KR101842689B1 - Material for molded packages - Google Patents

Abstract

An aluminum alloy molded package material having good moldability is provided. And the balance of Al and inevitable impurities, wherein the average grain size is 20 占 퐉 or less, and the ratio of the average grain size in the rolling direction to the grain size in the rolling direction is in the range of 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, and Cu: 0.0025 to 0.0200 mass% (1) having an aluminum alloy foil (8) having an average value YS of a 0.2% proof stress at 0 degrees, 45 degrees and 90 degrees and an average value TS of a maximum tensile strength of YS / TS? 0.60 .

Description

[0001] The present invention relates to a material for molded packages,

The present invention relates to a molding package material, a secondary battery using the same, a medicine packaging container, and a manufacturing method thereof.

The PTP (Press Through Package) that packs medicines is often packaged by a combination of a container and a cover material. The container side is formed by deep drawing molding. In a conventional strip package, a plastic film such as a plastic film such as polypropylene can be used as the container. In many cases, a composite in which an aluminum foil having high barrier properties and a resin film are bonded to one or both surfaces is often used for tablets or the like, which is required to have water vapor barrier properties when stored.

In recent years, various pharmaceuticals of various shapes and sizes have been circulating in the market, and the packaging body for packaging them has also been required to be formed into deeper or more complex shapes in accordance with the shape thereof.

In order to impart water vapor barrier properties to the outer sheath of the secondary battery, a molded package material having a composite structure in which a resin film is bonded to both surfaces of the aluminum foil can be used.

For example, secondary batteries such as lithium ion secondary batteries (including lithium ion capacitors, the same shall apply hereinafter) have recently become smaller and lighter as electronic equipment such as mobile communication devices, notebook PCs, headphone stereos, camcorders, ). The secondary battery has the structure shown in Fig. 1, for example. That is, the stacked body (secondary battery body) in which the positive electrode collector 2, the positive electrode 3, the separator 4, the negative electrode 5, and the negative electrode collector 6 are stacked in this order, (Exterior material) 1 as shown in Fig. The exterior member 1 is heat-sealed at the end portion 7 as necessary.

In the molded package 1 shown in Fig. 1, generally, as shown in Fig. 2, a heat sealing layer 9 is laminated and bonded to one surface of a facer material body 8, and on the other surface thereof, Are laminated and bonded to each other. As shown in Fig. 1, the molding pouch 1 has a concave portion at the center thereof, which is a housing portion thereof, for housing the positive electrode collector 2 and the like therein, and the periphery of the concave portion is formed into a flat portion.

The secondary battery is required to have a high charging capacity or a high output power that can withstand use for a long period of time. Therefore, the structure of the element composed of the electrode, the current collector and the separator of the battery is complicated and multi-layered, and molding under severe conditions such as deeper recess forming is required.

A metal foil, particularly an aluminum alloy foil, which is hardly permeable to moisture or air and is excellent in moldability has been conventionally used as the molded package 1 or the casing main body 8 so as not to adversely affect the quality of the contents. As the aluminum alloy foil, a composition specified in JIS 1100, 3003, 3004, 8079 or 8021 (JIS H 4160) is used. Such an aluminum alloy foil is excellent in tensile hardness and is not easily broken.

However, the aluminum alloy foil has a low degree of tensile elongation, and cracking or pinholes may occur if severe molding such as molding a deep recess is performed. That is, there is no problem in the case of forming the molding pavement body 1 or the exterior material main body 8 in the process of forming a relatively shallow recess in the aluminum alloy foil. However, in order to increase the capacity of the water- When a deep recess is formed in the center of the package, cracks or the like tend to occur at the boundary between the recess and the flat portion, and moisture, air and the like are easily permeated and adversely affect the quality of the contents. Particularly, when used as a secondary battery outer cover material, when water or air permeates, hydrofluoric acid is generated due to reaction with the electrolyte inside the battery, and the environment inside the battery is likely to be corroded.

Conventionally, an aluminum foil having a thickness of 20 to 60 占 퐉 and an elongation of 0%, 45%, and 90% in the rolling direction of 11% or more in all cases has been proposed as an exterior material body (Patent Document 1). Further, it has been proposed that when a specific amount of Fe or Si is added to Al as the casing material body, tensile elongation and tensile strength are improved, and an aluminum alloy foil suitable as a casing main body of the secondary battery can be obtained (Patent Document 2) .

Japanese Patent Application Laid-Open No. 2005-163077 Japanese Patent Laid-Open No. 2001-176459

However, the prior art described in the patent document has room for improvement in the following points.

First, the elongation values of the aluminum alloy foils of Patent Document 1 and Patent Document 2 are still insufficient to become a battery casing.

Second, in the field of secondary batteries used for automobiles and power tools in addition to the above-mentioned applications, in order to achieve high output, deeper drawing formability or protrusion formability is required. In order to realize the above object, It is required.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a molded package material having excellent elongation and good moldability and a method for producing the same.

As a result of repeated studies in view of the above circumstances, the inventors of the present invention have found that when the composition and the average crystal grain size of the aluminum alloy foil satisfy certain conditions, the three- It has been found that a molded package material having good moldability can be obtained by setting the average tensile strength and the 0.2% average proof stress to a specific ratio with respect to the mechanical properties.

In addition, a conventional aluminum alloy foil is manufactured by sequentially performing casting, homogenizing treatment, hot rolling, and cold rolling. Here, the inventors of the present invention have conducted researches on the conditions of each of these processes. As a result, they have found that, after homogenization treatment of an aluminum alloy ingot formed with a specific composition, the aluminum alloy ingot is maintained at a high temperature, It is possible to obtain a molded package material having good moldability by controlling the temperature condition of intermediate annealing before or during the cold rolling step, thereby completing the present invention.

That is, according to the present invention, there is provided a steel sheet comprising: 0.8 to 1.7% by mass of Fe, 0.05 to 0.20% by mass of Si, and 0.0025 to 0.0200% by mass of Cu and the balance of Al and inevitable impurities, And an aluminum alloy foil having an average value YS of a 0.2% proof stress at 0 degrees, 45 degrees and 90 degrees with respect to a rolling direction and an average value TS of a maximum tensile strength of YS / TS? 0.60 / RTI >

According to the molded package material, the composition and the average crystal grain size of the aluminum alloy foil satisfy certain conditions, and the average tensile strength in the three directions of the aluminum alloy foil and the average 0.2% proof stress have a specific ratio , A molded package material having good moldability can be obtained. Particularly, it is preferable that the aluminum alloy foil has an average value of elongation in the rolling direction of 0, 45, and 90 degrees of 20.0% or more. By such a provision, the molding package material of the present invention can be subjected to deep drawing molding under particularly harsh conditions and can accommodate relatively thick contents such as multilayer laminated parts such as secondary batteries, Can be suitably used as a material. Further, since it is specified in the above specific conditions, uneven deformation does not easily occur at the time of deep drawing forming, cracks at the corner of the molded article can be suppressed, and moisture or air from the outside does not enter the molded- The deterioration of the contents in the molding pavement material can be surely prevented.

According to the present invention, there is also provided a secondary battery using the molded package material.

According to the secondary battery, since the molded package material having the excellent formability is used, the secondary battery can be subjected to deep drawing molding and has a relatively thick outer shell for a secondary battery. Therefore, An excellent secondary battery having high output performance can be obtained. In addition, according to the secondary battery, since the molded package material of the present invention is used, uneven deformation does not easily occur during deep drawing molding, cracks and pinholes are not generated at the corners of the molded body, It is possible to prevent the inside of the battery from being corroded due to the reaction with the electrolytic solution in the inside of the battery due to the hydrofluoric acid generated by the reaction with the electrolytic solution in the battery.

Further, according to the present invention, there is provided a pharmaceutical packaging container using the above-mentioned molded package material.

According to the pharmaceutical packaging container, a deep-draw molding can be performed using the molding package material having the above-described good moldability, and a deeper molded pharmaceutical packaging container can be obtained. Further, according to the medicine packing container, since the average particle diameter of the aluminum alloy foil is small, uneven deformation does not easily occur at the time of deep drawing forming, and cracks at the corner portion of the molded article are reduced, It is possible to suitably pack the contents and the like that are difficult to enter into the body material and require water vapor barrier property when stored. Therefore, when the pharmaceutical packaging container of the present invention is used as a PTP of a pharmaceutical product, the pharmaceutical product can be stably held in the long term.

According to the present invention, there is provided a method for producing a molded package material, which comprises the steps of: 0.8 to 1.7 mass% of Fe, 0.05 to 0.20 mass% of Si, 0.0025 to 0.0200 mass% of Cu, A step of homogenizing and holding the aluminum alloy ingot made of unavoidable impurities at a temperature of 550 ° C or more and 610 ° C or less for 3 hours or more; a step of cooling to 400 ° C or more and 450 ° C or less after the homogenization and holding; A step of performing intermediate annealing which is carried out at a temperature of 300 ° C or higher and 450 ° C or lower before and during the cold rolling for 1 hour or longer; and a step of final annealing after the cold rolling to obtain the aluminum alloy foil Method is provided.

According to the above method, the aluminum alloy ingot formed in a specific composition is homogenized at a high temperature and then cooled, subjected to hot rolling, and the temperature condition of the intermediate annealing performed during the cold rolling step is controlled, It is possible to obtain a molded package material in which the average crystal grain size satisfies a specific condition and the average tensile strength in the three directions and the average 0.2% Body material can be obtained. In particular, a molding package material having an excellent elongation value having a high average elongation in three predetermined directions and having good moldability can be reliably obtained. Therefore, the molded package material obtained by the above method can be subjected to deep drawing molding under particularly harsh conditions, can increase the capacity of contents, and can package relatively thick contents. Therefore, As shown in FIG. In addition, the molded package material obtained by the above-described method is unlikely to undergo uneven deformation during deep drawing forming and has less cracks at the corners of the molded article, and moisture or air from outside does not enter the molded package material , It is possible to prevent deterioration of the contents of components for a secondary battery and medicines contained in the molded package.

According to the present invention, a molded package material, a secondary battery or a pharmaceutical packaging container having an excellent elongation value and having good moldability can be obtained because the composition and the average crystal grain size of the aluminum alloy foil satisfy certain conditions. Further, according to the present invention, a casting package material having an excellent elongation value and having good moldability can be efficiently obtained in treating an aluminum alloy ingot formed with a specific composition by a specified process.

1 is a schematic cross-sectional view showing an example of the internal structure of a sheet-shaped, thin, polymer lithium ion secondary battery.
2 is a schematic cross-sectional view showing a general example of a casing of a secondary battery.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and a description thereof will be omitted. In the embodiments of the present invention, "A to B" means A or more and B or less.

<Aluminum alloy foil>

 (1) Composition and mean grain size of aluminum alloy foil

The molded package material according to the present embodiment comprises an aluminum alloy foil containing Fe, Si, and Cu in a specific composition, the balance being Al and inevitable impurities, and having an average crystal grain size of 20 m or less.

Here, the content of Fe contained in the aluminum alloy foil is 0.8 to 1.7 mass%. When the Fe content is less than 0.8% by mass, both the tensile strength and elongation are lowered, and the formability is lowered. If the content of Fe exceeds 1.7% by mass, the tensile strength and the proof stress are increased together. The ratio of the tensile strength TS in the direction of 0, 45, and 90 degrees to the average of the tensile strength TS and the YS / Is more than 0.60, moldability is deteriorated. In particular, it is more preferable that the content be not less than 1.0% by mass and not more than 1.6% by mass from the viewpoint of balance of strength and elongation.

Further, the content of Si contained in the aluminum alloy foil is 0.05 to 0.20 mass%. If Si is less than 0.05% by mass, both the tensile strength and the elongation are lowered, which is not preferable. On the other hand, when Si is more than 0.20 mass%, the tensile strength is increased but the elongation is decreased and the formability is lowered. Further, since the crystal grain size becomes large, uniform deformation during molding hardly occurs. Of these values, in particular, not less than 0.06 mass% and not more than 0.10 mass% are preferable in view of strength and crystal grain size.

The content of Cu contained in the aluminum alloy foil is 0.0025 to 0.0200 mass%. When the content of Cu is less than 0.0025 mass%, the amount of a small amount is small, so that the elongation is decreased and the formability is lowered. When Cu exceeds 0.0200 mass%, the hardening at the time of rolling becomes large, and cracks tend to occur during rolling. Of these values, particularly 0.0050 mass% or more and 0.0100 mass% or less are preferable in view of the rolling property and the moldability.

The inevitable impurities contained in the aluminum alloy foil are each 0.05 mass% or less, in total not more than 0.15 mass%. In particular, if 0.05% by mass or more and inevitably 0.15% by mass or more of inevitable impurities such as Mn, Mg and Zn are contained, the curing at the time of rolling becomes large and cracks easily occur during rolling.

The average grain size of the aluminum alloy foil after final annealing is preferably 20 占 퐉 or less. The average crystal grain size is preferably 18 탆 or less, particularly 15 탆 or less from the viewpoint of preventing uneven deformation during molding. On the other hand, when the lower limit value is 5 占 퐉 or more, the tensile strength TS in the 0 占 direction, 45 占 and 90 占 direction of the foil rolling direction and the average value of the proof stress YS are preferable in view of satisfying YS / TS? Do. If the average crystal grain size is excessively large, the number of crystal grains in the cross-sectional direction becomes too small and localization of deformation occurs, so that the elongation value is lowered and the formability is lowered. Further, since the surface is roughened, the adhesion with the resin film is deteriorated.

On the other hand, in the present invention, the average crystal grain size can be measured as follows. First, an aluminum alloy foil was electrolytically polished at a voltage of 20 V using a mixed solution of 20% by volume of perchloric acid and 80% by volume of ethanol at a temperature of 5 占 폚 or less. After washing with water and drying, The anodic oxide film was formed in a mixed solution of phosphoric acid +47 volume% methanol + 3 volume% hydrofluoric acid at a voltage of 20 V, and then subjected to optical microscopy to observe the crystal grains and take a photograph. For the next photographed photograph, the average particle size is measured using the cutting method. The cutting method is a method of counting how many crystal positions are present in a predetermined line segment (line segment), and using a size obtained by dividing a line segment by the number.

(2) Physical properties of aluminum alloy foil

As described above, the aluminum alloy foil that can be used for the molding package material of the present embodiment has an aluminum alloy foil having a composition in which the composition and the grain size of the aluminum alloy foil satisfy the specific conditions, It is preferable that the average value of the tensile strength TS and the proof stress YS in the direction of 90 degrees satisfy YS / TS? 0.60. When the YS / TS value exceeds 0.60, the tensile strength and the proof stress can be greatly increased by making the crystal grains finer in order to make the molded package material a package composed of an alloy foil having the same thin plate thickness as the outer casing for a secondary battery However, the increase in work hardenability is reduced, the elongation value is lowered, and the formability is sometimes lowered. The YS / TS value is preferably 0.20 or more and 0.55 or less in view of improvement in moldability.

As described above, the aluminum alloy foil used in the molding pavement material of the present embodiment is preferably made of an aluminum alloy foil having a composition in the range of 0 degree, 45 degrees, 90 degrees to the rolling direction The average elongation is preferably 20.0% or more. Particularly, in order to perform molding such as forming a deep recess in order to improve the capacity of the package, as in the outer packaging material for a secondary battery or the packaging container for medicines of the present invention, Or more, particularly preferably 25% or more. When it is less than 20%, cracks easily occur at the boundary between the concave portion and the flat portion. On the other hand, the upper limit is not particularly limited.

The thickness of the aluminum alloy foil used for the molding pavement material of the present embodiment is arbitrary and can be appropriately adjusted depending on the application and molding conditions, but is generally preferably from 10 to 100 mu m. When the thickness of the aluminum alloy foil is 10 탆 or more, the tensile strength is also improved. If the thickness is less than 10 탆, the tensile strength may be lowered. On the other hand, if the thickness exceeds 100 m, the entire thickness of the package becomes very thick, which makes it difficult to obtain a molded package with a small size (small size). The thickness of the aluminum alloy foil is preferably 30 to 50 mu m. On the other hand, when used as a casing of a secondary battery for use in the present invention, a thickness of 50 μm or more, preferably 70 μm or more and 300 μm or less after processing is recommended from the viewpoint of ensuring the capacity of the secondary battery as a molded product. When it is used as a medicine packaging material, it is recommended that the thickness after processing is 30 占 퐉 or more, preferably 50 占 퐉 or more and 200 占 퐉 or less from the viewpoint of strength or moisture resistance, but the thickness is not particularly limited.

&Lt; Process for producing aluminum alloy foil &

The manufacturing method of the molded package material affecting the present embodiment is characterized in that it comprises 0.8 to 1.7 mass% of Fe, 0.05 to 0.20 mass% of Si, 0.0025 to 0.0200 mass% of Cu and the balance of Al and inevitable impurities A step of cooling the aluminum alloy ingot at a temperature of not less than 550 DEG C and not more than 610 DEG C for not less than 3 hours, a step of cooling the aluminum alloy ingot at a temperature of not less than 400 DEG C and not more than 450 DEG C after the homogenization and holding, A step of performing intermediate annealing which is carried out at a temperature of 300 ° C or higher and 450 ° C or lower before or during the cold rolling for 1 hour or longer; and a step of final annealing after the cold rolling to obtain the aluminum alloy foil .

According to this method, the aluminum alloy ingot formed in a specific composition is homogenized at a high temperature and then cooled to a lower temperature to control the temperature condition of the intermediate annealing performed during the cold rolling step, It is possible to obtain a molded package material in which the average crystal grain size of the aluminum alloy foil formed in the composition satisfies the specific conditions. Particularly, in order to have a specific ratio of the average tensile strength in the three directions and the average 0.2% proof stress, and to have a high average elongation in three directions, a molded package material having an excellent elongation value and having good moldability is obtained . Therefore, the molded package material obtained by the above-described method can be subjected to deep drawing molding under particularly harsh conditions, can increase the capacity of the contents, and can package relatively thick contents. Therefore, As shown in FIG. In addition, the molded package material obtained by the above method is unlikely to undergo uneven deformation at the time of deep drawing molding, and has less cracks at the corner of the molded article, and moisture or air from outside does not penetrate into the molded package material Therefore, deterioration of the contents in the molded package material can be prevented.

Hereinafter, a method for producing the molded package material will be described in detail.

In order to obtain an aluminum alloy foil having a good formability to be used for the molding package material, an ingot is first obtained by dissolving an aluminum alloy having the above composition, and then by half-continuous casting. The subsequent homogenization treatment is carried out at a temperature of 550 ° C or higher and 610 ° C or lower for 3 hours or longer, followed by cooling. As the cooling step, the temperature is 400 ° C or higher and 450 ° C or lower. The cooling rate is preferably 20 to 50 degrees / hr. On the other hand, after cooling from 400 ° C to 450 ° C, it may be maintained for several hours in the above temperature range.

In the homogenizing treatment, since the Fe-based precipitates are not sufficiently coarsened at a holding time of less than 550 ° C and less than 3 hours, the proof stress is increased, and the degree of 0, 45, 90 The ratio of the tensile strength TS in the direction to the average value of the proof stress YS and the value of YS / TS exceeds 0.60, the elongation value is lowered, and the formability is sometimes deteriorated. If the homogenization treatment temperature exceeds 610 DEG C, the ingot may locally melt, which is undesirable in manufacturing. In addition, it is not preferable since minute hydrogen gas mixed at the time of casting is likely to come out from the surface and be swollen on the surface of the material. The homogenization treatment temperature is preferably 580 캜 or higher and 610 캜 or lower.

In the production method of the present invention, after the homogenization treatment is performed, the solution is cooled to 400 ° C or more and 450 ° C or less. When the cooling temperature is lower than 400 ° C, the precipitation amount of Fe-based precipitates becomes excessively large, and crystal grains become coarse and the elongation value decreases. When the cooling temperature exceeds 450 DEG C, the high solid content of Fe increases and the ratio of the tensile strength TS to the average value of the tensile strength TS in the direction of 0 DEG, 45 DEG and 90 DEG with respect to the rolling direction and the YS / TS Is more than 0.60, the elongation value is lowered and the moldability is lowered, which is not preferable.

In the production method of the present invention, hot rolling is performed after the homogenization treatment and the cooling is finished. The finish temperature of the hot rolling is preferably 250 to 400 占 폚. From the viewpoint that it is necessary to recrystallize the aluminum alloy sheet after hot rolling more reliably, it is preferably 300 DEG C or higher.

In the production method of the present invention, cold rolling is performed after the hot rolling. The cold rolling may be performed by a known method, and is not particularly limited.

In the production method of the present invention, it is necessary to carry out the intermediate annealing at 300 DEG C or more and 450 DEG C or less for 1 hour or more before or during the cold rolling. When the temperature of the intermediate annealing is less than 300 ° C, the elongation value is lowered. If the intermediate annealing temperature exceeds 450 DEG C, the ratio of the tensile strength TS in the direction of 0 DEG, 45 DEG and 90 DEG to the average value of the yield strength YS and YS / TS value in the rolling direction exceeds 0.60, , And moldability is deteriorated. From the viewpoint of lowering the proof stress, the intermediate annealing preferably lowers the Fe solubility (solid solution amount), and is preferably 300 ° C or higher and 400 ° C or lower.

After completion of the cold rolling, final annealing is preferably carried out to make the aluminum alloy foil a complete soft foil. On the other hand, the holding temperature of the final annealing is preferably 200 to 400 DEG C for 5 hours or more to be completely recrystallized and also from the viewpoint of completely volatilizing the rolling oil. When the temperature is lower than 200 DEG C, it may be difficult to obtain a completely soft foil. Further, when the temperature exceeds 400 ° C, the Fe solubility increases and the proof stress increases. Therefore, the ratio of the average value of the tensile strength TS to the tensile strength TS in the direction of 0 deg., 45 deg., And 90 deg. Is more than 0.60, the elongation value is lowered and the moldability is lowered, which is not preferable. More preferably, the final annealing temperature is 240 ° C or higher and 320 ° C or lower. When the final releasing retention time is less than 5 hours, the rolling oil at the time of peel rolling is not sufficiently volatilized, so that the wettability of the foil surface is lowered and the adhesion with the laminate resin can be easily deteriorated. Further, it is preferable that the temperature raising rate at the time of final annealing is 50 DEG C / hr or less. When the temperature raising rate exceeds 50 DEG C / hr, coarse grains are easily generated, nonuniform deformation easily occurs at the time of molding, and the formability may be deteriorated.

<Molded package material>

The molding pavement material of the present invention may be composed of a plurality of layers including an aluminum alloy foil layer or the aluminum alloy foil layer 8, and is not particularly limited. In the case of a plurality of layers, an aluminum alloy foil As shown in FIG. Specifically, as shown in Fig. 2, a film 10 made of synthetic resin, an aluminum alloy foil 8, and a heat sealing layer 9 are laminated in this order. The film 10 made of a synthetic resin can be used for the purpose of further improving the moldability of the molded package material or for protecting the aluminum alloy foil 8 which is the main material of the package body, And is laminated and bonded to one surface of the alloy foil 8. As the film 10 made of such a synthetic resin, a polyester film, a nylon film, or the like can be used. The molding pavement material of the present invention can be used as a secondary battery or a medicine packaging container, and in particular, in the case of a secondary battery, the molding pavement material of the present invention can be used as a secondary battery exterior material. In this case, it is necessary to perform heat treatment, heat treatment, and the like of various battery members housed in the casing. Therefore, it is preferable to use a heat-resistant polyester film as the film 10 made of a synthetic resin.

The heat seal layer 9 is for sealing the end portion 7 of the package. As the heat sealing layer 9, conventionally known heat-melting synthetic resins can be used. In particular, any material may be used as long as it is excellent in adhesion with the aluminum alloy foil 8 used in the present invention and can protect the contents. Examples thereof include an unextended (non-oriented) polypropylene film, a biaxially oriented ) Polypropylene film or a maleic acid-modified polyolefin is preferably used.

When the molding pavement material of the present invention is made of a plurality of layers, the film 10 made of a synthetic resin, the aluminum alloy foil 8 used in the present invention, and the heat sealing layer 9 may be laminated in this order, And is not particularly limited as long as it satisfies suitability of contents such as moldability, adhesiveness and the like. For example, an unextended polypropylene film is placed on one side of an aluminum alloy foil through an adhesive film, and the aluminum alloy foil is adhered to the other side of the aluminum alloy foil, And a film made of a synthetic resin can be placed thereon and adhered thereto.

The pressing of the aluminum alloy foil and the polypropylene film is generally performed in a heating environment. The heating conditions are about 160 to 240 ° C. In addition, the pressing conditions are a pressure of 0.5 to 2 kg / cm 2 and a time of about 0.5 to 3 seconds.

As the adhesive for the film 10 made of a synthetic resin, conventionally known adhesives can be used. For example, a urethane adhesive or the like can be used.

The molding pavement material of the present invention can be molded by a known method, and the molding method is not particularly limited, but can be suitably used particularly for deep drawing molding. As one example of a method of obtaining a package using the molding package material according to the present embodiment, a molding package material is cut to a desired size to obtain a packaging material having a desired shape, and a center portion Deep drawing forming is carried out so that it becomes a concave portion, a peripheral portion becomes a flat portion, and a heat sealing layer side becomes an inner surface. Two sheets of the packaging material subjected to the deep drawing forming are used to bond the concave portions facing each other and the peripheral heat sealing layer in contact with each other. Then, a portion is left, and another peripheral portion is heat-sealed to obtain a package. The positive electrode collector 2, the positive electrode 3, the separator 4, the negative electrode 5, and the negative electrode collector 6 are housed in the central portion of the secondary battery so as to be further impregnated in the electrolyte The secondary battery can be manufactured, and further, the lead wire drawn from the secondary battery body is discharged to the outside, and the mouth of the bag is heat-sealed again.

According to the secondary battery of the present invention, in order to use the molding package material having the aluminum alloy foil having the excellent formability, deep drawing molding under severe conditions such as deepening of the recessed portion with an excellent growth rate, It is possible to form an outer casing for a secondary battery having a large capacity and thus a charging capacity or a high output secondary battery that can withstand use for a long time can be obtained. In addition, according to the above-described secondary battery, uneven deformation of the exterior material is unlikely to occur during deep drawing molding, and cracks and breakage at the corner of the molded article are suppressed. And deterioration of the contents of the battery can be prevented as much as possible.

When the pharmaceutical packaging container is obtained by using the molding package material of the present invention, the above-described method can be used for the molding method. For example, medicine (tablets, capsules, etc.) for PTP can be stored and used as a medicine packaging container. The pharmaceutical packaging container of the present invention can be manufactured by a known method, and the manufacturing method is not particularly limited.

According to the pharmaceutical packaging container, since the aluminum alloy molding package material having a high growth rate and good formability is used, it is possible to obtain a medicine packaging container which can perform deep drawing molding and desirably reduce the material of the molding package. Further, according to the pharmaceutical packaging container, since the average crystal grain size of the aluminum alloy foil is small, uneven deformation does not occur at the time of deep drawing forming and cracks at the corner of the molded article are reduced, It is difficult to penetrate into the package material, and it is also excellent in long-term quality control such as refining of contents requiring steam barrier property when stored.

Although the embodiments of the present invention have been described with reference to the drawings, these are only examples of the present invention, and various configurations other than the above may be used.

For example, in the above-described embodiment, the material for the secondary battery or the molding package for packing the medicines is used, but the material is not particularly limited and may be used for other packaging applications. For example, it may be used for a molding package material of a primary battery other than a secondary battery. In this case, even in the case of a primary battery requiring high durability, which is used under severe conditions, uneven deformation does not occur at the time of deep drawing molding and cracks and breakage at the corner of the molded article are suppressed. The moisture and air intrusion of the battery can be suppressed, and deterioration of the contents of the battery can be prevented as much as possible.

<Examples>

Hereinafter, the present invention will be further described with reference to Example E, but the present invention is not limited to these Examples.

&Lt; Example 1 >

An aluminum ingot having the composition shown in Table 1 was prepared and homogenized, cooled, hot rolled, cold rolled, thin rolled and finally annealed according to a conventional method to obtain an aluminum alloy foil having a thickness of 35 탆. The tensile strength, 0.2% proof stress and elongation at 0 deg., 45 deg., And 90 deg. Relative to the rolling direction of the obtained aluminum alloy foil were measured. Table 2 also shows the number of rolled sheets cut during cold rolling.

The tensile strength of the aluminum alloy foil was determined by performing a tensile test at a speed of 10 mm / min at a distance of 50 mm between the chucks, using a sample piece (sample piece) having a width of 10 mm, The maximum load associated with the specimen was measured and the stress divided by the cross-sectional area of the original specimen was calculated as the tensile strength. Further, the 0.2% proof stress is obtained by plotting a parallel line at a 0.2% permanent distortion value from the straight line in the elastic region indicated by the first rise of the load-elongation curve in a nearly straight line, Yield point) was obtained. The elongation is calculated as [(L-50) / 50] x 100 where L (mm) is the distance between the chucks when the unidirectional specimen is broken by the same measuring method as in the case of tensile strength.

Next, in order to test the degree of deep drawability of the molding pavement material using the aluminum alloy foil according to the embodiment, the following experiment was conducted. Specifically, 15 parts by weight of maleic anhydride-modified polypropylene having an average particle size of 6 to 8 μm and an organosol formed with 85 parts by weight of toluene were coated on one side of each of the aluminum alloy foils obtained in Examples and Comparative Examples, And dried for 20 seconds to obtain an adhesive film having a thickness of 2 m. Next, a polypropylene film having a thickness of 30 占 퐉 was adhered to the surface of the adhesive film at a temperature of 200 占 폚 under a pressure of 2 kg / cm2 for 1 second for adhesion. Finally, a heat-resistant polyester film having a thickness of 12 占 퐉 was adhered to the other side of the aluminum alloy foil (the surface to which the extruded film was not adhered) through a urethane adhesive agent to obtain a molded package material. The Erickson test was performed on the molded package material, and the degree of deformation capability of the molded package material was measured. The results are shown in Table 2. On the other hand, the Erickson test was conducted by a method based on the method described in JIS Z 2247, with the surface of the heat-resistant polyester film as a protruding surface. The larger the Ericsson value, the greater the deformability.

The average particle diameters of the aluminum alloy foils shown in this example and the comparative example were measured as follows. That is, each of the obtained aluminum alloy foils was electrolytically polished using a mixed solution of 20% by volume of perchloric acid and 80% by volume of ethanol at a temperature of 5 ° C or less, using a voltage of 20 V, washed with water and dried, The anodic oxide film was formed in a mixed solution of 50% phosphoric acid +47% by volume methanol + 3% by volume hydrofluoric acid at a voltage of 20 V, and then the crystal grains were observed using an optical microscope to observe the crystal grains . From the photographed photographs, the average particle size was measured using the cutting method. The cutting method counts how many crystal grains are present in any one line segment, and the size of line segments divided by the number is shown in Table 2.

As apparent from the above-mentioned results, the aluminum alloy foils according to Examples 1 to 18 had larger elongation than the aluminum alloy foils according to Comparative Examples 19 to 25, and had the above deformation ability Is large. The molded package material obtained by using the aluminum alloy foil according to Examples 1 to 18 has a larger Ericson value than that of Comparative Examples 19 to 25, indicating that the deformable capacity is large. Therefore, the molded package material obtained by using the aluminum alloy foil according to Examples 1 to 18 has a large elongation, can be satisfactorily subjected to deep draw forming, and is suitable for packing relatively thick contents. . On the other hand, the aluminum alloy foils according to Examples 1 to 18 hardly undergo rolling cutting during cold rolling, and are easy to manufacture.

&Lt; Example 2 >

An aluminum ingot having an element composition shown in Table 3 was prepared, homogenized, cooled and hot-rolled to obtain an aluminum plate having a thickness of 2.4 mm. The aluminum plate was subjected to cold rolling and then subjected to intermediate annealing under the conditions of the holding temperature and the holding time shown in Table 3 at a plate thickness of 0.55 mm and further subjected to cold rolling to obtain an aluminum alloy foil having a thickness of 35 탆 . Then, final annealing was performed under the conditions of the holding temperature, the holding time, and the heating rate shown in Table 3 to obtain an aluminum alloy foil. Table 4 shows the tensile strength, 0.2% proof stress, elongation, crystal grain size, Erickson value, and the number of rolling cuts of the obtained aluminum alloy foil.

As clearly shown in the above results, the aluminum alloy foils according to Examples 1 to 18 show larger elongation and greater deformability than the aluminum alloy foils 19 to 37 according to the comparative example. In addition, the molded package material obtained by using the aluminum alloy foil according to Examples 1 to 18 has a larger Erickson value than those relating to Comparative Examples 19 to 37, indicating that the deformation capacity is large. Therefore, it can be seen that the molded package material obtained by using the aluminum alloy foils according to Examples 1 to 18 can be preferably subjected to deep draw forming, and is suitable for packing relatively thick contents. On the other hand, the aluminum alloy foils according to Examples 1 to 18 hardly cause rolling cutting during cold rolling, and are easy to manufacture.

The present invention has been described above based on the embodiments. The above embodiments are merely examples, and various modifications are possible, and such modifications are also within the scope of the present invention.

1 Exterior material (molded package material)
2 positive electrode collector
3 Positive
4 Isolation material (separator)
5 negative
6 negative collector
7 End of casing
8 Exterior material body (aluminum alloy foil)
9 heat sealing layer
10 Film made of synthetic resin

Claims (8)

And the balance of Al and inevitable impurities, wherein the average grain size is 20 占 퐉 or less, and the ratio of the average grain size in the rolling direction to the grain size in the rolling direction is in the range of 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, and Cu: 0.0025 to 0.0200 mass% An aluminum alloy foil having an average value YS of a 0.2% proof stress and an average value TS of a maximum tensile strength at 0 degree, 45 degree and 90 degree satisfy YS / TS? 0.60,
Wherein the aluminum alloy foil has an aluminum alloy ingot containing Fe in an amount of 0.8 to 1.7 mass%, Si in an amount of 0.05 to 0.20 mass%, and Cu in an amount of 0.0025 to 0.0200 mass%, the balance being Al and inevitable impurities, And then further cooled to 400 DEG C or more and 450 DEG C or less and then subjected to hot rolling and cold rolling, and at or before 300 DEG C to 450 DEG C for 1 hour Or more, and performing final annealing after cold rolling to obtain a molded package material. The method according to claim 1,
Wherein said aluminum alloy foil has an average value of elongation in the directions of 0 deg., 45 deg. And 90 deg. Relative to the rolling direction of 20.0% or higher. The method according to claim 1,
A film made of a synthetic resin laminated on one side of the aluminum alloy foil,
And a heat sealing layer laminated on the other side of the aluminum alloy foil. The method according to claim 1,
Molded packaging material used for pharmaceutical packaging or secondary battery enclosure. A secondary battery using the molded package material according to any one of claims 1 to 4. A pharmaceutical packaging container using the molded package material according to any one of claims 1 to 4. The method of manufacturing a molded package material according to any one of claims 1 to 4,
An ingot of an aluminum alloy containing 0.8 to 1.7% by mass of Fe, 0.05 to 0.20% by mass of Si and 0.0025 to 0.0200% by mass of Cu and the balance of Al and inevitable impurities at 550 DEG C or more and 610 DEG C or less for 3 hours or more A step of performing homogenization maintenance,
After the homogenization is maintained, cooling to 400 DEG C or more and 450 DEG C or less;
A step of performing hot rolling and cold rolling after cooling,
A step of performing an intermediate annealing step of holding at least 300 ° C to 450 ° C for at least 1 hour before or during the cold rolling,
And performing final annealing after the cold rolling to obtain the aluminum alloy foil. delete

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