TWI564400B - Aluminum alloy foil and its manufacturing method, forming packaging material, secondary battery, pharmaceutical packaging container - Google Patents

Description

Aluminum alloy foil, manufacturing method thereof, formed packaging material, secondary battery, pharmaceutical packaging container

The present invention relates to an aluminum alloy foil having high formability, a method for producing the same, a molded package material, a secondary battery, and a pharmaceutical packaging container.

PTP (packaged by pressure), which is known as a molded package material for packaging pharmaceuticals, is often packaged by a combination container and a cover material. The container is required to be deep drawn (deeply twisted) In the conventional strip-shaped package, the container is formed of a plastic film such as a resin film of polypropylene or the like. In particular, a tablet or the like which requires a water vapor barrier property during storage is often used as a composite in which an aluminum foil having a high barrier property and a resin film are bonded to one side or both sides. In recent years, pharmaceuticals have various shapes and sizes, and the package in which they are packaged has also been matched with these forms, and it is now required to be formed deeper.

On the other hand, as an exterior material of the molded package material of the secondary battery, in order to impart water vapor barrier properties, a material having a structure in which a composite of a resin film is bonded to both surfaces of the aluminum alloy foil is used. In recent years, with electronic devices such as mobile communication devices, notebook personal computers, earphones, and cameras A secondary battery such as a small-sized, light-weight, thin-film lithium-ion secondary battery has been paid more and more attention as a driving source thereof, and a secondary battery is required to have a charging capacity or a high output for a long period of time. For this reason, the structure of the element composed of the electrode of the battery and the separator becomes complicated/multilayered, and it is increasingly required to be formed under severe conditions such as deeper recess forming.

In particular, in the exterior material of the sheet-like thin lithium ion secondary battery, the corner cylinder deep drawing of the shoulder portion and the corner portion of the four corners of the forming concave portion is made smaller and the forming height is deeper. As a result, the filling amount of the electrode material that can be accommodated in the molding recess increases, and the battery capacity can be further increased. At present, higher formability is required for the exterior material of the lithium ion secondary battery, and higher formability is also required for the aluminum alloy foil constituting the exterior material.

In general, as shown in FIG. 2, in the package 1 for molding, the heat seal layer 9 is laminated on one surface of the exterior material main body 8, and the synthetic resin film 10 is laminated on the other surface. As shown in FIG. 1 , in order to accommodate a laminate of the positive electrode current collector 2 and the like, the package 1 is formed such that a central portion thereof becomes a concave portion and a peripheral portion serves as a flat portion. Therefore, the exterior material main body 8, the heat seal layer 9, and the synthetic resin film 10 are required to have a material having good moldability.

Conventionally, as the exterior material main body 8, a metal foil which is difficult to permeate such as moisture or air and which has excellent moldability, particularly an aluminum alloy foil, is preferably used so as not to adversely affect the quality of the contents. As the aluminum alloy foil, a composition specified in JIS1100, 3003, 8079, or 8021 is mainly used.

For example, as the exterior material main body 8, a thickness of 20 to 60 μm is proposed, with respect to rolling. The aluminum foil whose elongation in the direction of 0 degree, 45 degree, and 90 degree is all 11% or more (patent document 1). Further, similarly, as the exterior material main body 8, an aluminum alloy foil having an excellent corrosion resistance of 0.8 to 2.0% of Fe, 0.02 to 0.05% of Cu, and 0.03 to 0.1% of Si is proposed. (Patent Document 2).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-163077

[Patent Document 2] Japanese Patent No. 4799903

However, in the prior art described in the above documents, it is difficult to sufficiently satisfy the characteristics of the high molding height required for the exterior materials such as PTP and lithium ion secondary batteries.

First, in the aluminum alloy foil of Patent Document 1, when a sharp corner forming such as a deep recess is formed, deep cracking of the corner cylinder may occur, and cracks and pinholes may be formed around the shoulder of the forming recess. That is, there is no problem in the molding process of the relatively shallow concave portion of the aluminum alloy foil. However, in order to increase the capacity of the content, the aluminum alloy foil is used to form a deep recess in the central portion of the package, and the outer body of the exterior material is In particular, the boundary portion between the concave portion and the flat portion is likely to be broken or the like, and is a disadvantage that the moisture, the air, and the like are easily transmitted, and the package is adversely affected by the quality of the contents. In particular, when it is used as a secondary battery exterior material, if moisture or air is transmitted, it is caused by electricity inside the battery. The environment in which the dehydrogenation reaction produces hydrofluoric acid and the inside of the battery is easily corroded.

Furthermore, in the aluminum alloy foil of the patent document 1, in order to improve moldability, the elongation value in the 0 degree, 45 degree, and 90 degree direction with respect to the rolling direction is 11 % or more, but with respect to each rolling direction mentioned above. The tensile strength and the value of the 0.2% proof stress are large, and since the resistance of the material flowing in from the flange portion is increased at the time of deep drawing of the corner cylinder, the forming height cannot be increased.

Secondly, in the aluminum alloy foil of Patent Document 2, the number of alloy components and intermetallic compounds is controlled in order to improve corrosion resistance and strength, but it is not sufficient to control the physical properties of these to improve formability.

The present invention has been conceived in view of the above circumstances, and an object thereof is to provide an aluminum alloy foil having a good moldability which solves the above problems, a method for producing the same, a molded package material, a secondary battery, and a pharmaceutical packaging container.

The present inventors have studied the aluminum alloy foil used as a forming packaging material, and as a result, found that the aluminum alloy foil, the molded package material, the secondary battery, and the pharmaceutical packaging container obtained by limiting the components within an appropriate range are particularly excellent. And found that in the process of the above aluminum alloy foil, by controlling the homogenization treatment temperature of the ingot and the intermediate annealing temperature, and further from the hot rolling to the cold rolling rate before the intermediate annealing and from the intermediate annealing to the final foil thickness The above-described excellent aluminum alloy foil is obtained stably and reliably at the rolling ratio, thereby achieving the present invention.

That is, according to the present invention, there is provided an aluminum alloy foil comprising Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, and the balance being composed of Al and unavoidable impurities, In the aluminum alloy foil, the Cube orientation density of the surface of the aluminum alloy foil is 5 or more and the R orientation density is 50 or less, and the average crystal grain size of the aluminum alloy foil is 7 to 20 μm.

According to the aluminum alloy foil, since the composition of the aluminum alloy foil and the crystal orientation of the surface, the Cube orientation density, the R orientation density, and the average crystal grain size satisfy specific conditions, an aluminum alloy foil having good moldability can be obtained.

In particular, it is preferable that the aluminum alloy foil has a tensile strength TS and a 0.2% proof stress YS in the direction of 0, 45, and 90 degrees with respect to the rolling direction in the aluminum alloy foil, and a direction of 45 degrees. The value of TS × (TS / YS) on the upper side is 200 N / mm ² or more, and the absolute value of the difference between TS × (TS / YS) in the 0 degree direction and the 45 degree direction is 30 N / mm ² or less, 45 degrees direction and 90 degrees. The absolute value of the difference between the TS × (TS / YS) in the degree direction is 30 N / mm ² or less.

According to such a rule, the aluminum alloy foil of the present invention can improve the ultimate deformability of the aluminum alloy foil, and can suppress the occurrence of minute breakage or the like in the initial stage of deep drawing of the corner cylinder. Therefore, the forming height can be improved. Further, since the resistance of the material flowing in from the flange portion at the time of deep drawing of the corner cylinder is reduced, the forming height can be improved.

Further, according to the present invention, it is preferable to provide a molded package material comprising the above-described aluminum alloy foil. According to the molded package material, the aluminum alloy foil having the above-described excellent moldability is used, so that the molding height can be improved, and a deeper recess can be formed as a molded package material such as an exterior material for a secondary battery. As a result, the amount that can be accommodated in the forming recess is increased, so that the capacity can be further increased.

Further, according to the present invention, it is preferable to provide a secondary battery using the above-described molded package material. According to the secondary battery, since the molded package material having the deeper formed concave portion described above is used, the filling amount of the battery material such as the electrode material that can be accommodated in the molded concave portion of the secondary battery exterior material is increased. Further improvement in battery capacity and the like can contribute to the improvement in performance of the secondary battery.

Further, according to the present invention, it is preferable to provide a pharmaceutical packaging container using the above-described molded package material. According to the pharmaceutical packaging container, since the molded package material having the above-described deep molded concave portion is used, it can be accommodated in the molded concave portion of the pharmaceutical packaging container, so that the medicine storage capacity and shape screening can be further improved. degree.

Further, according to the present invention, there is provided a method for producing an aluminum alloy foil as described above, which comprises: Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, and the remainder from Al and An aluminum alloy ingot having an unavoidable impurity composition is homogenized and maintained at 500 ° C to 620 ° C for 1 hour or more; after the homogenization is maintained, a step of hot rolling and cold rolling is performed; in the middle of the cold rolling, a step of performing intermediate annealing maintained at 300 ° C or higher and 450 ° C or lower; a step of performing cold rolling after the hot rolling to the intermediate rolling before the intermediate rolling is 85% or less; and from the intermediate annealing to the last The cold rolling ratio of the foil thickness is 80% or more and 93% or less, and the step of performing cold rolling; and the step of performing final annealing after the cold rolling to obtain the aluminum alloy foil.

According to the method for producing an aluminum alloy foil, since the aluminum alloy ingot of a specific composition is treated in a specific step, all of the following (1) to (3) can be satisfied, and the aluminum alloy foil having high formability can be reliably obtained. .

(1) The average crystal grain size of the aluminum alloy foil; (2) the crystal orientation density of the surface of the aluminum alloy foil; and (3) the intensity balance in the direction of 0, 45, and 90 degrees with respect to the rolling direction.

In the aluminum alloy foil of the present invention, since the average crystal grain size and the predetermined azimuth density of the aluminum alloy are optimally controlled, it is possible to provide a molding which is suitable for high moldability such as a lithium ion secondary battery or a pharmaceutical packaging container. Aluminum alloy foil for the package material.

1‧‧‧External materials (formed packaging materials)

2‧‧‧ positive current collector

3‧‧‧ positive

4‧‧‧Isolation material (spacer)

5‧‧‧negative

6‧‧‧Negative current collector

7‧‧‧End of the exterior material

8‧‧‧External material body (aluminum alloy foil)

9‧‧‧Heat seal

10‧‧‧Synthetic resin film

1 is a schematic cross-sectional view showing an example of an internal structure of a sheet-like thin lithium ion secondary battery.

2 is a schematic cross-sectional view showing a general example of an exterior material of a secondary battery.

(1) Composition of aluminum alloy foil

In the present embodiment, the content of Fe contained in the aluminum alloy foil is 0.8 to 2.0 mass%. When the content of Fe is less than 0.8 mass%, the tensile strength TS and the 0.2% proof stress YS are lowered together, so that the value of TS × (TS/YS) in the 45-degree direction with respect to the rolling direction becomes small, and the aluminum alloy foil The formability is degraded. In addition, if the content of Fe exceeds 2.0 mass%, it is easy to form a huge amount at the time of casting. The intermetallic compound easily becomes the starting point of cracking in the deep drawing test of the corner cylinder, and thus the formability is lowered. The content of the Fe is preferably 1.1 mass% or more and 1.6 mass% or less from the viewpoint of strength. The content of the Fe is, for example, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mass%, and may be any two values of the numerical values exemplified herein. Between the limits.

In the present embodiment, the content of Si contained in the aluminum alloy foil is 0.05 to 0.2 mass%. When the content of Si is less than 0.05 mass%, the tensile strength TS and the 0.2% proof stress YS are decreased. Therefore, the value of TS × (TS/YS) in the 45-degree direction with respect to the rolling direction is small, and the formability is lowered. Furthermore, it is not economical to use a high purity base metal (Al). On the other hand, when the content of Si exceeds 0.2 mass%, the crystal size in the aluminum alloy foil becomes large, and the number of crystals decreases. As a result, since the average crystal grain size after the final annealing is increased, uneven molding is likely to occur at the time of formation, and the moldability of the aluminum alloy foil is lowered. The content of Si is particularly preferably 0.06 mass% or more and 0.1 mass% or less from the viewpoint of strength and average crystal grain size. The content of the Si is, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20 mass%, which may be exemplified herein. The value is in the range between any 2 values.

In the present embodiment, the content of Cu contained in the aluminum alloy foil is 0.0025 to 0.2 mass%. The strength of the aluminum alloy foil is increased by adding Cu. When the content of Cu is less than 0.0025 mass%, the tensile strength TS and the 0.2% proof stress YS are respectively decreased, and the value of TS × (TS/YS) in the 45-degree direction with respect to the rolling direction becomes small, so that the aluminum alloy foil The formability is degraded. Further, when the content of Cu exceeds 0.2 mass%, the Cube azimuth density on the surface of the aluminum alloy foil is lowered, so that the formability of the aluminum alloy foil is lowered. The content of Cu is particularly preferable from the viewpoint of strength and crystal orientation of the surface of the aluminum alloy foil. 0.005 mass% or more and 0.05 mass% or less. The content of the Cu is, for example, 0.0025, 0.0100, 0.0150, 0.0200, 0.0250, 0.0300, 0.0350, 0.0400, 0.050, 0.0600, 0.0700, 0.0800, 0.0900, 0.1000, 0.1100, 0.1200, 0.1300, 0.1400, 0.1500, 0.1600, 0.1700. , 0.1800, 0.1900, 0.2000 mass%, may also be in the range between any two values of the numerical values exemplified herein.

In the present embodiment, the unavoidable impurities contained in the aluminum alloy foil are each 0.05 mass% or less, and the total amount is 0.15 mass% or less. In particular, if the unavoidable impurities of Ti, Mn, Mg, Zn, and the like are each 0.05 mass%, and the total amount exceeds 0.15 mass%, the hardening of the press is large, and cracks in rolling are likely to occur.

(2) Physical properties of aluminum alloy foil

In the present embodiment, the average crystal grain size after the final annealing in the aluminum alloy foil is 7 μm or more and 20 μm or less. It is preferably 10 μm or more and 18 μm or less. The average crystal grain size is, for example, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 μm, and may be any two of the numerical values exemplified herein. Within the scope.

Further, the average crystal grain size in the aluminum alloy foil can be measured by a conventional method, for example, by a cutting method. The cutting method is a method in which a plurality of crystal grains are present in a certain line segment, and the line segment is divided by the number of the number.

The average crystal grain size of the aluminum alloy foil after the final annealing is greatly affected by the amount of the element to be added and various conditions at the time of production. In particular, it is largely affected by the amount of Fe and Si added, after annealing from the middle to The effect of the cold rolling rate until the final foil thickness and the final annealing conditions. In order to obtain the average crystal grain size described above, it is necessary to appropriately adjust the amount of these added elements and the production conditions. In the case of less than 7 μm, since the average crystal grain size of the aluminum alloy foil is too small, the increase amount of the 0.2% proof stress YS is larger than the tensile strength TS, and therefore TS × (TS/YS) in the direction of 45 degrees with respect to the rolling direction The value is reduced, and the formability of the aluminum alloy foil is lowered. On the other hand, when the average crystal grain size of the aluminum alloy foil exceeds 20 μm, the number of crystal grains occupied by the cross-sectional direction of the plate thickness is small, so that localization of deformation is likely to occur, and the formability of the aluminum alloy foil is lowered.

In the present embodiment, after the final annealing of the aluminum alloy foil, the Cube azimuth density on the surface of the foil is 5 or more, and the R orientation density is 50 or less. More preferably, after the final annealing, the foil orientation density of the foil surface is 7 or more, and the R orientation density is 30 or less.

In addition, the values of Cube azimuth density and R azimuth density all indicate a multiple of the random crystal orientation density.

The Cube orientation is represented by {001}<100>, and the R orientation is represented by {123}<634>. When the crystal orientation density of the surface of the aluminum alloy foil was measured, the incomplete pole maps of {100}, {110}, and {111} were measured, and the three-dimensional crystal orientation analysis (ODF) was investigated based on these. Further, in the analysis of these, the data obtained by measuring the sample having a random crystal orientation made of aluminum powder is used as a normalized file used for analyzing the {100}, {110}, and {111} pole patterns. Thereby, various azimuth densities are obtained by multiplying the samples having random orientations. Further, in the present invention, the crystal orientation density is all based on three-dimensional crystal orientation analysis (ODF).

When the Cube azimuth density on the surface of the aluminum alloy foil is less than 5 and the R-azimuth density exceeds 50, minute breakage or the like is likely to be formed in the shoulder portion at the initial stage of deep drawing of the corner cylinder, and thus the formability of the aluminum alloy foil is lowered. As the Cube azimuth density, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 27, 28, 29, 30 or more may also be in the range of any two of the numerical values exemplified herein. Further, as the R orientation density, for example, 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or less may be This exemplified value is in the range between any two values.

In the aluminum alloy foil of the present embodiment, almost no material flows in from the flange portion at the initial stage of deep drawing of the corner cylinder, and the shoulder portion is formed by a bulging method. In particular, in the case of a lithium ion secondary battery requiring a high battery capacity, when the radius R of the shoulder portion is formed to be small, the shoulder portion is locally deformed, and defects such as minute breakage are likely to occur. This defect is the starting point leading to fracture. That is, in the initial stage of the deep drawing of the corner cylinder forming the shoulder, the occurrence of minute breakage or the like formed during the formation of the bulge is reduced, which is important for increasing the forming height.

By optimizing both the Cube azimuth density and the R azimuth density on the surface of the aluminum alloy foil, the ultimate deformation ability of the aluminum alloy foil is improved, and thus there is a large surface on the surface of the aluminum alloy foil such as partial bulge forming. In the strain deformation processing, the effect of plastic instability represented by necking is hard to occur. As a result, it is possible to suppress occurrence of minute breakage or the like in the initial stage of deep drawing of the corner cylinder in which the shoulder portion is formed, and thus it is possible to increase the forming height.

Here, the meaning of the TS × (TS / YS) equation will be described. The value of (TS/YS) is for tensile strength The ratio of the 0.2% yield strength YS of TS, the inventors found that the more the value is larger than the predetermined value, the more the region can be uniformly deformed, and the material tends to flow into the flange portion during deep drawing of the corner cylinder, and the tensile strength The higher the TS, the higher the fracture resistance. That is, it is preferable that the mechanical properties desired for the aluminum alloy foil which can be used in the present embodiment are those having a high tensile strength TS and a low 0.2% proof stress YS within a rationalized range. The value of the (TS/YS) is multiplied by the value of the tensile strength TS corresponding to the fracture resistance TS, which is TS × (TS / YS), and can be used as the correlation with the forming height in the present embodiment. One of the indicators of formability in the deep drawing test of the corner cylinder. In the direction of 0, 45, and 90 degrees with respect to the rolling direction of the aluminum alloy foil, TS × in the 45-degree direction of the rolling direction in which the material is difficult to flow in the corner flange portion during deep drawing of the corner cylinder The higher the TS/YS), the better the forming height of the aluminum alloy foil.

In the present embodiment, the aluminum alloy foil is preferably TS × (TS) in the direction of 45 degrees with respect to the rolling direction in the tensile strength TS and the 0.2% proof stress YS in the direction of 0, 45, and 90 degrees in the rolling direction. The value of /YS) satisfies 200 N/mm ² or more. More preferably, it is 210 N/mm<^2> or more. The value of TS × (TS / YS) in the 45-degree direction with respect to the rolling direction is, for example, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 215, 220, 230, 240 250N/mm ² may also be in the range between any two values of the numerical values exemplified herein.

In the aluminum alloy foil of the present embodiment, when the value of TS × (TS / YS) in the direction of 45 degrees with respect to the rolling direction is less than 200 N/mm ² , it is difficult to improve the moldability of the aluminum alloy foil. In the corner deep drawing test of the molded packaging material having a small thickness as in the present embodiment, as the forming height is increased, the corner flange portions of the four corners are deformed by the reduced flange, and the inflow resistance of the material is increased. It becomes difficult for materials to flow in. In particular, in the angular flange portion at the time of deep drawing of the corner cylinder, the direction is 45 degrees with respect to the rolling direction as compared with the 0 degree direction or the 90 degree direction corresponding to the rolling direction in the straight side direction or the short side direction. Since the material becomes difficult to flow in, it is possible to effectively increase the amount of material inflow in the direction of 45 degrees with respect to the rolling direction.

Further, in the present embodiment, a known method can be employed for the measurement of the tensile strength TS and the 0.2% proof stress YS in the direction of 0, 45, and 90 degrees with respect to the rolling direction of the aluminum alloy foil.

In the present embodiment, the aluminum alloy foil preferably has an absolute value of a difference of TS × (TS/YS) in a direction of 0° and a direction of 45 degrees in the rolling direction, and a TS in a direction of 45 degrees and a direction of 90 degrees with respect to the rolling direction. The absolute value of the difference of ×(TS/YS) satisfies 30 N/mm ² or less. More preferably, it is 10 N/mm<^2> or less. In the aluminum alloy foil according to the present embodiment, the absolute value of the difference between TS × (TS / YS) in the 0 degree direction and the 45 degree direction in the rolling direction, or the TS × YS direction in the 45 degree direction and the 90 degree direction (TS / YS) The absolute value of the difference is, for example, 30, ²⁵ , ²⁰ , 15, ¹⁰ , ⁹ , ⁸ , ⁷ , ⁶ , ⁵ , ⁴ , ³ , ² , ¹ , 0N/mm ² , and may be the numerical values exemplified herein The range between any 2 values.

Since the material in the corner flange portion becomes difficult to flow in the deep drawing of the corner cylinder, in particular, the inflow amount of the material in the direction of 45 degrees with respect to the rolling direction is increased, and the direction of 0 degree and 90 degrees with respect to the rolling direction is made. The amount of material inflow is also as good as possible without the difference between the absolute values.

Therefore, the absolute value of the difference in the inflow amount of the material in the direction of 0 degree and 45 degrees with respect to the rolling direction and the direction of 45 degrees with respect to the rolling direction is made as small as possible, which improves the formability of the aluminum alloy foil. It has a big effect. The absolute value of the difference between TS × (TS / YS) in the 0 degree direction and the 45 degree direction with respect to the rolling direction, and the 45 degree direction with respect to the rolling direction and the TS × (TS direction) in the 90 degree direction with respect to the rolling direction When the absolute value of the difference of /YS) exceeds 30 N/mm ² , the inflow balance of the material to the flange portion is deteriorated during deep drawing of the corner cylinder, and thus the formability of the aluminum alloy foil may be lowered.

In the present embodiment, the elongation of the aluminum alloy foil can be appropriately adjusted by changing the average crystal grain size, strength, and the like, and the higher the value, the better the moldability of the aluminum alloy foil. Specifically, when the elongation values of the aluminum alloy foil in the 0-degree, 45-degree, and 90-degree directions with respect to the rolling direction are all 17% or more, the moldability of the aluminum alloy foil is good, which is preferable. More preferably, the elongation values in the directions of 0, 45, and 90 degrees with respect to the rolling direction are all 20% or more.

In the present embodiment, the thickness of the aluminum alloy foil is an arbitrary value, and can be appropriately adjusted depending on the application, the formation conditions, and the like. However, it is generally preferably 10 to 100 μm. In the case of producing an aluminum alloy foil having a thickness of less than 10 μm, cracks or the like of pinholes or pressurization are liable to occur, so that production efficiency is easily lowered. In addition, when the thickness of the aluminum alloy foil exceeds 100 μm, the thickness of the entire package body becomes too thick, and it is difficult to reduce the size of the package body which can be obtained, which is not preferable.

(3) Method for producing aluminum alloy foil

The aluminum alloy foil in the present embodiment is produced by containing Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, and the remainder consisting of Al and unavoidable impurities. The aluminum alloy ingot is homogenized and maintained at 500 ° C or higher and 620 ° C or lower for 1 hour or more; after the homogenization is maintained, the steps of hot rolling and cold rolling are performed; and in the middle of the cold rolling, the temperature is 300 ° C. a step of intermediate annealing maintained at 450 ° C or lower; a cold rolling ratio of 85% or less from the hot rolling to the intermediate annealing to perform cold rolling; and a cold from the intermediate annealing to the final foil thickness The step of performing cold rolling at a rolling ratio of 80% or more and 93% or less; and a step of performing final annealing after the cold rolling to obtain the aluminum alloy foil. Hereinafter, the aluminum alloy foil in the present embodiment is manufactured. The method of production is described in detail.

In the method for producing an aluminum alloy foil according to the present embodiment, it is preferable to obtain an ingot according to a semi-continuous casting method after melting an aluminum alloy having the above composition. Thereafter, the aluminum alloy ingot was homogenized. The homogenization treatment is maintained at 500 ° C or higher and 620 ° C or lower for 1 hour or longer. After the homogenization treatment, hot rolling is started. In the homogenization treatment, the size of the Fe-based precipitates is increased, and the effect of reducing the amount of Fe solid solution can be expected.

When the conditions of the homogenization treatment are less than 500 ° C and a holding time of less than 1 hour, the Fe-based precipitates are not sufficiently coarsened, so that the amount of Fe solid solution is high and the amount of fine Fe-based precipitates is large. Therefore, the 0.2% yield strength becomes high, and in the tensile strength TS and the 0.2% proof stress YS in the direction of 45 degrees with respect to the rolling direction, the value of TS × (TS / YS) becomes less than 200 N / mm ² , and the aluminum alloy foil The formability is lowered, which is not preferable. In addition, the segregation formed during casting in the ingot is not sufficiently eliminated.

When the temperature of the homogenization treatment exceeds 620 ° C, the ingot may be partially melted, which is not preferable in terms of production. Further, it is not preferable because very little hydrogen gas mixed in during casting overflows the surface and easily swells on the surface of the material. The homogenization treatment temperature is preferably 550 ° C or more and 620 ° C or less, and more preferably 580 ° C or more and 615 ° C or less from the viewpoint of increasing the size of the Fe-based precipitates and making them more sparse. The temperature of the homogenization treatment is, for example, 550, 560, 570, 580, 590, 600, 610, 615, 620 ° C, and may be in a range between any two values of the numerical values exemplified herein.

Further, the holding time for homogenization is preferably 2 hours or longer, and more preferably 5 hours or longer. Further, the holding time of homogenization is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or more than 15 hours, and may be a numerical value exemplified herein. Any range between 2 values.

After the above homogenization treatment, the aluminum alloy ingot may be cooled to 400 ° C or higher and 500 ° C or lower, and hot rolling may be started. By performing this cooling, the size of the Al-Fe-based precipitate is increased while the amount of solid solution of Fe is lowered, whereby the 0.2% proof stress of the aluminum alloy foil can be reduced. When the starting temperature of hot rolling is less than 400 ° C, the precipitation amount of minute Al-Fe-based precipitates is excessive and the 0.2% yield strength is increased, and the tensile strength TS and 0.2% yield in the direction of 45 degrees with respect to the rolling direction are excessive. In the strength YS, the value of TS × (TS / YS) is less than 200 N / mm ² , and the moldability of the aluminum alloy foil is lowered, which is not preferable. When the starting temperature of the hot rolling exceeds 500 ° C, the amount of Fe dissolved in the aluminum alloy foil increases, so that the 0.2% yield strength becomes high, and the tensile strength TS and the 0.2% yield strength in the direction of 45 degrees with respect to the rolling direction are increased. In YS, the value of TS × (TS/YS) is less than 200 N/mm ² , and the moldability of the aluminum alloy foil is lowered, which is not preferable. From the viewpoint of increasing the size of the Fe-based precipitate, the starting temperature of the hot rolling is more preferably 400 ° C or more and 450 ° C or less. The starting temperature of hot rolling, for example, 400, 410, 425, 450, 475, 500 ° C, may also be in the range between any two values of the numerical values exemplified herein.

Since it is desirable to recrystallize the aluminum alloy sheet as much as possible during hot rolling, the end temperature of hot rolling is preferably 250 to 400 °C. From the viewpoint of more reliably recrystallizing the aluminum alloy sheet after hot rolling, it is more preferably 300 ° C or more and 400 ° C or less. The end temperature of hot rolling is, for example, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 ° C, which may also be the numerical values exemplified herein. Any range between 2 values. Further, after the hot rolling, the obtained aluminum alloy sheet was subjected to cold rolling. This cold rolling can be carried out by a known method, and is not particularly limited.

In the method for producing an aluminum alloy foil according to the present embodiment, it is necessary to perform intermediate annealing at 300 ° C or more and 450 ° C or less in the middle of the cold rolling of the aluminum alloy sheet. The temperature of the intermediate annealing is preferably 320 ° C or more and 400 ° C or less from the viewpoint of recrystallizing the aluminum alloy sheet and improving the rolling property. The temperature of the intermediate annealing is, for example, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450 ° C, and may be any of the numerical values exemplified herein. Within the range between 2 values.

When the temperature of the intermediate annealing is less than 300 ° C, the crystal grains of the aluminum alloy foil are likely to become coarse at the time of final annealing, and the uniformity of deformation is hindered, and the molding height is lowered, which is not preferable.

Further, if the temperature of the intermediate annealing exceeds 450 ° C, the amount of Fe solid solution increases, and thus the 0.2% yield strength increases, so in the tensile strength TS and the 0.2% proof stress YS in the direction of 45 degrees with respect to the above rolling direction, TS The value of ×(TS/YS) is less than 200 N/mm ² , and the moldability of the obtained aluminum alloy foil is lowered, which is not preferable.

By performing intermediate annealing, the aluminum alloy sheet is recrystallized to achieve the purpose of improving the rolling property. The implementation time of the intermediate annealing is not particularly limited, but is preferably 1 hour or more in order to recrystallize it. More preferably, it is 4 hours or more. The implementation time of the intermediate annealing is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 hours or more, and may be any of the numerical values exemplified herein. Within the range between 2 values.

Further, in the case where the intermediate annealing is not performed in the step of cold rolling, the cold rolling ratio from the hot rolling to the final foil thickness is increased, so that the crystal orientation of the aluminum alloy foil after the final annealing cannot be obtained. The desired Cube orientation density and R orientation density are not preferable because the moldability of the aluminum alloy foil is lowered.

In the method for producing an aluminum alloy foil according to the present embodiment, the aluminum alloy sheet obtained by the hot rolling is subjected to cold rolling at a cold rolling ratio of 85% or less from the hot rolling to the intermediate annealing. If cold rolling is performed from the hot rolling to the case where the cold rolling rate before the intermediate annealing exceeds 85%, the desired Cube azimuth density and R orientation cannot be obtained in the recrystallized aggregate structure of the aluminum alloy foil after the final annealing. The density and the ultimate deformability are lowered, so it is not preferable. For example, in the deformation processing in which a large strain is generated on the surface of the aluminum alloy foil such as partial bulging, plastic deformation such as a necking is caused, and the moldability of the aluminum alloy foil may be lowered. There is also a case where both the hot rolling end thickness and the cold rolling ratio from the intermediate annealing to the final foil thickness are achieved, but it is important to reduce the cold rolling ratio from the hot rolling to the intermediate annealing. The cold rolling ratio from hot rolling to intermediate annealing is, for example, 50, 55, 60, 65, 70, 75, 80, 85% or less, and may be a range between any two values of the numerical values exemplified herein. Inside.

In the method for producing an aluminum alloy foil according to the present embodiment, the cold rolling ratio is 80% or more and 93% or less from the intermediate annealing to the final foil thickness, and cold rolling is performed. The cold rolling ratio from the intermediate annealing to the final foil thickness is the average crystal grain size of the aluminum alloy foil after the final annealing, the crystal orientation of the surface of the aluminum alloy foil, and the direction of 0, 45, and 90 degrees with respect to the rolling direction. The intensity balance has an effect. When the cold rolling ratio is less than 80%, the crystal grains of the aluminum alloy foil after the final annealing become large, and the moldability of the aluminum alloy foil is lowered, which is not preferable. On the other hand, if the cold rolling ratio exceeds 93%, the average crystal grain size after the final annealing is fined to affect the increase amount of the 0.2% proof stress YS, and in the aluminum alloy foil with respect to the rolling direction. The value of TS × (TS / YS) in the 45-degree direction is small, and the formability of the aluminum alloy foil is lowered, which is not preferable. Further, by increasing the cold rolling ratio from the intermediate annealing to the final foil thickness, the desired Cube azimuth density and the R orientation density of the surface of the aluminum alloy foil after the final annealing are obtained, so that the aluminum alloy foil is in the rolling direction with respect to the rolling direction. 0, 45, 90 degree intensity balance, relative to the rolling direction The intensity in the 0 degree direction is greater than the 45 degree direction and the 90 degree direction. As a result, only the value of TS × (TS / YS) in the 0 degree direction with respect to the rolling direction becomes large, and the difference between TS × (TS / YS) in the 0 degree direction and the 45 degree direction in the rolling direction becomes large. Therefore, the moldability of the aluminum alloy foil is lowered, which is not preferable. The cold rolling ratio from the intermediate annealing to the final foil thickness is, for example, 80.0, 81.0, 82.0, 83.0, 84.0, 85.0, 86.0, 87.0, 88.0, 89.0, 90.0, 91.0, 92.0, 93.0%, or may be here. The range of values between any two values of the exemplified values.

After the end of the cold rolling, final annealing is preferably performed to make the aluminum alloy foil a completely soft foil. From the viewpoint of completely recrystallizing and completely volatilizing the rolling oil, the conditions for the final annealing are preferably carried out at 200 to 400 ° C for 5 hours or more. More preferably, it is carried out at 250 to 350 ° C for 20 hours or more. As the temperature for final annealing, for example, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 ° C It may also be in the range between any two values of the numerical values exemplified herein. The time for the final annealing is, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 hours or more, and may be the numerical values exemplified herein. The range between any 2 values.

When the temperature of the final annealing is less than 200 ° C, since it is not completely recrystallized, the desired foil may not be obtained. In addition, when the temperature of the final annealing exceeds 400 ° C, the crystals in the annealing are coarsened and the moldability of the aluminum alloy foil is lowered, which is not preferable. In the case where the holding time at the final annealing is less than 5 hours, the rolling-off rolling oil of the foil is not sufficiently volatilized, and thus the wettability of the surface of the foil is lowered, particularly in the aluminum foil of the present embodiment. In the case of a molded package material, the adhesion of the resin film laminated with the aluminum alloy foil may be easily lowered.

The temperature increase rate at the time of final annealing is not particularly limited, but is preferably carried out at 50 ° C / hr or less. When the temperature increase rate at the time of the final annealing exceeds 50° C./hr, a part of the crystal grains is coarsened, so that uneven deformation is likely to occur during deep drawing of the corner tube, and the moldability of the aluminum alloy foil may be lowered. From the viewpoint of the size of the average crystal grain size of the aluminum alloy foil, the temperature increase rate at the time of final annealing is preferably 40° C./hr or less. The temperature increase rate at the time of final annealing is, for example, 50, 45, 40, 35, 30, 25, 20, 15, or 10 ° C / hr or less, and may be in a range between any two values of the numerical values exemplified herein.

<Formed package material>

The aluminum alloy foil in the present embodiment can be suitably used as a molded package material. In the molded package material described in the present specification, the aluminum alloy foil of the present embodiment is molded into various packages such as a secondary battery or a PTP, and the packaged portion includes a pharmaceutical product. Lithium ion secondary battery materials (including electrode materials, separators, electrolytes, etc.) and the like.

In the molded package material of the present embodiment, the aluminum alloy foil according to the present embodiment can be suitably used for a molded material of a secondary battery or a pharmaceutical packaging container, that is, an external material. It contributes to the improvement of the performance of the secondary battery and the increase in the degree of freedom in the use of pharmaceuticals.

Hereinafter, the molded package material in the present embodiment will be described in detail with reference to the drawings. The embodiments in the following molded package materials are examples and are not limited.

1 is a schematic cross-sectional view showing an example of an internal structure of a sheet-like thin lithium ion secondary battery. In addition, FIG. 2 is a schematic cross-sectional view showing a general example of the exterior material of the secondary battery.

The molded package material 1 in the present embodiment may be a single member of the aluminum alloy foil 8 in the present embodiment or a multilayer including the aluminum alloy foil 8 in the present embodiment, and is not particularly limited, but a multilayer In this case, it is necessary to have at least an aluminum alloy foil as a constituent element. Specifically, as shown in FIG. 2, the synthetic resin film 10, the aluminum alloy foil 8, and the heat seal layer 9 are laminated in this order, but the laminated structure is not particularly limited.

In order to further improve the moldability of the molded package material 1, or to protect the aluminum alloy foil 8 which is the main material of the main body of the package, or to perform printing, the synthetic resin film 10 is laminated and bonded to one surface of the aluminum alloy foil 8. . As the synthetic resin film 10, a polyester film, a nylon film, or the like can be used. The molded package material 1 of the present embodiment can be used as a secondary battery or a pharmaceutical packaging container. In particular, when it is a secondary battery, the molded package material 1 of the present embodiment can be used as a secondary battery. For exterior materials. In this case, heat generation, heat dissipation treatment, and the like of various battery members housed in the exterior material are required. Therefore, it is preferable to use a heat-resistant polyester film as the synthetic resin film 10.

The heat seal layer 9 is used to seal the end portion 7 of the package. As the heat seal layer 9, a known hot melt synthetic resin can be used. In particular, as long as the adhesion to the aluminum alloy foil 8 used in the present embodiment is excellent and the content can be protected, for example, a non-stretched polypropylene film, a biaxially oriented polypropylene film, or a maleic acid modified polycondensation is preferably used. Olefins.

In the case where the molded package material 1 of the present embodiment is a plurality of layers, the aluminum alloy foil 8 of the present embodiment is not particularly limited, and the suitability of the contents is satisfied as long as the formability, the adhesion, and the like are satisfied. No special restrictions. For example, it can be placed on one side of the aluminum alloy foil 8 by a usual method. The adhesive film carries a non-stretched polypropylene film and is crimped. After bonding the aluminum alloy foil 8 and the non-stretched polypropylene film, an adhesive is applied to the other side of the aluminum alloy foil 8 to carry a composite thereon. The resin film 10 is bonded together.

The above-described crimping of the aluminum alloy foil 8 and the polypropylene film is generally carried out under heating. The heating conditions are not particularly limited and are usually about 160 to 240 °C. Further, the pressure bonding conditions are not particularly limited, and generally, the pressure is 0.5 to 2 kg/cm ² and the time is about 0.5 to 3 seconds.

In addition, as a binder of the synthetic resin film 10, a conventionally known material can be used, and for example, a urethane-based adhesive or the like can be used.

The molded package material in the present embodiment can be formed by a known method, and the forming method is not particularly limited, but is particularly suitably used in deep drawing. Here, the molded package material 1 according to the present embodiment is used as an example of a method of obtaining a package, and the molded package material 1 is cut into a desired size to obtain a packaging material having a desired shape, and the packaging material is obtained. The deep drawing is performed such that the central portion becomes a concave portion and the peripheral portion becomes a flat portion, and the heat seal layer 9 side becomes an inner surface. Two packaging materials subjected to deep drawing were used so that the concave portions faced each other, and the heat sealing layers 9 at the peripheral portions were bonded to each other. Further, a part is retained, and the other peripheral portions are heat-sealed to obtain a package. When it is used for the secondary battery exterior material, the secondary battery can be manufactured by accommodating the positive electrode current collector 2, the positive electrode 3, the separator 4, the negative electrode 5, and the negative electrode current collector 6 in the center portion, and then immersed in the electrolytic solution. The lead wire extending from the secondary battery main body can be produced by a known method such as heat sealing the bag mouth again.

According to the secondary battery of the present embodiment, the molded package material 1 having the aluminum alloy foil 8 having the above-described excellent moldability is used, so that the concave portion is formed deeper than the conventional one, and the formation can be improved. A secondary battery for a secondary battery having a large capacity can provide a secondary battery having a charging capacity or a high output that can withstand long-term use.

In the case where the molded packaging material 1 of the present embodiment is used to obtain a pharmaceutical packaging container, the above-described method can also be employed in the molding method. For example, in the case of PTP, a medicine (tablet, capsule, etc.) can be stored and used as a pharmaceutical packaging container. The pharmaceutical packaging container of the present invention can be produced by a known method, and the production method is not particularly limited.

According to the pharmaceutical packaging container, since the molded package material 1 having the aluminum alloy foil 8 having the above-described excellent moldability is used, it is possible to perform deep drawing under severe conditions such as angular deep drawing. Reduce the shaped package material 1. Further, according to the pharmaceutical packaging container, since the average crystal grain size of the aluminum alloy foil is small, uneven deformation is less likely to occur during deep drawing, and the crack of the molded body at the corner portion is small, so that it is difficult for the water vapor to be externally removed. The intrusion into the molded package material 1 is superior to the long-term quality control of tablets and the like which are required to block the contents of the water vapor during storage.

Although the present invention has been described above, various configurations other than those described above can be employed without departing from the gist of the present invention.

For example, in the above embodiment, the molded package material 1 for secondary battery or pharmaceutical packaging is used. However, it is not particularly limited and may be used as another packaging application. For example, it can also be used as a shaped package material for a primary battery, rather than a secondary battery. In this way, the deep drawing of the concave portion deeper than in the past is good, and the primary battery exterior material having a large capacity can be formed. Therefore, a primary battery having a charging capacity or a high output that can withstand long-term use can be obtained.

[Examples]

Hereinafter, the present invention will be further illustrated by way of experimental examples, but the present invention is not limited to these experimental examples.

An aluminum ingot having the composition shown in Table 1 was prepared, and homogenization treatment, cooling, hot rolling, cold rolling, foil rolling, and final annealing described in Table 1 were carried out to obtain an aluminum alloy foil having a thickness of 40 μm. The tensile strength TS, the 0.2% proof stress YS, and the elongation of the obtained aluminum alloy foil at 0, 45, and 90 degrees with respect to the rolling direction were measured, and the value of TS × (TS / YS) was calculated, and the result was calculated. Shown in Table 2. Further, also in Table 2, the average crystal grain size of the aluminum alloy foil and the crystal orientation density of the surface of the aluminum alloy foil were shown. Further, the laminated composite material simulating the actual battery exterior material was experimentally produced, and the results of the deep-drawn forming test of the corner cylinder are also shown in Table 2.

Regarding the tensile strength TS of the aluminum alloy foil, a long strip sample having a width of 10 mm was used, and the distance between the chucks was 50 mm, and a deep drawing test was performed at a deep drawing speed of 10 mm/min to measure the maximum of the long strips. For the load, the stress divided by the cross-sectional area of the original sample was calculated as the tensile strength. Further, regarding the 0.2% proof stress YS, the parallel line is drawn from the value of the permanent strain of 0.2% in the straight line in the elastic region indicated by the straight line from the initial rising edge of the load-elongation curve, and the above is obtained. The point at which the curves intersect, that is, the value of the point corresponding to the yield point of the steel material or the like. Further, regarding the elongation, when the distance between the chucks when the long sample piece is broken is L (mm) in the same measurement method as in the case of the tensile strength, [(L - 50) / 50] × 100 Calculation.

Next, in order to test the degree of deep drawability of the molded package material using the aluminum alloy foil according to the experimental example, the following experiment was conducted. An organic solution composed of 15 parts by weight of maleic anhydride-modified polypropylene and 85 parts by weight of toluene having an average particle diameter of 6 to 8 μm was applied to one surface of each of the aluminum alloy foils obtained in the experimental examples at 200 ° C for 20 seconds. The mixture was dried under the conditions to obtain an adhesive film having a thickness of 2 μm. Next, a polypropylene film having a thickness of 40 μm was bonded to the surface of the adhesive film under pressure bonding conditions of a temperature of 200 ° C, a pressure of 2 kg/cm ² and a time of 1 second. Finally, the other side of the aluminum alloy foil (the surface on which the extruded film was not bonded) was bonded to a two-axis stretch nylon having a thickness of 25 μm via a urethane-based adhesive to obtain a molded package material.

From the above-mentioned molded packaging material, it was cut at a size of 120 mm × 100 mm, and it was used as a sample for the deep drawing test of the corner cylinder. A deep drawing test of the corner cylinder was carried out with a wrinkle force of 300 kgf using a punch having a length of 60 mm, a width of 40 mm, a shoulder R and a corner R of 1.5 mm. The forming height was increased from 1.0 mm on a 0.5 mm scale, and the above-mentioned corner cylinder deep drawing test was performed five times at each forming height, and the maximum forming height at which pinholes and cracks did not occur in all five times is shown in Table 2.

Further, the average crystal grain size of the aluminum alloy foil was measured as follows. The obtained aluminum alloy foil was subjected to electrolytic polishing at a voltage of 20 V by a 20% by volume hydrochloric acid + 80% by volume ethanol mixed solution at 5 ° C or lower, followed by washing with water, drying, and then 50% by volume of phosphoric acid at 25 ° C or lower. In a mixed solution of +47 vol% methanol + 3 vol% hydrofluoric acid, an anodic oxide film was formed at a voltage of 20 V, and then polarized by an optical microscope. Vibrate, observe crystal grains, and take a photo. From the photograph taken, the average crystal grain size was measured by the cutting method. In the cutting method, there are several crystal grains in a certain line segment, and a method of dividing the number of the line segments by the number is obtained. The average crystal grain size is shown in Table 2.

The X-ray diffraction apparatus was used to measure the crystal orientation density of the surface of the aluminum alloy foil, and the incomplete pole maps of {100}, {110}, and {111} were measured according to the Schultz reflection method by X-ray diffraction. Based on the three-dimensional crystal orientation analysis (ODF) and investigated. In addition, in the analysis of these, the data obtained by measuring the sample having a random crystal orientation made of aluminum powder is used as a normalized file used for analyzing the {100}, {110}, and {111} pole patterns. This is to determine various azimuth densities for multiples of samples with random orientations. Further, in this experimental example, the crystal orientation density was all based on three-dimensional crystal orientation analysis (ODF).

Here, the Cube orientation is represented by {001}<100>, and the R orientation is represented by {123}<634>. Further, in general, there is an azimuth dispersion having a certain angle centering on the above orientation. In the present experimental example, the maximum azimuth density in the 15° rotation range around the azimuth is taken as a representative value of the azimuth density.

From the above results, in the aluminum alloy foils of Experimental Examples 1 to 21, 28, 29, and 31, the average crystal grain size and the orientation density of the aluminum alloy foil were controlled, so that the aluminum alloy foil 22 of the experimental example was used. Compared with 27, 30, and 32 to 39, the deep drawing forming test of the corner cylinder showed high forming height and excellent formability. Therefore, it is understood that the molded package material obtained by using the aluminum alloy foils of Experimental Examples 1 to 21, 28, 29, and 31 can be favorably deeply drawn, and is suitable for use in packaging a thick content. Further, in the aluminum alloy foils according to Experimental Examples 1 to 21, the strength balance in the direction of 0, 45, and 90 degrees with respect to the rolling direction was also controlled to be optimum, so that the forming height of the deep drawing test of the corner cylinder was further improved. High and good formability. On the other hand, in the aluminum alloy foils of Experimental Examples 22 to 27, 30, and 32 to 39, it was found that the forming height of the corner deep drawing test was low and the formability was poor. Therefore, the molded package material obtained by using the aluminum alloy foils of Experimental Examples 22 to 27, 30, and 32 to 39 cannot be deeply drawn and formed, and is not suitable for packaging a thick content.

In addition, as a result of the above, it was found that the aluminum alloy ingot of the specific composition was treated in a specific step, and the aluminum alloy foils of Experimental Examples 1 to 21 showed angles as compared with the aluminum alloy foils 22 to 39 of the experimental examples. The deep drawing test of the barrel has a high forming height and excellent formability. Therefore, it is understood that the molded package material obtained by using the aluminum alloy foils according to Experimental Examples 1 to 21 can be subjected to deep drawing, and is suitable for packaging a thick content.

In Experimental Example 22, since the amount of Si added was small, the value of TS × (TS / YS) in the 45-degree direction was low, and it was difficult for the material to flow into the flange portion during the deep barrel tensile test, and the forming height was not improved.

In Experimental Example 23, the amount of Si added was large, so not only TS × (TS / YS) in the direction of 45 degrees The value is low, and the average crystal grain size also becomes large, so that the forming height is not increased.

In Experimental Example 24, since the amount of added Fe was small, not only the value of TS × (TS / YS) in the 45-degree direction was low, but also the average crystal grain size was also increased, so that the forming height was not improved.

In Experimental Example 25, since the amount of added Fe was large, the crystal grains were minute, and the value of TS × (TS/YS) in the 45-degree direction was low, and the R orientation density was increased, so that the molding height was not improved.

In Experimental Example 26, since the amount of added Cu was small, the value of TS × (TS/YS) in the direction of 45 degrees was low, and it was difficult for the material to flow into the flange portion, and the forming height was not improved.

In Experimental Example 27, since the amount of Cu added was large, the Cube azimuth density on the surface of the aluminum alloy foil was low, and the forming height was not improved.

In Experimental Example 28, since the homogenization treatment temperature was low, the value of TS × (TS / YS) in the direction of 45 degrees was low, and it was difficult for the material to flow into the flange portion during the deep drawing test of the corner cylinder, so that the molding height was not increased.

In Experimental Example 29, since the holding time at the time of the homogenization treatment was short, the value of TS × (TS / YS) in the direction of 45 degrees was low, and it was difficult for the material to flow into the flange portion during the deep drawing test of the corner cylinder, so that the forming height was obtained. The increase is small.

In Experimental Example 30, since the intermediate annealing temperature was low, not only the value of TS × (TS / YS) in the 45-degree direction was low, but also the average crystal grain size was also increased, so that the forming height was not improved.

In Experimental Example 31, since the intermediate annealing temperature was high, the value of TS × (TS / YS) in the 45-degree direction was low, and it was difficult for the material to flow into the flange portion during the deep barrel tensile test, and the increase in the forming height was small.

In Experimental Example 32, since the intermediate annealing was not performed, the crystal grains were minute, the value of TS × (TS/YS) in the 45-degree direction was low, the Cube orientation density was small, the R orientation density was high, and the 0 degree direction and the 45 degree were The difference between the TS × (TS / YS) direction, the 45 × direction, and the TS × (TS / YS) in the 90-degree direction also increases, so that the molding height is not increased.

In Experimental Example 33, since the cold rolling ratio from the hot rolling to the intermediate annealing was large, the Cube azimuth density on the surface of the aluminum alloy foil was small, and the initial fracture of the corner tube deep drawing test was minutely broken, so that the forming height was not improved.

In Experimental Example 34, since the cold rolling ratio from the intermediate annealing to the final foil thickness was small, the value of TS × (TS/YS) in the 45-degree direction was low, and the average crystal grain size was also large. Thus, the forming height is not increased.

In Experimental Example 35, the cold rolling ratio from the intermediate annealing to the final foil thickness was large, so that the value of TS × (TS/YS) in the 45-degree direction was low, and the Cube orientation density was small, and the R orientation density was small. When the height is increased, the difference between TS × (TS / YS) in the 0 degree direction and the 45 degree direction becomes large, so that the forming height is not increased.

In Experimental Example 36, the value of TS × (TS/YS) in the direction of 45 degrees was low, and the aluminum alloy foil was no longer crystallized, so that the forming height was lowered.

In Experimental Example 37, not only the value of TS × (TS/YS) in the 45-degree direction was low, but also the average crystal grain size was also increased, so that the forming height was not improved.

In Experimental Example 38, not only the value of TS × (TS/YS) in the 45-degree direction was low, but also the average crystal grain size was also increased, so that the forming height was not improved.

In Experimental Example 39, the value of TS × (TS / YS) in the direction of 45 degrees was low, and the aluminum alloy foil was no longer crystallized, so that the forming height was lowered.

1‧‧‧External materials (formed packaging materials)

8‧‧‧External material body (aluminum alloy foil)

9‧‧‧Heat seal

10‧‧‧Synthetic resin film

Claims (6)

An aluminum alloy foil containing Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, and the remainder consisting of Al and unavoidable impurities, in the aluminum alloy foil, The crystal orientation of the surface of the aluminum alloy foil is 5 or more, and the R orientation density is 50 or less, and the average crystal grain size of the aluminum alloy foil is 7 to 20 μm, wherein the aluminum alloy foil is relatively In the respective tensile strength TS and 0.2% proof stress YS in the direction of 0, 45, and 90 degrees in the rolling direction, the value of TS × (TS / YS) in the direction of 45 degrees is 200 N / mm ² or more, 0 The absolute value of the difference between TS × (TS / YS) in the direction of 45 degrees and the direction of 45 degrees is 30 N / mm ² or less, and the absolute value of the difference between TS × (TS / YS) in the direction of 45 degrees and 90 degrees is 30 N / mm. ² or less. A formed package material comprising the aluminum alloy foil according to claim 1. The molded package material according to claim 2, further comprising: a synthetic resin film laminated on one side of the aluminum alloy foil, and heat laminated on the other side of the aluminum alloy foil Sealing layer. A secondary battery using the shaped package material as described in claim 3. A pharmaceutical packaging container using the shaped package material as claimed in claim 3. A method for producing the aluminum alloy foil according to claim 1, which comprises: Fe: 0.8 to 2.0 mass%, Si: 0.05 to 0.2 mass%, Cu: 0.0025 to 0.2 mass%, the remainder from Al and inevitable An aluminum alloy ingot composed of impurities, which is homogenized and maintained at 500 ° C or more and 620 ° C or lower for 1 hour or more; After the homogenization is maintained, a step of hot rolling and cold rolling is performed; in the middle of the cold rolling, a step of intermediate annealing maintained at 300 ° C or higher and 450 ° C or lower is performed; and after the hot rolling to before the intermediate annealing a step of performing cold rolling at a cold rolling ratio of 85% or less; a step of performing cold rolling after the intermediate annealing to a final foil thickness of 80% or more and 93% or less; and after the cold rolling The final annealing is performed to obtain the aluminum alloy foil.