JPWO2012036181A1 - Molded packaging material - Google Patents

Abstract

Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, which provides aluminum alloy molded packaging material having good formability The balance is made of Al and inevitable impurities, the average crystal grain size is 20 μm or less, the average value YS of 0.2% proof stress and the average of the maximum tensile strength at 0 °, 45 °, and 90 ° with respect to the rolling direction. Provided is a molded package material 1 including an aluminum alloy foil 8 having a value TS satisfying YS / TS ≦ 0.60.

Description

  The present invention relates to a molded packaging material, a secondary battery using the molded packaging material, a pharmaceutical packaging container, and a method for producing the same.

  In many cases, a PTP (press-through package) for packaging pharmaceutical products takes a packaging form by a combination of a container and a lid. Deep drawing is required on the container side, and in a normal strip package, a plastic film, for example, a resin film such as polypropylene is used as the container. In the case of tablets or the like whose contents require water vapor barrier properties during storage, they are often used as composites in which an aluminum foil having a high barrier property and a resin film are bonded to one or both sides.

  In recent years, various forms and sizes of pharmaceutical products have been put on the market, and the need to make the packaging for packaging these products deeper or more complicated to match these forms has increased. .

  Further, a molded package material having a composite structure in which a resin film is bonded to both surfaces of an aluminum foil is also used for an exterior material of a secondary battery in order to impart water vapor barrier properties.

  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 in electronic devices such as mobile communication devices, notebook computers, headphone stereos, and camcorders. It is useful as its driving source. For example, the secondary battery has a configuration as shown in FIG. That is, a laminated body (secondary battery body) in which the positive electrode current collector 2, the positive electrode 3, the separator (separator) 4, the negative electrode 5, and the negative electrode current collector 6 are laminated in this order is formed into a molded packaging body (exterior material) 1. It is stored in. And the exterior material 1 is heat-sealed in the edge part 7 as needed.

  Here, as shown in FIG. 2, the molded packaging body 1 of FIG. 1 is generally laminated with a heat sealing layer 9 on one side of the exterior material body 8 and a synthetic resin film 10 on the other side. It is an aspect that is laminated. As shown in FIG. 1, the molded package 1 is molded such that the central portion, which is the storage portion, becomes a concave portion and the periphery of the concave portion becomes a flat portion in order to accommodate the positive electrode current collector 2 and the like inside. Yes.

  Secondary batteries are required to have a charge capacity or high output that can withstand long-term use. Therefore, the structure of the element composed of battery electrodes, current collectors, and separators has become complicated and multi-layered, and molding under harsh conditions such as deeper recess formation is required. I came.

  Conventionally, as the molded packaging body 1 and the exterior material body 8, a metal foil, particularly an aluminum alloy foil, which is difficult to permeate moisture, air, etc., and has excellent moldability so as not to adversely affect the quality of the contents. It is used. As the aluminum alloy foil, one having a composition defined in JIS 1100, 3003, 3004, 8079 or 8021 (JIS H 4160) is used. Such an aluminum alloy foil is excellent in tensile strength and hardly breaks.

  However, some of the above aluminum alloy foils have a low tensile elongation, and cracks and pinholes may occur when severe molding is performed to form deep recesses. That is, when obtaining the molded packaging body 1 and the exterior material main body 8, there is no problem when the aluminum alloy foil is formed into a relatively shallow recess, but the aluminum alloy foil is used to increase the capacity of the contents. If a deep recess is formed in the center of the package, cracks and the like are likely to occur at the boundary between the recess and the flat part, moisture and air are easily transmitted, and the quality of the contents is adversely affected. . In particular, when used as a secondary battery exterior material, when moisture or air permeates, hydrofluoric acid is generated by reaction with the electrolyte inside the battery, and the inside of the battery is easily corroded.

  Conventionally, an aluminum foil having a thickness of 20 to 60 μm and an elongation of 0%, 45 degrees, and 90 degrees in the rolling direction of 11% or more has been proposed as an exterior material body (Patent Document 1). Similarly, when a specific amount of Fe or Si is added to Al as an exterior material body, both tensile elongation and tensile strength are improved, and an aluminum alloy foil suitable as an exterior material body for a secondary battery can be obtained. It has been proposed (Patent Document 2).

JP 2005-163077 A Japanese Patent Laid-Open No. 2001-176659

  However, the prior art described in the above literature 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 as battery exterior materials.

  Secondly, in the field of secondary batteries used for automobiles and power tools in addition to the above applications, deeper drawability or stretch formability is required in order to aim at high output, and higher tensile strength for this purpose is required. There is a need for an aluminum alloy foil having elongation.

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

  As a result of intensive studies in view of the above circumstances, the present inventors have found that when the composition of the aluminum alloy foil and the average crystal grain size satisfy specific conditions, 3 degrees in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction. Regarding the mechanical properties in the direction, it was found that a molded packaging material having good moldability can be obtained by setting the average tensile strength and the average 0.2% proof stress to a specific ratio.

  In general, an aluminum alloy foil is manufactured by sequentially performing steps of casting, homogenization treatment, hot rolling, and cold rolling. Therefore, as a result of intensive studies on the conditions of each of these steps, the present inventors held at a high temperature during homogenization treatment of an aluminum alloy ingot having a specific composition, and then cooled to a low temperature. The inventors have found that a molded package material having good formability can be obtained by controlling the temperature conditions of the intermediate annealing performed before or during the rolling process, and have reached the present invention.

  That is, according to the present invention, Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, the balance being Al and inevitable It consists of impurities, the average crystal grain size is 20 μm or less, the average value YS of 0.2% proof stress and the average value TS of the maximum tensile strength at 0 °, 45 ° and 90 ° with respect to the rolling direction are YS / TS ≦ 0 A molded packaging material comprising an aluminum alloy foil satisfying .60 is provided.

  According to this molded packaging material, the composition and average crystal grain size of the aluminum alloy foil satisfy specific conditions, and the average tensile strength in three directions and the average 0.2% proof stress of the aluminum alloy foil have a specific ratio. Therefore, a molded package material having good moldability can be obtained. In particular, the aluminum alloy foil preferably further has an average value of elongation of 20.0% or more in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction. By such a regulation, the molded packaging material of the present invention can be deep-drawn under particularly severe conditions, and accommodates relatively thick contents such as components laminated in multiple layers such as a secondary battery. Therefore, it can be suitably used as a molding packaging material for various uses. In addition, because it is specified in the above specific conditions, non-uniform deformation is unlikely to occur during deep drawing, cracks at the corners of the molded body can be suppressed, and moisture and air from the outside are contained in the molded packaging material. Since it does not invade, the deterioration of the contents in the molded packaging material can be reliably prevented.

  Moreover, according to this invention, the secondary battery using said shaping | molding package body material is provided.

  According to this secondary battery, since the molded packaging material having the above-mentioned good moldability is used, deep drawing can be performed, and the outer battery is provided with a relatively thick secondary battery. It is possible to obtain an excellent secondary battery having a charging capacity that can withstand the use of time and a high output performance. Further, according to this secondary battery, since the molded packaging material of the present invention is used, non-uniform deformation hardly occurs at the time of deep drawing, cracks and pinholes do not occur at the corner of the molded body, Since it has an exterior material that makes it difficult for moisture and air from the outside to enter the molded package, it can prevent the hydrofluoric acid from being generated by the reaction with the electrolyte inside the battery and corroding the inside of the battery. It is also excellent in stability.

  Moreover, according to this invention, the pharmaceutical packaging container using said shaping | molding package material is provided.

  According to this pharmaceutical packaging container, since the molded packaging material having the above-mentioned good moldability is used, deep drawing can be performed, and a pharmaceutical packaging container molded more deeply can be obtained. Further, according to this pharmaceutical packaging container, since the average particle diameter of the aluminum alloy foil is small, non-uniform deformation hardly occurs at the time of deep drawing molding, and there are few cracks at the corner of the molded body, so that water vapor from the outside is not generated. It is difficult to penetrate into the molded packaging material, and it is possible to suitably package tablets or the like whose contents require water vapor barrier properties when stored. Therefore, if the pharmaceutical packaging container of the present invention is used as a PTP for pharmaceuticals, the pharmaceuticals can be stably held over a long period of time.

  Moreover, according to this invention, it is the method of said shaping | molding package material, Comprising: Fe: 0.8-1.7mass%, Si: 0.05-0.20mass%, Cu: 0.0025-0. A step of homogenizing and holding an aluminum alloy ingot containing 0200 mass%, the balance being Al and inevitable impurities at 550 ° C. or more and 610 ° C. or less for 3 hours or more, and 400 to 450 ° C. or less after the homogenization holding A step of cooling to a temperature, a step of performing hot rolling and cold rolling, a step of performing an intermediate annealing to be held at 300 ° C. or higher and 450 ° C. or lower for 1 hour or longer before or during the cold rolling, and the cold And subjecting to a final annealing after rolling to obtain the above aluminum alloy foil.

  According to this method, after holding at a high temperature during homogenization treatment of an aluminum alloy ingot of a specific composition, it is cooled and then hot-rolled, and the intermediate annealing performed in the middle of the cold-rolling process By controlling the temperature condition, it is possible to obtain a molded packaging material whose average crystal grain size satisfies a specific condition, and the above-described average tensile strength in three directions and average 0.2% proof stress are in a specific ratio. Thus, a molded package material having an excellent elongation value and good moldability can be obtained. In particular, since the average elongation in three predetermined directions has a high value, a molded package material having an excellent elongation value and good moldability can be obtained with certainty. Therefore, the molded packaging material obtained by this method can be deep-drawn under particularly severe conditions, can increase the content capacity, and can wrap relatively thick contents. It can be suitably used as a molding packaging material for various uses. In addition, the molded packaging material obtained by this method is less susceptible to non-uniform deformation during deep drawing molding, and there are few cracks at the corners of the molded product, and moisture and air from the outside penetrate into the molded packaging material. Therefore, it is possible to prevent deterioration of contents such as secondary battery parts and medicines contained in the molded package.

  According to the present invention, since the composition and average crystal grain size of the aluminum alloy foil satisfy specific conditions, the molded packaging material, secondary battery, or pharmaceutical packaging having an excellent elongation value and good moldability A container is obtained. Moreover, according to this invention, since the aluminum alloy ingot of a specific composition is processed by a specific process, the molded package material which has the outstanding elongation value and favorable moldability is obtained efficiently.

It is typical sectional drawing which showed an example of the internal structure of a sheet-like thin polymer lithium ion secondary battery. It is typical sectional drawing which showed the general example of the exterior material of a secondary battery.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. Further, in the embodiment of the present invention, “A to B” means A or more and B or less.

<Aluminum alloy foil>
(1) Composition and average crystal grain size of aluminum alloy foil The molded package material according to the present embodiment contains Fe, Si, Cu in a specific composition, the balance is made of Al and inevitable impurities, and the average crystal grain An aluminum alloy foil having a diameter of 20 μm or less is provided.

  Here, content of Fe contained in said aluminum alloy foil is 0.8-1.7 mass%. When Fe is less than 0.8 mass%, both the tensile strength and the elongation are lowered, and the moldability is lowered. Further, when Fe exceeds 1.7 mass%, both the tensile strength and the proof stress increase, and the ratio between the tensile strength TS and the average value of the proof strength YS in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction, YS / Since the value of TS exceeds 0.60, the moldability is lowered. In particular, 1.0 mass% or more and 1.6 mass% or less are more preferable from the viewpoint of the balance between strength and elongation.

  Moreover, content of Si contained in said aluminum alloy foil is 0.05-0.20 mass%. If Si is less than 0.05 mass%, both the tensile strength and the elongation decrease, which is not preferable. On the other hand, when Si exceeds 0.20 mass%, the tensile strength increases, but the elongation decreases and the formability decreases. In addition, since the crystal grain size becomes large, uniform deformation during molding hardly occurs. Among these numerical values, 0.06 mass% or more and 0.10 mass% or less are particularly preferable from the viewpoint of strength and crystal grain size.

  Moreover, content of Cu contained in said aluminum alloy foil is 0.0025-0.0200 mass%. If the Cu content is 0.0025 mass% or less, the amount of solid solution is small, so the elongation is lowered and the formability is lowered. Moreover, when Cu exceeds 0.0200 mass%, hardening at the time of rolling will be large and it will become easy to produce the cut | disconnection during rolling. Among these numerical values, 0.0050 mass% or more and 0.0100 mass% or less are particularly preferable from the viewpoints of rollability and formability.

  Moreover, the inevitable impurities contained in the aluminum alloy foil are individually 0.05 mass% or less, and the total is 0.15 mass% or less. Alternatively, in particular, if inevitable impurities such as Mn, Mg, Zn, etc. individually exceed 0.05 mass% and the total amount is 0.15 mass%, the curing during rolling is large, and breakage during rolling tends to occur. .

  Moreover, it is preferable that the average crystal grain diameter after final annealing of said aluminum alloy foil is 20 micrometers or less. The average crystal grain size is preferably 18 μm or less, and particularly preferably 15 μm or less from the viewpoint of preventing uneven deformation during molding. In addition, as a lower limit, it is recommended that the average value of the tensile strength TS and the proof stress YS in the 0 degree, 45 degree, and 90 degree directions with respect to the foil rolling direction is 5 μm or more from the viewpoint of satisfying YS / TS ≦ 0.60. The When this average crystal grain size becomes too large, the number of crystal grains occupying in the cross-sectional direction is too small and localization of deformation occurs, resulting in a decrease in elongation value and a decrease in moldability. Moreover, since the surface roughens, adhesiveness with a resin film falls.

  In the present invention, the average crystal grain size can be measured as follows. That is, first, an aluminum alloy foil was subjected to electropolishing at a voltage of 20 V using a 20 volume% perchloric acid + 80 volume% ethanol mixed solution at 5 ° C. or less, washed with water, dried, and then 50 volume% phosphoric acid at 25 ° C. or less + 47 An anodic oxide film is formed at a voltage of 20 V in a mixed solution of volume% methanol + 3 volume% hydrofluoric acid, and then polarized with an optical microscope to observe crystal grains and take a photograph. Next, from the photograph taken, the average particle diameter is measured by a cutting method. The cutting method is a method of counting the number of crystal grains in a predetermined line segment and using a size obtained by dividing the line segment by the number.

(2) Physical Properties of Aluminum Alloy Foil As described above, the aluminum alloy foil used in the molded packaging material of the present embodiment has a composition and a crystal grain size that satisfy specific conditions. It is preferable that the average value of the tensile strength TS and the proof stress YS in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction satisfy YS / TS ≦ 0.60. If the value of YS / TS exceeds 0.60, the crystal grains must be refined in order to make the molded package material into a package made of an alloy foil having a thin plate thickness, such as a secondary battery exterior material. However, although tensile strength and proof stress are greatly increased, there is little increase in work-curing property, elongation value is decreased, and moldability may be decreased. The value of YS / TS is preferably 0.20 or more and 0.55 or less from the viewpoint of improving moldability.

  As described above, the aluminum alloy foil used for the molded packaging material of the present embodiment satisfies the specific conditions for the composition and crystal grain size of the aluminum alloy foil, and therefore, the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction. The average elongation is preferably 20.0% or more. In particular, in order to perform molding so as to form deep recesses in order to increase the capacity of the package, such as the outer packaging material for a secondary battery or a pharmaceutical packaging container, the average elongation in the above three directions is 20. It is preferably 0% or more, particularly 25% or more. If it is less than 20%, cracks at the boundary between the recess and the flat portion are likely to occur. The upper limit is not particularly limited.

  The thickness of the aluminum alloy foil used for the molded packaging material of the present embodiment is arbitrary, and can be appropriately adjusted according to the application, molding conditions, etc., but generally 10 to 100 μm is preferable. If the thickness of the aluminum alloy foil is 10 μm or more, the tensile strength is improved. On the other hand, if the thickness is less than 10 μm, the tensile strength may decrease. On the other hand, if the thickness exceeds 100 μm, the thickness of the entire package becomes too thick and it is difficult to reduce the size of the resulting molded package, which may be undesirable. As for the thickness of this aluminum alloy foil, 30-50 micrometers is especially preferable. In addition, when used for an outer packaging material of a secondary battery which is an application of the present invention, a thickness after processing is 50 μm or more, preferably 70 μm or more and 300 μm or less from the viewpoint of securing a capacity as a molded article of a secondary battery. Recommended by In addition, when used as a packaging material for pharmaceuticals, the thickness after processing is recommended to be 30 μm or more, preferably 50 μm or more and 200 μm or less from the viewpoint of strength and moisture resistance, but these thicknesses are particularly limited. It is not something.

<Method for producing aluminum alloy foil>
The manufacturing method of the molded package material according to the present embodiment contains Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, A step of homogenizing and holding an aluminum alloy ingot consisting of Al and inevitable impurities at 550 ° C. or more and 610 ° C. or less for 3 hours or more, and cooling to 400 ° C. or more and 450 ° C. or less after the homogenization holding; A step of performing hot rolling and cold rolling after the cooling, a step of performing an intermediate annealing to be held at 300 ° C. or higher and 450 ° C. or lower for 1 hour or more before or during the cold rolling, and a final step after the cold rolling And performing the annealing to obtain the aluminum alloy foil.

  According to this method, after holding at a high temperature during homogenization treatment of an aluminum alloy ingot of a specific composition, it is further cooled to a low temperature, and the temperature conditions of intermediate annealing performed in the middle of the cold rolling process are controlled. By doing so, it is possible to obtain a molded package material in which the average crystal grain size of the obtained aluminum alloy foil having a specific composition satisfies a specific condition. In particular, since the average tensile strength in the three directions and the average 0.2% proof stress are in a specific ratio, the average elongation in the three directions has a high value, and thus has an excellent elongation value and good moldability. A molded packaging material having the following is obtained. Therefore, the molded packaging material obtained by this method can be deep-drawn under particularly severe conditions, can increase the content capacity, and can wrap relatively thick contents. Therefore, it can be suitably used as a molding and packaging material for various applications. In addition, the molded packaging material obtained by this method is less susceptible to non-uniform deformation during deep drawing molding, and there are few cracks at the corners of the molded product, and moisture and air from the outside penetrate into the molded packaging material. Therefore, deterioration of the contents in the molded package material can be prevented.

Hereinafter, the method for producing the molded packaging material will be described more specifically.
In order to obtain an aluminum alloy foil having good formability for use in the above-described molded package material, first, an aluminum alloy having the above composition is melted, and then an ingot is obtained by a semi-continuous casting method. Thereafter, the homogenization is cooled after holding at 550 ° C. or more and 610 ° C. or less for 3 hours or more, and is cooled to 400 ° C. or more and 450 ° C. or less as a cooling step. The cooling rate is preferably 20 to 50 ° C./hr. In addition, after cooling to 400 degreeC or more and 450 degrees C or less, you may hold | maintain several hours in this temperature range.

  In the homogenization treatment, when the holding time is less than 550 ° C. and less than 3 hours, the Fe-based precipitates are not sufficiently coarsened, so the yield strength is increased, and the tensile strength in the 0, 45, and 90 degrees directions with respect to the rolling direction is increased. The ratio of the strength TS and the average value of the proof stress YS, the value of YS / TS, exceeds 0.60, the elongation value decreases, and the moldability may be inferior. If the homogenization temperature exceeds 610 ° C., the ingot may be locally melted, which is not preferable in production. Moreover, since very little hydrogen gas mixed at the time of casting comes out on the surface and it becomes easy to produce a swelling on the material surface, it is not preferable. The homogenization temperature is preferably 580 ° C or higher and 610 ° C or lower.

  The manufacturing method of the present invention is cooled to 400 ° C. or higher and 450 ° C. or lower after the homogenization treatment. When the cooling temperature is less than 400 ° C., the amount of Fe-based precipitates increases too much, the crystal grains become coarse, and the elongation value decreases. When the cooling temperature exceeds 450 ° C., the solid solution amount of Fe increases, so the yield strength increases, and the average value of the tensile strength TS and the yield strength YS in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction The ratio of YS / TS exceeds 0.60, and the elongation value decreases and the moldability decreases.

  In the production method of the present invention, hot rolling is performed after the homogenization treatment and cooling are completed. The end temperature of hot rolling is preferably 250 to 400 ° C. From the viewpoint that it is necessary to recrystallize the aluminum alloy sheet after hot rolling more reliably, it is recommended that the temperature is preferably 300 ° C. or higher.

  The manufacturing method of this invention implements cold rolling after the said hot rolling. This cold rolling can be performed by a known method and is not particularly limited.

  In the production method of the present invention, it is necessary to perform intermediate annealing at 300 ° C. or more and 450 ° C. or less for 1 hour or more before or during the cold rolling. When the intermediate annealing temperature is less than 300 ° C., the elongation value decreases. When the temperature of the intermediate annealing exceeds 450 ° C., the ratio of the tensile strength TS and the average value of the proof stress YS in the 0 degree, 45 degree and 90 degree directions with respect to the rolling direction, the value of YS / TS exceeds 0.60. Thus, the elongation value is lowered, and the moldability is lowered. The intermediate annealing is preferably performed at a temperature of 300 ° C. or more and 400 ° C. or less from the viewpoint of reducing the yield strength by reducing the amount of Fe solid solution.

  After the end of the cold rolling, it is preferable to perform final annealing to make the aluminum alloy foil a complete soft foil. In addition, the holding temperature of final annealing is preferable from a viewpoint which volatilizes rolling oil completely, recrystallizing at 200-400 degreeC for 5 hours or more. If it is less than 200 degreeC, it may be difficult to obtain perfect soft foil. Further, when the temperature exceeds 400 ° C., the amount of solid solution of Fe increases and the yield strength increases, so the ratio between the tensile strength TS and the average value of the yield strength YS in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction. The value of YS / TS exceeds 0.60, which is not preferable because the elongation value decreases and the moldability may decrease. A more preferable final annealing temperature is 240 ° C. or higher and 320 ° C. or lower. If the holding time of the final annealing is less than 5 hours, the rolling oil at the time of foil rolling is not sufficiently volatilized, so that the wettability of the foil surface is lowered and the adhesiveness with the laminate resin is likely to be lowered. Furthermore, it is desirable that the temperature increase rate during the final annealing is 50 ° C./hr or less. When the rate of temperature rise exceeds 50 ° C./hr, coarse particles are likely to be generated, and non-uniform deformation is likely to occur during molding, which may reduce moldability.

<Molded packaging material>
The molded packaging material of the present invention may be composed of a single layer of aluminum alloy foil or a plurality of layers including the above-described eight layers of aluminum alloy foil, and is not particularly limited. It is necessary that at least an aluminum alloy foil is provided as a constituent element. Specifically, as illustrated in FIG. 2, an example in which a synthetic resin film 10, an aluminum alloy foil 8, and a heat sealing layer 9 are laminated in this order can be exemplified. The synthetic resin film 10 is used to further improve the moldability of the molded packaging material, to protect the aluminum alloy foil 8 that is the main material of the packaging body, or to enable printing. Is laminated and adhered to one side. As such a synthetic resin film 10, a polyester film, a nylon film, or the like is used. The molded packaging material of the present invention can be used as a secondary battery or a pharmaceutical packaging container. In particular, when a secondary battery is used, the molded packaging material of the present invention is used for a secondary battery exterior material. Can do. In this case, since it is necessary to perform heat generation and heat dissipation treatment of various battery members housed in the exterior material, it is preferable to use a heat-resistant polyester film as the synthetic resin film 10.

  The heat sealing layer 9 is for sealing the end 7 of the package. As the heat sealing layer 9, a conventionally known heat-sealable synthetic resin can be used. In particular, any material may be used as long as it has excellent adhesion to the aluminum alloy foil 8 used in the present invention and can protect the contents. For example, an unstretched polypropylene film, a biaxially stretched polypropylene film, or a maleic acid-modified polyolefin is used. It is preferable to use it.

  When the molded packaging material of the present invention has a plurality of layers, the synthetic resin film 10, the aluminum alloy foil 8 used in the present invention, and the heat sealing layer 9 may be laminated in this order. There is no particular limitation as long as the suitability of the contents is satisfied. For example, after placing an unstretched polypropylene film on one side of an aluminum alloy foil through an adhesive film, pressure bonding, and pasting the aluminum alloy foil and the film, on the other side of the aluminum alloy foil, An adhesive can be applied, and a synthetic resin film can be placed thereon for pasting.

The pressure bonding between the aluminum alloy foil and the polypropylene film is generally performed under heating. Heating conditions are about 160-240 degreeC. The pressure bonding 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 synthetic resin film 10, a conventionally known one is used, and for example, a urethane-based adhesive or the like is used.

  The molded package 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. Here, as an example of a method for obtaining a package using the molded package material according to the present embodiment, a packaging material obtained by cutting the molded package material into a desired size to obtain a desired shape is obtained. The packaging material is deep-drawn so that the central portion becomes a concave portion and the peripheral portion becomes a flat portion, and the heat sealing layer side becomes an inner surface. Using two packaging materials subjected to deep drawing, the concave portions are opposed to each other, and the heat sealing layers in the peripheral portion are bonded to each other to be bonded. And a part is left and the other peripheral part is heat-sealed, and a package is obtained. For secondary battery exterior materials, a secondary battery is manufactured by storing 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 and further impregnating with an electrolyte. In addition, the lead wire extending from the secondary battery body can be taken out to the outside, and the bag mouth can be heat-sealed again.

  According to the secondary battery of the present invention, since the molded packaging material provided with the aluminum alloy foil having the above-mentioned good formability is used, it has an excellent elongation rate and is more harsh such as making the recess deeper than before. Under such conditions, deep drawing can be favorably formed, and a secondary battery exterior material having a large capacity can be formed. Therefore, a secondary battery having a charge capacity or high output that can withstand long-time use can be obtained. In addition, according to this secondary battery, the exterior material is unlikely to be deformed unevenly during deep drawing, and cracks and breakage at the corners of the molded body are also suppressed. It suppresses moisture and air intrusion and can prevent deterioration of battery contents as much as possible.

  The method described above can also be adopted as a molding method when a pharmaceutical packaging container is obtained using the molded packaging material of the present invention. For example, in the case of PTP, medicines (tablets, capsules, etc.) can be stored and used as pharmaceutical packaging containers. 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 this pharmaceutical packaging container, since the aluminum alloy molded packaging material having a high elongation rate and good formability is used, the pharmaceutical packaging container can be deep-drawn and the molded packaging material can be reduced. Can be obtained. Further, according to this pharmaceutical packaging container, since the average crystal grain size of the aluminum alloy foil is small, non-uniform deformation hardly occurs at the time of deep drawing, and there are few cracks at the corners of the molded body, so that water vapor from the outside However, it is difficult to penetrate into the molded packaging material, and it is excellent in long-term quality controllability such as tablets of contents that require a water vapor barrier property during storage.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  For example, in the above-described embodiment, the molded package material is used for a secondary battery or a pharmaceutical package. However, the material is not particularly limited, and may be used for other packaging applications. For example, it can also be used as a molded battery material for primary batteries, not secondary batteries. In this way, even in a primary battery that requires high durability used under severe conditions, non-uniform deformation is unlikely to occur during deep drawing, and cracks and breakage at the corners of the molded body are also suppressed. Therefore, it is possible to suppress moisture and air intrusion from the outside in the case of a battery and prevent deterioration of the battery contents as much as possible.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further, this invention is not limited to these Examples.

<Example 1>
An aluminum ingot having the composition shown in Table 1 was prepared, and subjected to homogenization treatment, cooling, hot rolling, cold rolling, foil rolling and final annealing according to a conventional method to obtain an aluminum alloy foil having a thickness of 35 μm. Obtained. The obtained aluminum alloy foil was measured for tensile strength, 0.2% proof stress and elongation at 0 °, 45 ° and 90 ° with respect to the rolling direction, and the results are shown in Table 2. Table 2 also shows the number of rolling breaks during cold rolling.

  The tensile strength of the aluminum alloy foil was a strip-shaped sample piece having a width of 10 mm, a distance between chucks of 50 mm, and a tensile speed of 10 mm / min. The maximum load applied to the strip-shaped sample piece was measured at a speed of 1 mm, and the stress divided by the cross-sectional area of the original sample was calculated as the tensile strength. In addition, 0.2% proof stress is the point where a parallel line is drawn from the permanent strain value of 0.2% from this straight line in the elastic region indicated by a straight line at the initial rise of the load-elongation curve diagram, and intersects with the above curve. That is, the value of the point corresponding to the yield point of the steel material or the like was obtained. Elongation is [(L-50) / 50] × 100, where L (mm) is the distance between chucks when the strip-shaped sample piece is broken by the same measurement method as in the case of tensile strength. It is calculated.

Next, the following experiment was conducted to test the degree of deep drawability of the molded package material using the aluminum alloy foil according to the example. That is, an organosol consisting of 15 parts by weight of maleic anhydride-modified polypropylene having an average particle size of 6 to 8 μm and 85 parts by weight of toluene was applied to one side of each aluminum alloy foil obtained in the examples and comparative examples. The film was dried for 2 seconds to obtain an adhesive film having a thickness of 2 μm. Next, a polypropylene film having a thickness of 30 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, a heat-resistant polyester film having a thickness of 12 μm was attached to the other surface of the aluminum alloy foil (the surface on which the extruded film was not attached) via a urethane adhesive to obtain a molded packaging material. . An Erichsen test was performed on the molded packaging material, and the degree of deformability of the molded packaging material was measured. The results are shown in Table 2. The Erichsen test was conducted by a method based on the method described in JIS Z 2247 with the heat-resistant polyester film surface as the overhanging surface. The larger the Eriksen value, the greater the deformability.

  The average particle size of each aluminum alloy foil shown in this example and the comparative example was measured as follows. That is, each aluminum alloy foil obtained was electropolished at a voltage of 20 V using a 20 volume% perchloric acid + 80 volume% ethanol mixed solution of 5 ° C. or less, washed with water, dried, and then cooled to 50 ° C. of 25 ° C. or less. An anodized film was formed at a voltage of 20 V in a mixed solution of volume% phosphoric acid + 47 volume% methanol + 3 volume% hydrofluoric acid, and then polarized with an optical microscope, the crystal grains were observed and photographed. . From the photograph taken, the average particle diameter was measured by a cutting method. In the cutting method, the number of crystal grains in a certain line segment was counted, and the size obtained by dividing the line segment by the number is shown in Table 2.

  As is clear from the above results, the aluminum alloy foils according to Examples 1 to 18 have a large elongation and a large so-called deformability that can cope with severe forming compared to the aluminum alloy foils according to Comparative Examples 19 to 25. It is shown that. Further, the molded packaging material obtained using the aluminum alloy foils according to Examples 1 to 18 has a large Erichsen value and a large deformability compared to those according to Comparative Examples 19 to 25. Yes. Therefore, the molded packaging material obtained by using the aluminum alloy foils according to Examples 1 to 18 has a large elongation, can perform deep drawing well, and is suitable for packaging a relatively thick content. I understand that In addition, the aluminum alloy foil which concerns on Examples 1-18 hardly produces rolling breakage in the middle of cold rolling, and is easy to manufacture.

<Example 2>
An aluminum ingot having the elemental composition shown in Table 3 was prepared, and subjected to homogenization, cooling, and hot rolling to obtain an aluminum plate having a thickness of 2.4 mm. The aluminum plate was cold-rolled, the plate thickness was 0.55 mm, and after intermediate annealing was performed under the conditions of holding temperature and holding time shown in Table 3, cold-rolling was further performed to obtain 35 μm. An aluminum alloy foil was obtained. And final annealing was performed on each conditions of the holding temperature and holding time which were shown in Table 3, and the temperature increase rate, and aluminum alloy foil was obtained. The obtained aluminum alloy foil was subjected to various evaluations in the same manner as in Example 1. Table 4 shows the tensile strength, 0.2% proof stress, elongation, crystal grain size, Erichsen value, and number of rolling breaks. .

  As is clear from the above results, the aluminum alloy foils according to Examples 1 to 18 have a larger elongation and a higher deformability than the aluminum alloy foils 19 to 37 according to the comparative examples. In addition, the molded packaging material obtained using the aluminum alloy foils according to Examples 1 to 18 has a large Erichsen value and a large deformability compared to those according to Comparative Examples 19 to 37. Yes. Therefore, the molded packaging material obtained using the aluminum alloy foils according to Examples 1 to 18 can be well formed by deep drawing and is suitable for packaging a relatively thick content. I understand. In addition, the aluminum alloy foil which concerns on Examples 1-18 hardly produces rolling breakage in the middle of cold rolling, and is easy to manufacture.

  In the above, this invention was demonstrated based on the Example. It is to be understood by those skilled in the art that this embodiment is merely an example, and that various modifications are possible and that such modifications are within the scope of the present invention.

1 Exterior material (molded packaging material)
2 Positive current collector 3 Positive electrode 4 Separator (separator)
5 Negative Electrode 6 Negative Electrode Current Collector 7 Exterior Material End 8 Exterior Material Body (Aluminum Alloy Foil)
9 Heat sealing layer 10 Synthetic resin film

Claims (8)

  Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, the balance is made of Al and inevitable impurities, and the average crystal grain size Is an aluminum alloy foil satisfying YS / TS ≦ 0.60 with an average value YS of 0.2% proof stress and an average value TS of maximum tensile strength at 0 °, 45 ° and 90 ° with respect to the rolling direction. Molded packaging material provided.   The aluminum alloy foil contains Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, and the balance from Al and inevitable impurities The aluminum alloy ingot is homogenized and maintained at 550 ° C. or more and 610 ° C. or less for 3 hours or more, and further cooled to 400 ° C. or more and 450 ° C. or less, and then subjected to hot rolling and cold rolling. The molded packaging material according to claim 1, which is obtained by performing intermediate annealing that is held at 300 ° C. or higher and 450 ° C. or lower for 1 hour or longer before and during the course, and then performing final annealing after cold rolling.   The molded packaging material according to claim 1 or 2, wherein the aluminum alloy foil has an average value of elongation of 20.0% or more in the 0 degree, 45 degree, and 90 degree directions with respect to the rolling direction. A synthetic resin film laminated on one side of the aluminum alloy foil;
A heat sealing layer laminated on the other side of the aluminum alloy foil;
The molded packaging material according to any one of claims 1 to 3, further comprising:   The shaped packaging material according to any one of claims 1 to 4, which is used for a pharmaceutical packaging or a secondary battery exterior.   The secondary battery using the shaping | molding package body material in any one of Claims 1-5.   A pharmaceutical packaging container using the molded packaging material according to any one of claims 1 to 5. A method for producing a molded package material according to any one of claims 1 to 5,
An aluminum alloy ingot containing Fe: 0.8 to 1.7 mass%, Si: 0.05 to 0.20 mass%, Cu: 0.0025 to 0.0200 mass%, and the balance consisting of Al and inevitable impurities A step of maintaining homogenization at 550 ° C. or more and 610 ° C. or less for 3 hours or more;
Cooling to 400 ° C. or more and 450 ° C. or less after the homogenization holding;
A step of performing hot rolling and cold rolling after the cooling;
Before or during the cold rolling, performing an intermediate annealing that is held at 300 ° C. or higher and 450 ° C. or lower for 1 hour or longer;
Performing the final annealing after the cold rolling to obtain the aluminum alloy foil;
Including a method.