの固溶量が、添加したSnの前記効果を発揮できるに足る量であることを示している。一方、0.5質量%以上のSnを含む化合物の個数(平均個数)の割合が50%以上になると、析出するSnが多くなって、Snの固溶量が、添加したSnの前記効果を発揮しないような少ない量であることを示している。 The ratio of the number of compounds containing 0.5 mass% or more of Sn (average number) out of the total number of compounds measured by SEM having an equivalent circle diameter of 0.3 to 20 μm is less than 50%. Indicates that the amount of Sn that precipitates is small and the solid solution amount of Sn is sufficient to exhibit the effect of the added Sn. On the other hand, when the ratio of the number of compounds containing 0.5 mass% or more of Sn (average number) is 50% or more, the amount of precipitated Sn increases, and the solid solution amount of Sn contributes to the effect of the added Sn. The amount is so small that it does not show.
 本発明における、特定サイズの化合物中の特定量以上のSnを含む化合物の個数割合という、間接的なSn固溶量の測定は、再現性良く、簡便にSnの固溶量の評価が可能である。 In the present invention, indirect measurement of the amount of Sn solid solution, that is, the ratio of the number of compounds containing Sn in a specific amount or more in a compound of a specific size, allows easy evaluation of the solid solution amount of Sn with good reproducibility. is there.
 また、このSnを含む化合物の個数割合によるSn固溶量の評価は、間接的な測定方法でありながら、円相当直径が0.3~20μmの範囲の0.5質量%以上のSnを含む化合物が測定の対象であれば、固溶したSnの発揮する効果と良く相関する。すなわち、固溶したSnの発揮する効果は、X線分光装置によってSnを0.5質量%以上含有するか否か識別される、Snを含む化合物の個数(平均個数)の割合と、良く相関する。この点は、後述する実施例によって裏付けられる。 Further, the evaluation of the Sn solid solution amount by the number ratio of the Sn-containing compound is an indirect measurement method, but includes 0.5 mass% or more of Sn having an equivalent circle diameter in the range of 0.3 to 20 μm. If the compound is the object of measurement, it correlates well with the effect exhibited by solid solution Sn. That is, the effect exhibited by solid solution Sn correlates well with the ratio of the number of compounds containing Sn (average number), which is identified by the X-ray spectrometer whether or not Sn is contained by 0.5 mass% or more. To do. This point is supported by the examples described later.
 前記規定の通り、0.5質量%以上のSnを含む化合物の平均個数の割合を50%未満とし、Snの固溶量を確保して初めて、室温における原子空孔の捕獲による、室温でのMgやSiの拡散の抑制や、室温における強度増加(室温時効)を長期に亘って抑制の効果が発揮される。この結果、この室温時効後の板のパネルへのプレス成形時に、プレス成形性や、特にヘム加工性が向上する。また、成形されたパネルの塗装焼き付け処理などの人工時効処理時に、前記捕獲していた空孔を放出する効果も発揮され、MgやSiの拡散を促進して、BH性を高くすることができる。 As stated above, the ratio of the average number of compounds containing Sn of 0.5% by mass or more is less than 50%, and only after securing the solid solution amount of Sn, the capture of atomic vacancies at room temperature is not possible. The effect of suppressing the diffusion of Mg and Si and the increase in strength at room temperature (room temperature aging) are exhibited over a long period of time. As a result, the press formability, particularly the hem workability, is improved at the time of press forming the panel after aging at room temperature onto the panel. In addition, during the artificial aging treatment such as paint baking treatment of the molded panel, the effect of releasing the trapped holes is also exhibited, and the diffusion of Mg and Si can be promoted to increase the BH property. .
 0.5質量%以上のSnを含む化合物の個数(平均個数)の割合の下限は、理論的には、Snが全て固溶した場合で、Snを含む化合物の個数が0個で、0%の場合である。ただ、後述する板の製法の通り、常法ではSnは析出しやすく、一旦析出したSnを、再度固溶させることはなかなか難しい。したがって、製造の効率を無視すれば、Snを含む化合物の個数割合を0%とすることもできるが、効率的な(工業的な)製造限界からくる、Snを含む化合物の個数(平均個数)の割合の下限は、0.1%程度である。 The lower limit of the ratio (average number) of compounds containing 0.5 mass% or more of Sn is theoretically 0% when the number of compounds containing Sn is 0 when all Sn is dissolved. This is the case. However, as in the plate manufacturing method described later, Sn is likely to precipitate in the conventional method, and it is difficult to re-dissolve Sn once precipitated. Therefore, if the production efficiency is ignored, the number ratio of compounds containing Sn can be reduced to 0%, but the number of compounds containing Sn (average number) coming from an efficient (industrial) production limit. The lower limit of the ratio is about 0.1%.
化合物の測定:
 円相当直径が0.3~20μmの範囲の化合物の数密度の500倍のSEMによる測定は、供試板の表面から板厚方向1/4部の任意の点、10箇所について行い(試料を10個採取し)、これら各試料の各数密度を平均化して平均数密度(個/mm)とする。後述する0.5質量%以上のSnを含む化合物の個数割合の測定も、このSEMに測定に伴って行い、同様に、各試料の個数割合を平均化した平均の個数割合(%)とする。具体的には、調質処理直後の供試板の板厚方向の直角断面につき、表面から板厚方向1/4部の任意の点を通り、板表面に平行な面について、500倍のSEM(Scanning Electron Microscope)を用いて測定する。試料は、上記部位から10個サンプリングした板断面試料表面を機械研磨して、板表面から約0.25mmを機械研磨により削り落とし、更に、バフ研磨を行なって表面を調整した試料を用意する。次に、反射電子像を利用し、自動解析装置により、前記円相当直径範囲の化合物の個数を測定して、数密度を算出する。測定部位は試料研磨表面、1試料あたりの測定領域は240μm×180μmとする。
Compound measurement:
Measurement by SEM, which is 500 times the number density of the compound having an equivalent circle diameter of 0.3 to 20 μm, is performed at 10 points at an arbitrary point of 1/4 part in the plate thickness direction from the surface of the test plate (samples Ten samples are collected), and the number density of each sample is averaged to obtain an average number density (pieces / mm 2 ). The measurement of the number ratio of the compound containing 0.5 mass% or more of Sn, which will be described later, is also performed along with this SEM, and similarly, the average number ratio (%) is obtained by averaging the number ratio of each sample. . Specifically, with respect to a cross section perpendicular to the plate thickness direction of the test plate immediately after the tempering treatment, an SEM of 500 times the surface parallel to the plate surface passes through an arbitrary point from the surface in a 1/4 part of the plate thickness direction. Measure using (Scanning Electron Microscope). A sample is prepared by mechanically polishing a plate cross-section sample surface sampled 10 pieces from the above-mentioned site, cutting off about 0.25 mm from the plate surface by mechanical polishing, and further performing buffing to adjust the surface. Next, using the backscattered electron image, the number of compounds in the equivalent circle diameter range is measured by an automatic analyzer to calculate the number density. The measurement site is the sample polishing surface, and the measurement area per sample is 240 μm × 180 μm.
 また、Snを含む化合物の個数割合の測定に用いるX線分光装置は、エネルギー分散型X線分光法(Energy Dispersive X-ray Spectroscopy)による分析装置として周知であり、通常EDXと称される。このX線分光装置は、本発明で用いるSEMに通常付属して、観察される化合物の組成などの定量分析に汎用される。このX線分光装置によって、前記SEMにより測定された円相当直径が0.3~20μmの範囲の化合物の全個数のうち、Snを含むと識別された化合物の個数を測定し、前記10個の試料測定結果につき平均化して、平均個数割合として算出する。 Further, an X-ray spectrometer used for measuring the number ratio of compounds containing Sn is well known as an analyzer using energy dispersive X-ray spectroscopy (Energy Dispersive X-ray Spectroscopy), and is usually called EDX. This X-ray spectrometer is generally attached to the SEM used in the present invention and is widely used for quantitative analysis of the composition of the observed compound. Using this X-ray spectrometer, the number of compounds identified as containing Sn out of the total number of compounds having an equivalent circle diameter of 0.3 to 20 μm measured by the SEM was measured. The sample measurement results are averaged and calculated as an average number ratio.
(製造方法)
 次ぎに、本発明アルミニウム合金板の製造方法について以下に説明する。
 本発明アルミニウム合金板は、製造工程自体は常法あるいは公知の方法であり、上記6000系成分組成のアルミニウム合金鋳塊を鋳造後に均質化熱処理し、熱間圧延、冷間圧延が施されて所定の板厚とされ、更に溶体化焼入れなどの調質処理が施されて製造される。
(Production method)
Next, a method for producing the aluminum alloy plate of the present invention will be described below.
The aluminum alloy sheet of the present invention is a conventional process or a known process, and the aluminum alloy ingot having the above-mentioned 6000 series component composition is subjected to homogenization heat treatment after casting, and then subjected to hot rolling and cold rolling to obtain a predetermined process. It is manufactured by being subjected to a tempering treatment such as solution hardening and quenching.
 但し、これらの製造工程中で、Snを固溶させ、規定するSnを含む化合物の個数(平均個数)の割合とするためには、後述する通り、鋳造時の平均冷却速度制御に加えて、冷間圧延途中の中間焼鈍を規定する好ましい条件とする。このような中間焼鈍条件としなければ、Snを固溶させ、規定するSnを含む化合物の個数(平均個数)の割合とすることが難しくなる。 However, in these manufacturing processes, in order to make Sn a solid solution and to make the ratio of the number of compounds containing Sn to be defined (average number), as described later, in addition to controlling the average cooling rate during casting, It is set as the preferable conditions which prescribe | regulate the intermediate annealing in the middle of cold rolling. Unless such intermediate annealing conditions are used, it is difficult to make Sn a solid solution and to obtain the ratio of the number of compounds containing Sn (average number).
(溶解、鋳造冷却速度)
 先ず、溶解、鋳造工程では、上記6000系成分組成範囲内に溶解調整されたアルミニウム合金溶湯を、連続鋳造法、半連続鋳造法(DC鋳造法)等の通常の溶解鋳造法を適宜選択して鋳造する。ここで、本発明で規定する、円相当直径が0.3μm以上の化合物の数密度とし、Snを含む化合物の個数(平均個数)の割合とするためには、鋳造時の平均冷却速度について、液相線温度から固相線温度までを30℃/分以上と、できるだけ大きく(速く)することが好ましい。
(Dissolution, casting cooling rate)
First, in the melting and casting process, an ordinary molten casting method such as a continuous casting method and a semi-continuous casting method (DC casting method) is appropriately selected for the molten aluminum alloy adjusted to be dissolved within the above-mentioned 6000 series component composition range. Cast. Here, in order to obtain the number density of compounds having an equivalent circle diameter of 0.3 μm or more as defined in the present invention and the ratio of the number of compounds containing Sn (average number), the average cooling rate during casting is as follows: It is preferable that the liquidus temperature to the solidus temperature be as large (fast) as possible at 30 ° C./min or more.
 このような、鋳造時の高温領域での温度(冷却速度)制御を行わない場合、この高温領域での冷却速度は必然的に遅くなる。このように高温領域での平均冷却速度が遅くなった場合、この高温領域での温度範囲で粗大に生成する晶出物の量が多くなって、鋳塊の板幅方向、厚さ方向での晶出物のサイズや量のばらつきも大きくなる。この結果、本発明の規定範囲に、円相当直径が0.3μm以上の化合物の数密度や、Snを含む化合物の個数(平均個数)の割合を制御することができなくなる可能性が高くなる。 If such temperature (cooling rate) control in the high temperature region during casting is not performed, the cooling rate in this high temperature region is inevitably slow. In this way, when the average cooling rate in the high temperature region becomes slow, the amount of crystallized material generated coarsely in the temperature range in this high temperature region increases, and in the plate width direction and thickness direction of the ingot. Variations in the size and amount of crystallized material also increase. As a result, there is a high possibility that the number density of compounds having an equivalent circle diameter of 0.3 μm or more and the ratio of the number of compounds containing Sn (average number) cannot be controlled within the specified range of the present invention.
(均質化熱処理)
 次いで、前記鋳造されたアルミニウム合金鋳塊に、熱間圧延に先立って、均質化熱処理を施す。この均質化熱処理(均熱処理)は、組織の均質化、すなわち、鋳塊組織中の結晶粒内の偏析をなくすことを目的とする。この目的を達成する条件であれば、特に限定されるものではなく、通常の1回または1段の処理でも良い。
(Homogenization heat treatment)
Next, the cast aluminum alloy ingot is subjected to a homogenization heat treatment prior to hot rolling. The purpose of this homogenization heat treatment (soaking) is to homogenize the structure, that is, eliminate segregation in crystal grains in the ingot structure. The conditions are not particularly limited as long as the object is achieved, and normal one-stage or one-stage processing may be performed.
 均質化熱処理温度は、500℃以上で融点未満、均質化時間は4時間以上の範囲から適宜選択される。この均質化温度が低いと結晶粒内の偏析を十分に無くすことができず、これが破壊の起点として作用するために、伸びフランジ性や曲げ加工性が低下する。この後、直ちに熱間圧延を開始又は、適当な温度まで冷却保持した後に熱間圧延を開始しても良い。 The homogenization heat treatment temperature is appropriately selected from the range of 500 ° C. or more and less than the melting point, and the homogenization time is 4 hours or more. When this homogenization temperature is low, segregation within the crystal grains cannot be sufficiently eliminated, and this acts as a starting point of fracture, so that stretch flangeability and bending workability are deteriorated. Thereafter, the hot rolling may be started immediately, or the hot rolling may be started after cooling to an appropriate temperature.
 この均質化熱処理を行った後、300℃~500℃の間を20~100℃/hの平均冷却速度で室温まで冷却し、次いで20~100℃/hの平均加熱速度で350℃~450℃まで再加熱し、この温度域で熱間圧延を開始することもできる。 After performing this homogenization heat treatment, it is cooled to room temperature at an average cooling rate of 20 to 100 ° C./h between 300 ° C. and 500 ° C., and then 350 ° C. to 450 ° C. at an average heating rate of 20 to 100 ° C./h. It is possible to reheat up to this temperature and start hot rolling in this temperature range.
 この均質化熱処理後の平均冷却速度および、その後の再加熱速度の条件を外れると、粗大なMg-Si化合物が形成される可能性が高くなり、Snの効果発揮以前に、前提として必要な、6000系アルミニウム合金板の、強度や伸びなどの基本的な機械的性質が低下する。 When the average cooling rate after the homogenization heat treatment and the subsequent reheating rate are not satisfied, there is a high possibility that a coarse Mg—Si compound will be formed. Basic mechanical properties such as strength and elongation of the 6000 series aluminum alloy plate are lowered.
(熱間圧延)
 熱間圧延は、圧延する板厚に応じて、鋳塊 (スラブ) の粗圧延工程と、仕上げ圧延工程とから構成される。これら粗圧延工程や仕上げ圧延工程では、リバース式あるいはタンデム式などの圧延機が適宜用いられる。
(Hot rolling)
Hot rolling is composed of an ingot (slab) rough rolling process and a finish rolling process according to the thickness of the rolled sheet. In these rough rolling process and finish rolling process, a reverse or tandem rolling mill is appropriately used.
 この際、熱延(粗圧延)開始温度が固相線温度を超える条件では、バーニングが起こるため熱延自体が困難となる。また、熱延開始温度が350℃未満では熱延時の荷重が高くなりすぎ、熱延自体が困難となる。したがって、熱延開始温度は好ましくは350℃~固相線温度、更に好ましくは400℃~固相線温度の範囲とする。 At this time, under conditions where the hot rolling (rough rolling) start temperature exceeds the solidus temperature, burning occurs, making hot rolling itself difficult. On the other hand, when the hot rolling start temperature is less than 350 ° C., the load during hot rolling becomes too high, and the hot rolling itself becomes difficult. Therefore, the hot rolling start temperature is preferably 350 ° C. to the solidus temperature, more preferably 400 ° C. to the solidus temperature.
(熱延板の焼鈍)
 この熱延板の冷間圧延前の焼鈍(荒鈍)は必ずしも必要ではないが、結晶粒の微細化や集合組織の適正化によって、成形性などの特性を更に向上させる為に実施しても良い。
(Hot rolled sheet annealing)
Annealing (roughening) before cold rolling of this hot-rolled sheet is not always necessary, but it can be performed to further improve properties such as formability by refining crystal grains and optimizing the texture. good.
(冷間圧延)
 冷間圧延では、上記熱延板を圧延して、所望の最終板厚の冷延板(コイルも含む)に製作する。但し、結晶粒をより微細化させるためには、パス数に関わらず、合計の冷間圧延率は60%以上であることが望ましい。
(Cold rolling)
In cold rolling, the hot-rolled sheet is rolled to produce a cold-rolled sheet (including a coil) having a desired final thickness. However, in order to further refine the crystal grains, the total cold rolling rate is desirably 60% or more regardless of the number of passes.
(中間焼鈍)
 この冷間圧延前(熱延後)か、冷間圧延の途中(パス間)で、板を480℃以上、融点以下の高温で0.1~10秒間保持し、次いで、3℃/秒以上の平均冷却速度で室温まで強制冷却(急冷)する中間焼鈍を、繰り返して2回以上行い、それまでの熱延工程などで化合物として生成したSnを固溶させることが好ましい。常法ではSnは析出しやすく、一旦析出したSnを再度固溶させることもなかなか難しく、前記した特定のサイズの化合物の個数のうち、Snを含む化合物の平均個数の割合を50%未満とするためには、このような高温での短時間の熱処理を複数回行う必要がある。ただし、この条件範囲内であれば、複数回の熱処理条件を同じとせずとも、変えても良い。
(Intermediate annealing)
Before this cold rolling (after hot rolling) or in the middle of cold rolling (between passes), the plate is held at a high temperature of 480 ° C or higher and below the melting point for 0.1 to 10 seconds, and then 3 ° C / second or higher It is preferable to repeat the intermediate annealing forcibly cooling (rapid cooling) to room temperature at an average cooling rate of 2 times or more, so that Sn produced as a compound in the hot rolling step or the like is dissolved. In the usual method, Sn is likely to precipitate, and it is difficult to re-dissolve once precipitated Sn, and the ratio of the average number of compounds containing Sn is less than 50% of the number of compounds of the specific size described above. In order to achieve this, it is necessary to perform such short-time heat treatment at a high temperature a plurality of times. However, as long as it is within this condition range, a plurality of heat treatment conditions may not be the same, but may be changed.
 この中間焼鈍条件につき、板の温度が480℃未満では、たとえ中間焼鈍を2回以上行っても、Snの固溶量が不足する。これは、焼鈍温度や急冷条件が範囲内である中間焼鈍の回数が1回のみでも同じである。また、保持時間は、0.1秒などの瞬間的も含む短時間で良いが、10秒を超えると板の機械的性質が著しく低下する。また、焼鈍後の冷却を、3℃/秒以上の平均冷却速度とする、空冷やミスト、水冷などによる、室温までの強制冷却(急冷)としないと、すなわち平均冷却速度が3℃/秒未満では、一旦固溶したSnが再析出して化合物化してしまう。 For this intermediate annealing condition, if the temperature of the plate is less than 480 ° C., the amount of Sn solid solution is insufficient even if the intermediate annealing is performed twice or more. This is the same even if the number of intermediate annealings in which the annealing temperature and the rapid cooling conditions are within the range is only one. Further, the holding time may be a short time including momentary such as 0.1 seconds, but if it exceeds 10 seconds, the mechanical properties of the plate are remarkably deteriorated. In addition, if the cooling after annealing is not the forced cooling (rapid cooling) to room temperature by air cooling, mist, water cooling or the like with an average cooling rate of 3 ° C./second or more, that is, the average cooling rate is less than 3 ° C./second. Then, Sn once dissolved is reprecipitated and compounded.
 このような条件での焼鈍は、急冷も含めて、バッチ炉では無理で、板を巻き戻しながら炉に通板して巻き取る、連続的な熱処理炉が必要となる。このように、急冷が可能な連続焼鈍を用いる場合でも、本発明者らの知見によれば、1回だけの連続焼鈍だけでは、どうしてもSnの固溶量が不足する。このため、連続焼鈍による中間焼鈍を2回以上繰り返すものとする。但し、連続焼鈍の繰り返しは、回数が増すほど、製造工程の効率を大きく低下させるので、繰り返し回数は2回程度とすることが好ましい。 Annealing under such conditions is impossible in a batch furnace, including rapid cooling, and requires a continuous heat treatment furnace that winds the sheet through the furnace while unwinding it. Thus, even when continuous annealing capable of rapid cooling is used, according to the knowledge of the present inventors, the solid solution amount of Sn is inevitably insufficient by only one continuous annealing. For this reason, the intermediate annealing by continuous annealing shall be repeated twice or more. However, the number of repetitions of continuous annealing is preferably about 2 because the efficiency of the manufacturing process is greatly reduced as the number of repetitions increases.
(溶体化および焼入れ処理)
 冷間圧延後、溶体化焼入れ処理を行う。溶体化処理焼入れ処理については、通常の連続熱処理ラインによる加熱、冷却でよく、特に限定はされない。ただ、各元素の十分な固溶量を得ること、および板組織の結晶粒はより微細であることが望ましいことから、520℃以上、溶融温度以下の溶体化処理温度に、加熱速度5℃/秒以上で加熱して、0~10秒保持する条件で行うことが好ましい。
(Solution and quenching)
After cold rolling, a solution hardening treatment is performed. The solution treatment and quenching treatment may be heating and cooling using a normal continuous heat treatment line, and is not particularly limited. However, since it is desirable to obtain a sufficient solid solution amount of each element and that the crystal grains of the plate structure are finer, the solution treatment temperature is 520 ° C. or higher and the melting temperature or lower. It is preferable that the heating be performed for at least 2 seconds, and the conditions are maintained for 0 to 10 seconds.
 そして、溶体化温度から焼入れ停止温度までの平均冷却速度を好ましくは3℃/秒以上とする。冷却速度が小さいと、冷却中にMg-Si系化合物などが析出しやすくなり、プレス成形や曲げ加工時の割れの起点となり易く、これら成形性が低下する。この冷却速度を確保するために、焼入れ処理は、ファンなどの空冷、ミスト、スプレー、浸漬等の水冷手段や条件を各々選択して用いる。 The average cooling rate from the solution temperature to the quenching stop temperature is preferably 3 ° C./second or more. When the cooling rate is low, Mg—Si compounds and the like are likely to be precipitated during cooling, which tends to be the starting point of cracks during press molding and bending, and these formability is reduced. In order to ensure this cooling rate, the quenching treatment is performed by selecting water cooling means and conditions such as air cooling such as a fan, mist, spray, and immersion, respectively.
(再加熱処理)
 続いて、BH処理時に生成するMg-Si系化合物の核となる原子の集合体(クラスタ)を形成させるために、溶体化焼入れ処理後に、予備時効処理(再加熱処理)を行う。板の到達温度(実体温度)は80~150℃の温度範囲かつ、保持時間は3~50時間の範囲であることが望ましい。再加熱処理後の室温までの冷却は、放冷でも、生産の効率化のために前記焼入れ時の冷却手段を用いて強制急冷しても良い。
(Reheating treatment)
Subsequently, a pre-aging treatment (reheating treatment) is performed after the solution quenching treatment in order to form an aggregate (cluster) of atoms serving as nuclei of the Mg—Si-based compound generated during the BH treatment. The ultimate temperature (substance temperature) of the plate is preferably in the temperature range of 80 to 150 ° C., and the holding time is preferably in the range of 3 to 50 hours. The cooling to room temperature after the reheating treatment may be allowed to cool or may be forcibly quenched using the cooling means at the time of quenching in order to increase production efficiency.
 以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも可能であり、それらは何れも本発明の技術的範囲に含まれる。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.
 本発明の実施例を説明する。本発明で規定するSnの固溶量が異なる6000系アルミニウム合金板を、前記中間焼鈍条件によって作り分けて、前記化合物の数密度や、これに基づくSnの固溶量を調査した。そして、この板を室温に100日間保持後のBH性(塗装焼付け硬化性)や、ヘム加工性も評価した。この結果を表2に示す。 Embodiments of the present invention will be described. 6000 series aluminum alloy plates having different Sn solid solution amounts defined in the present invention were prepared according to the intermediate annealing conditions, and the number density of the compounds and the Sn solid solution amount based thereon were investigated. And BH property (coating bake hardenability) after holding this board at room temperature for 100 days and hem workability were also evaluated. The results are shown in Table 2.
 これらアルミニウム合金板の具体的な製造条件は以下の通りとした。表1に示す各組成のアルミニウム合金鋳塊を、DC鋳造法により共通して溶製した。この際、各例とも共通して、鋳造時の平均冷却速度について、液相線温度から固相線温度までを50℃/分とした。各例の6000系アルミニウム合金板の組成を示す表1中の各元素の含有量の表示において、各元素における数値をブランクとしている表示は、その含有量が検出限界以下で、これらの元素を含まない0%であることを示す。 The specific production conditions for these aluminum alloy plates were as follows. Aluminum alloy ingots having respective compositions shown in Table 1 were commonly melted by DC casting. At this time, in common with each example, the average cooling rate during casting was set to 50 ° C./min from the liquidus temperature to the solidus temperature. In the display of the content of each element in Table 1 showing the composition of the 6000 series aluminum alloy plate of each example, the display in which the numerical value in each element is blank, the content is below the detection limit and includes these elements No 0%.
 続いて、前記鋳塊を、各例とも共通して、540℃×4時間均熱処理した後、熱間粗圧延を開始した。そして、各例とも共通して、続く仕上げ圧延にて、厚さ2.5mmまで熱延し、熱間圧延板とした。熱間圧延後のアルミニウム合金板を、各例とも共通して、500℃×1分の荒焼鈍を施した後、冷間圧延のパス途中(パス間)に、表2に示すように、連続焼鈍炉による中間焼鈍を、その回数や温度、平均冷却速度などを変えた、種々の条件で行って、最終的に厚さ1.0mmの冷延板(製品板)とした。 Subsequently, the ingot was subjected to soaking treatment at 540 ° C. for 4 hours in common with each example, and then hot rough rolling was started. And in each example, it was hot rolled to a thickness of 2.5 mm in the subsequent finish rolling to obtain a hot rolled sheet. As shown in Table 2, the aluminum alloy plate after hot rolling was subjected to rough annealing at 500 ° C. for 1 minute in common with each example, and then during the cold rolling pass (between passes) as shown in Table 2. Intermediate annealing with an annealing furnace was performed under various conditions with different numbers, temperatures, average cooling rates, and the like, and finally a cold-rolled sheet (product sheet) having a thickness of 1.0 mm was obtained.
 更に、これらの各冷延板を、各例とも共通して、560℃の硝石炉にて溶体化処理を行い、目標温度に到達後10秒保持し、水冷にて焼入れ処理した。この焼入れ後直ちに、100℃で5時間保持する予備時効処理を行った(保持後は冷却速度0.6℃/時間で徐冷)。 Furthermore, these cold-rolled sheets were subjected to a solution treatment in a 560 ° C. glass stone furnace in common with each example, held for 10 seconds after reaching the target temperature, and quenched by water cooling. Immediately after this quenching, a preliminary aging treatment was carried out by holding at 100 ° C. for 5 hours (after holding, slow cooling at a cooling rate of 0.6 ° C./hour).
 これらの調質処理直後の各板から供試板(ブランク)を切り出し、各供試板の組織(化合物の数密度、Snを含む化合物の個数割合)を測定した。また、前記調質処理後に100日間室温で放置した後の各板から供試板(ブランク)を切り出し、各供試板の強度(AS耐力)とBH性とを調査した。これらの結果を表2に示す。 A test plate (blank) was cut out from each plate immediately after the tempering treatment, and the structure (number density of compounds, number ratio of compounds containing Sn) of each test plate was measured. Moreover, the test plate (blank) was cut out from each plate after being left at room temperature for 100 days after the tempering treatment, and the strength (AS proof stress) and BH property of each test plate were examined. These results are shown in Table 2.
(供試板の組織)
 調質処理直後の各供試板の組織として、前記した測定方法により、500倍のSEMにて、円相当直径が0.3~20μmの範囲の化合物の平均数密度(個/mm)を測定し、この測定された化合物のうち、X線分光装置により識別される、0.5%以上のSnを含む化合物の平均個数割合(%)を調査した。
(Test plate structure)
As the structure of each test plate immediately after the tempering treatment, the average number density (pieces / mm 2 ) of the compound having a circle equivalent diameter in the range of 0.3 to 20 μm was measured with the SEM of 500 times by the measurement method described above. The average number ratio (%) of compounds containing 0.5% or more of Sn identified by the X-ray spectroscopic apparatus among the measured compounds was investigated.
(引張試験)
 前記引張試験は、前記調質処理後に100日間室温で放置した後の各供試板から、各々JISZ2201の5号試験片(25mm×50mmGL×板厚)を採取し、室温にて引張り試験を行った。このときの試験片の引張り方向を圧延方向の直角方向とした。引張り速度は、0.2%耐力までは5mm/分、耐力以降は20mm/分とした。機械的特性測定のN数は5とし、各々平均値で算出した。なお、前記BH後の耐力測定用の試験片には、この試験片に、板のプレス成形を模擬した2%の予歪をこの引張試験機により与えた後に、前記BH処理を行った。
(Tensile test)
In the tensile test, JISZ2201 No. 5 test pieces (25 mm × 50 mmGL × plate thickness) were sampled from each test plate after being left at room temperature for 100 days after the tempering treatment, and a tensile test was performed at room temperature. It was. The tensile direction of the test piece at this time was the direction perpendicular to the rolling direction. The tensile speed was 5 mm / min up to 0.2% proof stress and 20 mm / min after proof stress. The N number for the measurement of mechanical properties was 5, and each was calculated as an average value. The test piece for measuring the yield strength after the BH was subjected to the BH treatment after giving a pre-strain of 2% simulating press forming of the plate to the test piece by the tensile tester.
(BH性)
 各供試板を各々共通して、前記100日間の室温時効させた後に、185℃×20分の人工時効硬化処理した後(BH後)の、供試板の0.2%耐力(BH後耐力)を前記引張試験により求めた。そして、これら0.2%耐力同士の差(耐力の増加量)から各供試板のBH性を評価し、0.2%耐力の増加量が100MPa以上ある場合を合格とした。
(BH property)
Each test plate was commonly aged at room temperature for 100 days and then subjected to an artificial age-hardening treatment at 185 ° C. for 20 minutes (after BH). Yield strength) was determined by the tensile test. And the BH property of each test plate was evaluated from the difference between these 0.2% proof stresses (increased proof stress), and the case where the increased amount of 0.2% proof stress was 100 MPa or more was regarded as acceptable.
(ヘム加工性)
 ヘム加工性は、前記100日間室温放置後の各供試板について行った。試験は、30mm幅の短冊状試験片を用い、ダウンフランジによる内曲げR1.0mmの90°曲げ加工後、1.0mm厚のインナを挟み、折り曲げ部を更に内側に、順に約130度に折り曲げるプリヘム加工、180度折り曲げて端部をインナに密着させるフラットヘム加工を行った。
(Heme workability)
Hem workability was measured for each test plate after standing at room temperature for 100 days. In the test, a strip-shaped test piece with a width of 30 mm was used, and after bending 90 ° with an internal bend R of 1.0 mm by a down flange, a 1.0 mm thick inner was sandwiched, and the bent portion was further bent inwardly to about 130 degrees. Pre-hem processing was performed, and flat hem processing was performed in which the end was closely attached to the inner by bending 180 degrees.
 このフラットヘムの曲げ部(縁曲部)の、肌荒れ、微小な割れ、大きな割れの発生などの表面状態を目視観察し、以下の基準にて目視評価し、基準0~2までを合格とした。
0;割れ、肌荒れ無し、1;軽度の肌荒れ、2;深い肌荒れ、3;微小表面割れ、4;線状に連続した表面割れ、5;破断
The flat hem bend (edge bend) is visually observed for surface conditions such as rough skin, minute cracks, and large cracks, and visually evaluated according to the following criteria. .
0: No cracking, rough skin, 1: Mild rough skin, 2; Deep rough skin, 3: Small surface crack, 4; Continuous surface crack, 5: Break
 表2の番号1~4、12~23に示す各発明例は、本発明成分組成範囲内(表1の合金番号1~13)で、かつ、中間焼鈍を含めて前記した好ましい条件範囲内で製造している。このため、これら各発明例は、表2に示す通り、本発明で規定する化合物の平均数密度と、0.5質量%以上のSnを含む化合物の平均個数割合を満たし、含有するSnの析出が抑制されており、Snの固溶量が高い。 Each of the inventive examples shown in the numbers 1 to 4 and 12 to 23 in Table 2 is within the composition range of the present invention (alloy numbers 1 to 13 in Table 1) and within the above-mentioned preferable condition range including the intermediate annealing. Manufacture. For this reason, as shown in Table 2, each of these inventive examples satisfies the average number density of the compound defined in the present invention and the average number ratio of the compound containing 0.5 mass% or more of Sn, and precipitates Sn contained. Is suppressed, and the solid solution amount of Sn is high.
 この結果、前記各発明例は、表2に示す通り、前記調質処理後100日の長期の室温時効後であっても、As耐力が90~110MPaのレベルであっても、BH(ベークハード)後の耐力が190MPaのレベルで、耐力差が100MPa以上と、BH性に優れている。また、前記調質処理後の長期の室温時効後であってもAs耐力が比較的低いために、自動車パネルなどへのプレス成形性に優れ、ヘム加工性にも優れている。 As a result, as shown in Table 2, each of the above-mentioned invention examples has a BH (baked hard) even after the long-term room temperature aging for 100 days after the tempering treatment, or even when the As proof strength is 90 to 110 MPa. ) The yield strength is 190 MPa and the difference in yield strength is 100 MPa or more. Further, even after long-term aging after the tempering treatment, the As yield strength is relatively low, so that it is excellent in press formability to automobile panels and the like, and is excellent in hem workability.
 また、表2から分かる通り、同じ表1の合金番号1を用いても、中間焼鈍条件の違いによって、化合物の平均数密度やSnの固溶状態(Snを含む化合物の平均個数割合)が大きく異なり、特性が大きく異なっている。すなわち、発明例1~4の中でも、中間焼鈍温度が比較的低く、平均冷却速度も比較的小さい発明例1、2に比して、中間焼鈍温度が比較的高く、平均冷却速度も比較的大きい発明例3、4は、化合物の平均数密度が少ない一方で、Snを含む化合物の平均個数割合が低く、含有するSnの析出が抑制されており、Snの固溶量が高い。この結果、発明例1、2に比して、発明例3、4は、前記調質処理後100日の長期の室温時効後であっても、BH後の耐力差がより高く、BH性がより優れている。 Further, as can be seen from Table 2, even when alloy number 1 in Table 1 is used, the average number density of compounds and the solid solution state of Sn (average number ratio of compounds containing Sn) are large due to the difference in intermediate annealing conditions. The characteristics are very different. That is, among Invention Examples 1 to 4, the intermediate annealing temperature is relatively low and the average cooling rate is relatively small, compared to Invention Examples 1 and 2, the intermediate annealing temperature is relatively high and the average cooling rate is also relatively large. In Invention Examples 3 and 4, while the average number density of the compounds is small, the average number ratio of the compounds containing Sn is low, the precipitation of the contained Sn is suppressed, and the solid solution amount of Sn is high. As a result, compared to Invention Examples 1 and 2, Invention Examples 3 and 4 have a higher yield strength difference after BH and a higher BH property even after 100 days after room temperature aging. Better.
 これに対して、これら発明例と同じ表1の合金番号1を用いている、表2の比較例5~11は、中間焼鈍条件が好ましい範囲から外れる例である。このため、これら比較例は、本発明で規定する化合物が多すぎ、その平均数密度が上限を超えて外れる。また、たとえ化合物の平均数密度が本発明の規定範囲内であっても、0.5質量%以上のSnを含む化合物の平均個数割合が50%を超えて高く、含有するSnの析出が抑制できておらず、Snの固溶量が低い。このため、同じ合金組成である前記発明例に比して、自動車パネルなどへのプレス成形性やヘム加工性に劣り、耐力差が100MPa未満と、BH性も劣っている。 On the other hand, Comparative Examples 5 to 11 in Table 2 using the same alloy number 1 in Table 1 as those of the invention examples are examples in which the intermediate annealing conditions deviate from the preferred range. For this reason, these comparative examples have too many compounds prescribed | regulated by this invention, and the average number density remove | deviates beyond an upper limit. Moreover, even if the average number density of the compound is within the specified range of the present invention, the average number ratio of the compound containing 0.5 mass% or more of Sn is higher than 50%, and precipitation of contained Sn is suppressed. It is not made, and the solid solution amount of Sn is low. For this reason, compared with the said invention example which is the same alloy composition, it is inferior to the press moldability and hem workability to a motor vehicle panel etc., and a yield strength difference is less than 100 Mpa, and BH property is also inferior.
 比較例5は中間焼鈍していない。
 比較例6は、温度、保持時間、平均冷却速度の条件は満たすが、1回のみの中間焼鈍である。
 比較例7は、2回目の中間焼鈍は、温度、保持時間、平均冷却速度の条件を満たしているが、1回目の中間焼鈍の温度が480℃未満で低すぎる。
 比較例8は、1回目の中間焼鈍は、温度、保持時間、平均冷却速度の条件を満たしているが、2回目の中間焼鈍の温度が480℃未満で低すぎる。
 比較例9は、1回目、2回目の中間焼鈍の温度が、2回とも480℃未満で低すぎる。
 比較例10、11は、1回目、2回目の中間焼鈍の温度、保持時間は条件を満たしているが、1回目か2回目かの平均冷却速度が遅すぎる。
Comparative Example 5 is not subjected to intermediate annealing.
Although the comparative example 6 satisfy | fills the conditions of temperature, holding time, and average cooling rate, it is an intermediate annealing only once.
In Comparative Example 7, the second intermediate annealing satisfies the conditions of temperature, holding time, and average cooling rate, but the temperature of the first intermediate annealing is too low at 480 ° C.
In Comparative Example 8, the first intermediate annealing satisfies the conditions of temperature, holding time, and average cooling rate, but the temperature of the second intermediate annealing is too low at 480 ° C.
In Comparative Example 9, the temperatures of the first and second intermediate annealings are both less than 480 ° C. and too low.
In Comparative Examples 10 and 11, the temperature and holding time of the first and second intermediate annealing satisfy the conditions, but the average cooling rate of the first or second time is too slow.
 また、表2の比較例24~29は、中間焼鈍条件を含めて好ましい範囲で製造しているものの、表1の合金番号14~19を用いており、必須元素のMg、Si、Snの含有量が各々本発明範囲を外れている。このため、これら比較例24~29は、表2に示す通り、各発明例に比して、特に100日間室温保持後のAs耐力が比較的高すぎて自動車パネルなどへのプレス成形性やヘム加工性に劣るか、BH性が劣っている。また、比較例27は、Snが多すぎ、熱延時に割れが発生して熱延板自体が製造できなかった。 Further, although Comparative Examples 24 to 29 in Table 2 are manufactured within a preferable range including intermediate annealing conditions, Alloy Nos. 14 to 19 in Table 1 are used, and inclusion of essential elements Mg, Si, and Sn Each amount is outside the scope of the present invention. For this reason, as shown in Table 2, these Comparative Examples 24 to 29 have a relatively high As yield strength after holding at room temperature for 100 days, as compared with each invention example. It is inferior in workability or BH property. In Comparative Example 27, Sn was too much, and cracking occurred during hot rolling, so that the hot rolled sheet itself could not be manufactured.
 比較例24は表1の合金14であり、Siが少なすぎる。
 比較例25は表1の合金15であり、Siが多すぎる。
 比較例26は表1の合金16であり、Snが少なすぎる
 比較例27は表1の合金17であり、Snが多すぎる。
 比較例28は表1の合金18であり、Mgが少なすぎる。
 比較例29は表1の合金19であり、Mgが多すぎる。
The comparative example 24 is the alloy 14 of Table 1, and there is too little Si.
The comparative example 25 is the alloy 15 of Table 1, and there is too much Si.
The comparative example 26 is the alloy 16 of Table 1, and there is too little Sn The comparative example 27 is the alloy 17 of Table 1, and there is too much Sn.
The comparative example 28 is the alloy 18 of Table 1, and there is too little Mg.
The comparative example 29 is the alloy 19 of Table 1, and there is too much Mg.
 以上の実施例の結果から、Snを含む6000系アルミニウム合金板の長期室温時効後のヘム加工性やBH性向上に対して、本発明で規定する組成や化合物組織とすることや、中間焼鈍条件などの好ましい製造条件の、臨界的な意義乃至効果が裏付けられる。 From the results of the above examples, the composition and compound structure defined in the present invention and intermediate annealing conditions for the improvement of heme workability and BH property after long-term aging of a 6000 series aluminum alloy plate containing Sn The critical significance or effect of preferable manufacturing conditions such as the above is supported.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
 なお、本出願は、2014年8月27日付けで出願された日本特許出願(特願2014-173278)に基づいており、その全体が引用により援用される。
Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on August 27, 2014 (Japanese Patent Application No. 2014-173278), which is incorporated by reference in its entirety.
 本発明によれば、長期室温時効後のBH性や成形性を兼備する6000系アルミニウム合金板を提供できる。この結果、自動車、船舶あるいは車両などの輸送機、家電製品、建築、構造物の部材や部品用として、また、特に、自動車などの輸送機の部材に6000系アルミニウム合金板の適用を拡大できる。 According to the present invention, it is possible to provide a 6000 series aluminum alloy plate having both BH properties and formability after long-term room temperature aging. As a result, the application of the 6000 series aluminum alloy plate can be expanded as a member for a transport device such as an automobile, a ship or a vehicle, a home appliance, a building or a structure, and particularly as a member for a transport device such as an automobile.

Claims (2)

  1.  質量%で、Mg:0.2~2.0%、Si:0.3~2.0%およびSn:0.005~0.3%を各々含み、残部がAlおよび不可避的不純物からなるAl-Mg-Si系アルミニウム合金板であって、前記アルミニウム合金板の組織として、500倍のSEMを用いて測定した際の円相当直径が0.3~20μmの範囲の化合物の平均数密度が0個/mm超5000個/mm以下であり、前記SEMにて測定された化合物のうち、X線分光装置により識別される、0.5質量%以上のSnを含む化合物の平均個数割合が0%以上50%未満であることを特徴とする成形用アルミニウム合金板。 In mass%, Mg: 0.2 to 2.0%, Si: 0.3 to 2.0% and Sn: 0.005 to 0.3%, respectively, with the balance being Al and inevitable impurities Al -Mg-Si based aluminum alloy plate, wherein the average number density of the compound having an equivalent circle diameter in the range of 0.3 to 20 μm when measured using an SEM of 500 times is 0 as the structure of the aluminum alloy plate pieces / mm 2 ultra-5000 / mm 2 or less, of the compound measured by the SEM, is identified by the X-ray spectrometer, the average number ratio of the compound containing 0.5% by mass or more of Sn An aluminum alloy sheet for forming, characterized by being from 0% to less than 50%.
  2.  更に、質量%で、Mn:0%超1.0%以下、Cu:0%超1.0%以下、Fe:0%超1.0%以下、Cr:0%超0.3%以下、Zr:0%超0.3%以下、V:0%超0.3%以下、Ti:0%超0.05%以下、Zn:0%超1.0%以下およびAg:0%超0.2%以下からなる群から選択される1種または2種以上を含む請求項1に記載の成形用アルミニウム合金板。 Further, by mass%, Mn: more than 0% and 1.0% or less, Cu: more than 0% and 1.0% or less, Fe: more than 0% and 1.0% or less, Cr: more than 0% and 0.3% or less, Zr: more than 0% and 0.3% or less, V: more than 0% and 0.3% or less, Ti: more than 0% and 0.05% or less, Zn: more than 0% and 1.0% or less, and Ag: more than 0% and 0% The aluminum alloy sheet for forming according to claim 1, comprising one or more selected from the group consisting of 2% or less.
PCT/JP2015/074297 2014-08-27 2015-08-27 Aluminum alloy sheet for forming WO2016031937A1 (en)

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