Form packaging material and battery container

Abstract

Forming packaging material (1) for forming a battery container, comprising an outer substrate layer (2) comprising a heat-resistant resin, an inner sealing layer (3) comprising a thermoplastic resin, and a metallic foil (4) as a barrier layer provided between the layers, wherein at least one inner surface (4a) of the metallic foil layer (4) is subjected to a chemical conversion treatment, wherein an inner adhesive resin layer (5) exhibiting adhesion to both the metallic foil and (4) the barrier layer as well as the resin of the inner sealing layer (3) is laminated onto the surface that has undergone chemical conversion, and wherein the inner sealing layer (3) is further laminated by means of the adhesive resin layer (5), wherein the outer substrate layer (2) comprises a biaxially oriented polyethylene terephthalate film.and the film satisfies the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa, |MB − TB| ≤ 30 MPa, where MB is a tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film, and TB is a tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film, wherein the inner adhesive resin layer (5) contains an adhesive comprising a polyolefin resin having a carboxyl group and a multifunctional isocyanate compound, wherein the inner sealing layer (3) contains a propylene homopolymer or a copolymer comprising at least propylene and ethylene as a copolymerization component, and wherein the inner sealing layer (3) is the polymer or copolymer having a melting point of 130°C to 160°C and a melt mass flow rate of 1 to 25 g / 10 min.

Description

Technical field

[0001] The present invention relates to a laminated molded packaging material that is formed into a tray shape by deep drawing or forming for use. More specifically, the present invention relates to a laminated molded packaging material suitable for use as a container material for secondary batteries, such as lithium-ion batteries for notebook personal computers, mobile phones, and in-vehicle or stationary power sources, and which is furthermore also suitable for use as a packaging material for food, pharmaceuticals, and the like. Technical background

[0002] Until now, a laminate packaging material has been widely used as packaging material for foodstuffs, such as ready meals, pharmaceuticals or chemicals, which has a metallic foil that has excellent barrier properties against oxygen or moisture, and in which the metallic foil is laminated between a substrate film and a sealing layer to prevent chemical change, deterioration, decay and the like of the contents (Patent document 1).

[0003] On the other hand, in recent years, in conjunction with the reduction in size and weight of numerous electronic devices, such as office automation equipment (e.g., personal computers), mobile phones, gaming devices, headphone stereo systems, and electronic notebooks, lithium-ion polymer secondary batteries have been increasingly used to achieve this reduction in size and weight, and in many cases, they have also been used as the battery in a power source section. In lithium-ion polymer secondary batteries, a reduction in battery performance or leakage of fluid occurs due to corrosion of the casing when an electrolyte solution in the battery reacts with water to produce hydrofluoric acid.Therefore, the same laminate packing material as described above, which has excellent water vapor barrier properties and good sealing properties, has increasingly been used as a material for use in this case (storage / storage case).

[0004] More specifically, the container material of the lithium-ion polymer secondary battery (packing material) is a laminated packing material in which an outer layer comprising a heat-resistant resin film of a polyester, epoxy, acrylic, or similar type, an intermediate layer comprising primarily an aluminum foil as a water vapor barrier layer, and an inner sealing layer comprising a heat-adhesive polyolefin resin for sealing a polymer electrolyte, which is the contents, are arranged and integrated. (Patent documents 2 and 3).

[0005] The laminate packing material for the battery container, as described above, is formed into a three-dimensional rectangular parallelepiped shape or a similar shape by means of dodging or deep drawing to maximize the capacity to charge / accumulate a polymer electrolyte, and is then used in many cases as a battery container. Related technology documents, patent documents

[0006] Patent document 1: Unexamined Japanese patent application publication number 2004-319414 Patent document 2: Unexamined Japanese patent application publication number 2001-202928 Patent document 3: Unexamined Japanese patent application publication number 2001-266810 Brief description of the invention: Problems solved by the invention

[0007] However, the dimensional properties of the known laminate packaging materials described above are generally poor when formed into a shell shape, and there is a possibility that cracks and holes / pores will be created by the warping or deep drawing process. Therefore, laminate packaging materials have the disadvantage that it is difficult to form them to a desired depth with a sufficiently high capacity.

[0008] Furthermore, since the aluminum foil, acting as a barrier layer, and the inner sealing layer in most of the known laminate packaging materials described above are bonded using a mixed two-component adhesive containing a main agent with a general hydroxyl group and a hardener with an isocyanate group, the lamination strength between the aluminum foil and the sealing layer decreases over time due to the presence of an electrolyte solution, and consequently, this solution can leak out. Therefore, the desired increase in service life is not achieved.

[0009] The present invention was made in light of the technical background described above. A first object of the invention is to provide a molding packaging material whose molding properties are improved and which enables molding with sharpness and great depth without producing cracks and holes.

[0010] It is a further object of the present invention to provide a molded packing material in which a reduction in the interlayer lamination thickness caused by the influence of an electrolyte solution can be prevented, and in which a reduction in the interlayer lamination thickness caused by the influence of heat generation due to repeated charging and discharging and expansion and contraction of the packing material can be prevented, so that the interlayer lamination thickness is excellent, and to prevent a poor external appearance caused when an electrolyte solution adheres to the surface, and furthermore to provide a manufacturing process that can produce such a molded packing material with high productivity.

[0011] The other tasks and advantages of the present invention will become clear from a description of the preferred embodiments, which are described below. Means for solving the tasks

[0012] To solve the aforementioned problems, the present invention provides the following measures / means. [1] A molded packaging material comprises an outer substrate layer containing a heat-resistant resin, an inner sealing layer containing a thermoplastic resin, and a metallic foil as a barrier layer provided between the layers, wherein the substrate layer contains a biaxially oriented polyethylene terephthalate film and this film satisfies the following expressions (I) and (II), 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa Expression (II) MB: Tensile breaking load in the direction M of the biaxially oriented polyethylene terephthalate film, TB: Tensile breaking load in the T direction of biaxially oriented polyethylene terephthalate film. [2] Molded packaging material comprising an outer substrate layer comprising a heat-resistant resin, an inner sealing layer comprising a thermoplastic resin, and a metallic foil as a barrier layer provided between the layers, wherein at least one inner surface of the metallic foil layer is subjected to a chemical transformation, wherein an inner adhesive resin layer exhibiting adhesion to both the metallic foil as the barrier layer and the resin of the inner sealing layer is laminated onto the surface that has been chemically transformed, and wherein the inner sealing layer is further laminated by means of the adhesive resin layer, wherein the outer substrate layer comprises a biaxially oriented polyethylene terephthalate film and this film satisfies the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa Expression (II) , with MB: Tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film, and TB: Tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film. [3] Mold packaging material as described above in [2], in which the inner adhesive resin layer comprises an adhesive comprising a polyolefin resin having a carboxyl group and a multifunctional isocyanate compound. [4] Form packaging material as described above in [3], in which an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin is 1.0 to 10.0. [5] Mold packaging material as described above in [3] or [4] in which the melt mass flow rate (MFR) of the polyolefin resin having a carboxyl group, measured at 130°C, is 5 to 40 g / 10 min. [6] Mold packaging material as described above in [2], in which the inner adhesive resin layer contains an adhesive containing polyolefin polyol and a multifunctional isocyanate hardener. [7] Mold packaging material as described above in [6], in which the inner adhesive resin layer further contains a thermoplastic elastomer and / or a tackifier. [8] Form packaging material as described above in one of [1] to [7], in which the inner sealing layer contains a propylene homopolymer or a copolymer containing at least propylene and ethylene as a copolymerization component. [9] Form packaging material as described above in [8], in which the inner sealing layer is the polymer or copolymer having a melting point of 130°C to 160°C and a melt mass flow rate of 1 to 25 g / 10 min.

[10] Battery container produced by deep drawing or dodging the mold packaging material described above in [1] to [9].

[11] Form packaging material as described above in one of [1] to [9], which is used as packaging material for food or pharmaceuticals.

[12] A method for producing a molded packaging material, comprising a process of exposing at least one surface of a metallic foil for a barrier layer to a chemical conversion treatment, a process of bonding a biaxially oriented polyethylene terephthalate film to the other surface of the metallic foil by means of an outer adhesive to form an outer substrate layer, a process of forming an inner adhesive resin layer having adhesion to both the metallic foil as the barrier layer and an inner sealing resin, which will be described later, on that surface of the metallic foil which has been chemically converted, a process of laminating and forming the sealing layer having a thermoplastic resin on the inner adhesive resin layer, and a process of heat-treating a laminate produced by the above-mentioned processes,so with a hot roller heated to 130°C to 220°C such that the outer substrate layer is on the side of the hot roller, using a biaxially oriented polyethylene terephthalate film that satisfies the following expressions (I) and (II): , 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa Expression (II) , with MB: Tensile breaking load in the M direction of the biaxially oriented polyethylene terephthalate film, and TB: Tensile breaking load in the T direction of the biaxially oriented polyethylene terephthalate film.

[13] Method for producing a molded packaging material as described above in

[12] , wherein a resin comprising a propylene homopolymer or a copolymer resin comprising at least propylene and ethylene as a copolymerization component having a melting point of 130°C to 160°C and a melt mass flow rate of 1 to 25 g / 10 min is used as the thermoplastic resin of the sealing layer.

[14] Method for producing a molded packaging material as described above in

[12] or

[13] , wherein the inner adhesive resin layer is formed by applying and drying an adhesive resin which contains a polyolefin resin with a carboxyl group and a multifunctional isocyanate compound and which has an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin of 1.0 to 10.0.

[15] Method for producing a molded packaging material as described above in

[12] or

[13] , wherein the inner adhesive resin layer is formed with an adhesive composition comprising polyolefin polyol and a multifunctional isocyanate hardener, and further comprising a thermoplastic elastomer and / or a tackifier. Effects of the invention

[0013] According to the invention in [1], the molded packing material has excellent chemical resistance compared to the use of other heat-resistant resins, such as polyamide resin and acrylic resin, because the heat-resistant resin forming the outer substrate layer is a biaxially oriented polyethylene terephthalate resin. For example, when the molded packing material is used for a battery container, fading and deterioration of appearance do not occur, and the electrolyte solution adhesion and appearance retention properties remain good without the need for a separate protective surface layer.

[0014] Furthermore, because the polyethylene terephthalate film of the outer substrate layer has a biaxially oriented polyethylene terephthalate resin that satisfies the following expressions [1] and [2], wherein 500 MPa ≤ MB + TB ≤ 700 MPa Printout (I) and |MB – TB| ≤ 30 MPa Expression (II) If the tensile breaking load in the M direction of the biaxially oriented polyethylene terephthalate film is defined as “MB” and the tensile breaking load in the T direction of the biaxially oriented polyethylene terephthalate film is defined as “TB”, a molding packaging material can be provided that has ideal molding properties and that can enable molding with sharpness and sufficient depth without the formation of holes and cracks when subjected to a molding process such as deep drawing, warping or the like.

[0015] The “direction M” in the above description is an extrusion film formation direction of the polyethylene terephthalate film, and the “direction T” is a direction that is perpendicular to direction M.

[0016] According to the invention in [2], the molded packaging material comprises the outer substrate layer, the inner sealing layer, and the metallic foil as a barrier layer provided between these layers, wherein at least one inner surface of the metallic foil is subjected to a chemical conversion treatment, and an adhesive resin layer, which has adhesion to both the metallic foil and the resin of the inner sealing layer, is laminated onto the surface that has been chemically converted, so that the interlayer lamination thickness of the sealing layer and the metallic foil can be sufficiently ensured.Furthermore, because the outer substrate layer is a biaxially oriented polyethylene terephthalate film, the molding packaging material has excellent dimensional properties and its appearance is not noticeably deteriorated even when electrolyte solution and the like adhere to it; and also because a polyethylene terephthalate film with a tensile strength difference in a certain range, which in particular fulfills the above-mentioned expressions (I) and (II), is used as the polyethylene terephthalate film, the molding packaging material can be provided with even better dimensional properties and which can be molded into a container with a sharpness and a great depth while avoiding dimensional problems.Furthermore, since at least a portion of the metallic foil layer is subjected to chemical conversion treatment, corrosion of the metallic foil surface caused by its contents (a battery electrolyte solution, food, pharmaceuticals, etc.) can be adequately prevented. When the molded packaging material is used as a battery container, a reduction in the interlayer lamination thickness of the metallic foil barrier layer and the inner sealing layer caused by exposure to an electrolyte solution can be prevented, as can a reduction in interlayer lamination thickness caused by heat generation and expansion and contraction of the packaging material due to repeated charging and discharging, thus ensuring sufficient sealing performance.

[0017] According to the invention in [3], a reduction in the lamination thickness between the metallic foil and the inner sealing layer over time, caused by the influence of an electrolyte solution when used as a battery container, can be reduced and prevented more efficiently because the inner adhesive resin layer has an adhesive comprising a polyolefin resin having a carboxyl group and a multifunctional isocyanate compound.

[0018] According to the invention in [4], a packing material for battery containers is provided in which the interlayer adhesion strength hardly decreases over a longer period of time because the equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin is 1.0 to 10.0.

[0019] According to the invention in [5], because the polyolefin resin, which has a carboxyl group, of the inner adhesive resin layer is one which has a melt mass flow rate (MFR) measured at 130°C of 5 to 40 g / 10 min, a uniform coating formation of it can be carried out easily and safely, and a reduction in the lamination thickness of the barrier layer of the metallic foil and the inner sealing layer over time can be reduced more effectively, and the usable service life can be increased.

[0020] According to the invention in [6], a deterioration of the lamination strength between the metallic foil as the barrier layer and the inner sealing layer over time, caused by the influence of an electrolyte solution and the like, can be effectively suppressed and the water vapor barrier properties can also be advantageously maintained because the inner adhesive resin layer has an adhesive containing polyolefin polyol and a multifunctional isocyanate hardener.

[0021] According to the invention in [7], a further improvement in the interlayer lamination strength can be achieved because an adhesive composition in which a thermoplastic elastomer and / or an adhesive is additionally added to the adhesive of the invention according to [6] is used.

[0022] According to the invention in [8], sufficient heat resistance and excellent sealing performance can be ensured, since the sealing layer is formed with a propylene homopolymer or a copolymer resin which has at least propylene and ethylene as copolymerization components.

[0023] According to the invention in [9], sufficient heat resistance can be ensured and moderate fluidity can be achieved during sealing, so that excellent sealing performance can be ensured because the melting point of the polymer or copolymer of the invention above in [8] is 130 to 160°C and the melt mass flow rate of this is 1 to 25 g / 10 min.

[0024] According to the invention in

[10] , a battery container is provided which has a high interlayer lamination thickness and a long service life without shape defects.

[0025] According to the invention in

[11] , a food packaging material or a pharmaceutical packaging material is provided which has a high interlayer lamination thickness and excellent dimensional properties.

[0026] According to the invention in

[12] , the method for producing a molded packaging material comprises the process of exposing at least one surface of a metallic foil for a barrier layer to a chemical conversion treatment, the process of bonding a biaxially oriented polyethylene terephthalate film to the other surface of the metallic foil by means of an outer adhesive to form an outer substrate layer, the process of forming an inner adhesive resin layer, which has adhesion to both the metallic foil as the barrier layer and an inner sealing resin, which will be described later, on that surface of the metallic foil which has been chemically converted, the process of laminating and forming the sealing layer, which has a thermoplastic resin, on the inner adhesive resin layer, and the process of heat-treating a laminate produced by the above-mentioned processes.with a hot roll heated to 130°C to 220°C, wherein the outer substrate layer is located on the side of the hot roll, wherein a biaxially oriented polyethylene terephthalate film is used as the biaxially oriented polyethylene terephthalate film that fulfills the above expressions (I) and (II). This allows the efficient production of the molded packaging material, which exhibits the numerous effects described above, and furthermore, the molded packaging material can be obtained which has excellent properties, particularly with regard to the interlayer adhesion strength of the metallic foil and the inner sealing layer, i.e., lamination strength.

[0027] Therefore, when the resulting molded packing material is formed into a battery container, for example, a reduction in the interlayer lamination thickness caused by the influence of an electrolyte solution can be prevented, and a reduction in the interlayer lamination thickness caused by the influence of heat generation and expansion and contraction of the packing material due to repeated charging and discharging can also be prevented, and sufficient sealing performance can be ensured.Furthermore, the mold packaging material, in which corrosion of the surface of the metallic foil caused by the contents (electrolyte solution of a battery, food, pharmaceuticals and the like) is sufficiently prevented, can be produced because at least one surface onto which a treatment fluid is applied is exposed to the metallic foil as the barrier layer of the chemical conversion treatment.

[0028] According to the invention in

[13] , a molded packaging material which has sufficient heat resistance and in which moderate fluidity can be achieved during sealing, so that excellent sealing performance can be ensured, can be produced by using a propylene homopolymer or a copolymer resin which contains at least propylene and ethylene as a copolymerization component, which has a melting point of 130°C to 160°C and a melt mass flow rate of 1 g / 10 min to 15 g / 10 min as the thermoplastic resin of the sealing layer.

[0029] According to the invention in

[14] , a reduction in the adhesive strength between the aluminum foil and the inner sealing layer over time due to the electrolyte solution of the battery is sufficiently suppressed for a long period of time because the inner adhesive layer is formed by applying and drying an adhesive resin containing a polyolefin resin having a carboxyl group and a multifunctional isocyanate compound, and exhibiting an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin of 1.0 to 10.0. This results in excellent resistance to electrolyte solutions and, furthermore, low moisture penetration, which is why a stable packing material for a long-life battery container can be produced.

[0030] According to the invention in

[15] , a molded packaging material can be provided in which a deterioration of the lamination strength between the metallic foil as the barrier layer and the inner sealing layer can be effectively suppressed over time and which also has excellent water vapor barrier properties because the inner adhesive resin layer is formed with an adhesive composition that contains polyolefin polyol and a multifunctional isocyanate curing agent and which further contains a thermoplastic elastomer and / or a tackifier. Brief description of the characters

[0031] The Fig. Figure 1 shows a sectional view illustrating an embodiment of a molded packaging material according to the present invention.

[0032] The Fig. Figure 2 shows a schematic, explanatory view illustrating a method for producing a molded packaging material according to the present invention. Embodiments for carrying out the invention

[0033] A preferred embodiment of a molded packaging material 1 According to the invention, in the Fig. 1 shown. The mold packaging material ( 1 ) is formed into an approximately rectangular parallelepiped shape, which has a top surface that is manufactured to be open, for example to be used as a container for a lithium-ion polymer secondary battery.

[0034] In the molded packaging material ( 1 ) becomes an outer substrate layer ( 2 ), which has a heat-resistant resin film, on / to a surface of a metallic foil ( 4 ) as a barrier layer by means of an adhesive layer ( 11 ) laminated and integrated. On / to another surface ( 4A ) of the metallic foil an inner sealing layer ( 3 ) by means of an inner layer of adhesive resin ( 5), which exhibits an adhesive ability with both the metallic foil ( 4 ) as well as with a resin of the inner sealing layer ( 3 ) has, laminated and integrated.

[0035] The outer substrate layer ( 2 ) can be one in which a biaxially oriented polyethylene terephthalate resin layer, which will be described later, is used for at least the outermost layer, and it can have a single-layer configuration or it can have a multi-layer configuration in which numerous types of heat-resistant resin, which are different in their nature and properties, are laminated.

[0036] Similarly, the inner sealing layer ( 3 ) one that has a heat-adhesive resin layer, which has polypropylene, at least for the innermost layer, and there may be another resin intermediate layer that is located between the inner adhesive resin layer ( 5) and the innermost layer of the inner sealing layer ( 3 ) is located in between. In this case, according to the invention, the resin intermediate layer provided between these is considered part of the sealing layer ( 3 ) considered. The inner adhesive resin layer ( 5 ) can be, for example, a simple / pure composition of a polyolefin resin that has a carboxyl group, or it can be a mixed composition of two or more types of substances that have different melting points. (Outer surface substrate layer)

[0037] The outer substrate layer ( 2 ), which contains a heat-resistant resin, has strength and good dimensional properties as a packing material. According to the invention, it is essential that the outer substrate layer ( 2) has a biaxially oriented polyethylene terephthalate film and the tensile strength in the direction M and the tensile strength in the direction T thereof and the difference thereof are set in a range which satisfies the following expressions (I) and (II). 500 MPa ≤ MB + TB ≤ 700 MPa Printout (I) |MB – TB| ≤ 30 MPa Expression (II) MB: Tensile strength in the M direction of the biaxially oriented polyethylene terephthalate film TB: Tensile strength in the T direction of the biaxially oriented polyethylene terephthalate film.

[0038] In particular, because of the use of biaxially oriented polyethylene terephthalate film as the heat-resistant resin, the outer substrate layer can be achieved which has excellent chemical resistance, heat resistance and the like compared to the use of another type of heat-resistant resin, such as a polyamide resin or an acrylic resin, while ensuring the necessary formability.

[0039] By using the film that fulfills the above expressions (I) and (II), namely the biaxially oriented polyethylene terephthalate resin, a film can be obtained that has excellent forming properties in secondary forming processes such as deep drawing and warping. Therefore, for example, hardly any forming defects such as cracks and holes are produced when the mold packaging material is formed into a shell mold, even when the mold packaging material is formed into a container mold that has a relatively sharply curved section and a relatively large depth, i.e., one that has a large capacity.

[0040] Therefore, the strength required to bear the load of a packaging material is that of the outer substrate layer ( 2The strength is insufficient if the value of MB + TB of expression (I) is less than 500 MPa. If the value exceeds 700 MPa, the strength exceeds a necessary limit and assumes an excessive value that is essentially useless; on the contrary, it may cause a deterioration of the forming properties, and warping after forming may be noticeable, which is why this value may not be desirable. The range of the value MB + TB is preferably in the range of 520 MPa to 650 MPa and is particularly preferably in the range of 550 MPa to 600 MPa.

[0041] If the value of |MB – TB| exceeds 30 MPa and there is a large difference in strength between the M and T directions, this will also result in impaired formability of the packaging material. More specifically, it is likely that forming defects, such as the formation of holes and, in the worst case, cracks, will occur in a formed product after deep drawing and / or warping. Considering the difficulty of film production, the value of |MB – TB| is preferably in the range of substantially 20 MPa or lower, and particularly preferably 10 MPa or lower.

[0042] The thickness of the film that forms the outer substrate layer ( 2The thickness of the forming material is preferably set in the range of 10 to 50 μm. By setting the value to a level equal to or higher than a suitable lower limit, sufficient thickness as packaging material can be ensured. Furthermore, stress during bending and deep drawing can be minimized by setting the value to a level equal to or lower than a suitable upper limit, thus improving the forming properties. An even more preferred thickness range is approximately 12 to 20 μm.

[0043] A method for producing the film described above, which satisfies expressions (I) and (II), is not limited and is implemented, for example, by extruding a film with a slot die at a temperature of 270°C to 320°C, cooling the film with a cooling roller, forming the film into a sheet shape, drawing the film vertically two to four times with a roller heated to 80°C to 90°C, subsequently drawing the film horizontally two to four times at a temperature of 95°C to 110°C, subsequently heat-treating the film in a heating chamber at 150°C to 250°C, and then cooling and winding the film. In such a manufacturing process, the drawing ratio and the heat-treatment temperature are controlled so that the film satisfies the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa Printout (I) |MB – TB| ≤ 30 MPa, expression (II) when the tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film is defined as “MB” and a tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film is defined as “TB”. (Outer adhesive layer)

[0044] An adhesive that strengthens the adhesive layer ( 11The adhesive layer consists of, for example, a two-component, hardened urethane adhesive containing a polyol component and an isocyanate component, and similar compounds, but is not limited to these. This two-component, hardened urethane adhesive is suitable for bonding using a dry lamination process. The polyol component may contain, for example, polyester polyol, polyether polyol, and similar compounds, but is not limited to these. The isocyanate component may contain, for example, diisocyanates such as TDI (tolylene diisocyanate), HDI (hexamethylene diisocyanate), and MDI (methylenebis(4,1-phenylene) diisocyanate), but is not limited to these. The thickness of the adhesive layer ( 11 ) is preferably set to 2 μm to 5 μm and particularly preferably to 3 μm to 4 μm. (Barrier layer - metallic foil)

[0045] The metallic foil ( 4), which forms the barrier layer, has the function of providing gas barrier properties to prevent the penetration of oxygen or moisture into the mold packaging material ( 1 ) to provide inside. The metallic foil ( 4 The material may include, for example, aluminum foil, copper foil, and similar materials, but is not limited to these, although aluminum foil is generally used. The thickness of the metallic foil is preferably 20 μm to 100 μm. Since the thickness is 20 μm or more, the formation of holes during rolling in the production of the metallic foil can be prevented. Since the thickness is 100 μm or less, stress during bending and deep drawing can be kept low, thus improving the form properties.

[0046] At least the inner surface ( 4a ), that is, the area on the side of the sealing layer ( 3 ), the metallic foil ( 4The barrier layer is subjected to a chemical conversion treatment. By subjecting the metallic foil to such a chemical conversion treatment, corrosion of the foil's surface caused by its contents (electrolyte solution from a battery, food, pharmaceuticals, and the like) can be sufficiently prevented. For example, the metallic foil undergoes the following chemical conversion treatment. More specifically, for example... 1) an aqueous solution containing a mixture of metal salts of phosphoric acid, chromic acid and fluorides, 2) an aqueous solution containing a mixture of phosphoric acid, chromic acid and metallic and non-metallic fluoride salts, 3) an aqueous solution containing a mixture of an acrylic resin and / or a phenolic resin, phosphoric acid, chromic acid and a metallic fluoride salt, and 4) an aqueous solution containing a mixture of an acrylic resin and / or a phenolic resin, a phosphate or phosphoric acid compound, a chromate or chromic acid compound, and a metallic fluoride salt, applied to the surface of the metallic foil which has undergone a degreasing treatment and then dried to form a chemical conversion film. (Inside adhesive resin layer)

[0047] With regard to the inner adhesive resin layer ( 5 ) to connect / bond the barrier layer ( 4 ) and the inner sealing layer ( 3 The choice of material is particularly important to prevent a decrease in lamination strength over time caused by exposure to the electrolyte solution and similar substances. An adhesive resin that exhibits good adhesion to at least both the metallic foil (aluminum) ( 4) as the barrier layer and a bonding resin of the inner sealing layer ( 3A specific resin type, for example, is a resin obtained by carrying out graft-addition modification or copolymerization of dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, and mesaconic acid; dicarboxylic acid anhydrides, such as maleic anhydride, fumaric anhydride, itaconic anhydride, and mesaconic anhydride; monomers having a carboxyl group, such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; and the like, together with polypropylene. Of the above, a resin obtained by carrying out graft-addition modification with maleic anhydride, acrylic acid, and methacrylic acid is preferably used, and in particular, maleic anhydride-modified polyolefin resin is a preferably used resin.A method for producing the resin is not particularly restricted, and a solution process comprising dissolving polypropylene in an organic solvent and then reacting the solution with acid (maleic anhydride and similar) in the presence of a radical-generating agent, a melting process comprising heating and melting polypropylene followed by reacting the resulting substance with acid (maleic anhydride or similar) in the presence of a radical-generating agent, and similar processes may be mentioned as examples.

[0048] The inner adhesive resin layer ( 5) is particularly preferably formed by an adhesive composition containing a polyolefin resin having a carboxyl group in its chemical structure and a multifunctional isocyanate compound to increase the service life of the parking material by ensuring sufficient resistance to electrolyte solutions. The formation of the adhesive resin layer ( 5 ) is normally carried out by applying an adhesive fluid containing a polyolefin resin having a carboxyl group, a multifunctional isocyanate compound and an organic solvent to the metallic foil ( 4 ) as the barrier layer and / or on the inner sealing layer ( 3 ) and the subsequent drying of it.

[0049] The polyolefin resin containing a carboxyl group (hereafter sometimes also referred to as "carboxyl-group-containing polyolefin resin") exhibits, for example, a modified polyolefin resin obtained by grafting polymerization of an ethylene unsaturated carboxylic acid or an acid anhydride thereof with polyolefin, a copolymer resin of an olefin monomer and an ethylene unsaturated carboxylic acid, and the like, but is not particularly limited to these. The polyolefin exhibits, for example, homopolymers of olefin monomers such as ethylene, propylene, and butene, or copolymers of these olefin monomers, and the like, but is not limited to these. The ethylene unsaturated carboxylic acid exhibits, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and the like. The ethylenic unsaturated carboxylic acid can be used alone / pure or as a mixture of two or more types thereof.Preferably, a polyolefin resin containing a carboxyl group is used that is soluble in an organic solvent.

[0050] Of the above, a modified polyolefin resin is preferably used as a polyolefin resin having a carboxyl group, which is obtained by carrying out graft copolymerization of ethylene unsaturated carboxylic acid or an acid anhydride thereof with a homopolymer of propylene or with a copolymer of propylene and ethylene.

[0051] The multifunctional isocyanate compound reacts with the carboxyl-group-containing polyolefin resin and acts as a hardener to cure an adhesion promoter composition. The multifunctional isocyanate compound may include, for example, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanurate-modified substances, biuret-modified substances of diisocyanate compounds, or substances obtained by adduct modification of diisocyanate compounds with polyhydric alcohols, such as trimethylolpropane, and the like. The multifunctional isocyanate compounds can be used alone or as a mixture of two or more types. Preferably, a multifunctional isocyanate compound that dissolves in an organic solvent is used.

[0052] The organic solvents are not particularly restricted, as long as they can dissolve or disperse the carboxyl-containing polyolefin resin. Of those mentioned above, organic solvents capable of dissolving the carboxyl-containing polyolefin resin are preferred. Organic solvents that evaporate readily and can be removed from the adhesive liquid by heating or similar means are also preferred.Examples of organic solvents that can dissolve carboxyl-group-containing polyolefin resins and that can be evaporated and removed by heating or similar processes include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as n-hexane, alicyclic organic solvents such as cyclohexane and methylcyclohexane (MCH), organic ketone solvents such as methyl ethyl ketone (MEK), and similar solvents. These organic solvents can be used alone or in combination with other types.

[0053] In the adhesive liquid or adhesive resin composition, an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the carboxyl-containing polyolefin resin is preferably adjusted to 1.0 to 10.0. When the ratio is set within this range, an adhesive composition with excellent initial adhesion performance can be achieved, and a reduction in adhesion strength over time between the metallic foil layer ( 4 ) and the inner sealing layer ( 3 The corrosion caused by the electrolyte solution of a battery can be sufficiently suppressed for a longer period of time, thus further increasing the electrolyte solution's resistance. The [NCO] / [OH] equivalence ratio is preferably set to 1.5 to 9.0 and particularly preferably to 1.5 to 6.0.

[0054] The adhesive fluid and the adhesive composition may contain additives, such as a reaction accelerator, a tackifier, and a plasticizer, as necessary. Inorganic or organic antiblocking agents and amide lubricants may be added to the resin component as described above, provided that the effects of the invention are not impaired.

[0055] The thickness of the adhesive resin layer ( 5 The thickness is preferably set to 1 μm to 15 μm. Sufficient adhesion strength can be achieved with a thickness of 1 μm or more. Water vapor barrier properties can also be improved with a thickness of 15 μm or less.

[0056] The polyolefin resin of the adhesive resin layer containing a carboxyl group ( 5) can be a single / pure composition or can be a mixture of two or more types of substances that have different melting points. (Inside sealing layer)

[0057] The resin that forms the inner sealing layer ( 3 ) forms, for example 1) a statistical copolymer resin containing propylene and ethylene as a copolymerization component, 2) a copolymer resin containing propylene, ethylene and butene as a copolymerization component, 3) a block copolymer resin containing propylene and ethylene as a copolymerization component, 4) a propylene homopolymer or a multilayer substance having any of the above 1) to 4), but is not limited to.

[0058] Each of the copolymer resins according to the above-mentioned 1) to 4) may contain a thermoplastic olefin elastomer.

[0059] For the resin of the inner sealing layer ( 3 A copolymer resin with a melting point of 130°C to 160°C is preferably used. This copolymer resin has a peak temperature (melting point), measured by DSC (difference scanning calorimetry) at a temperature rise rate of 20°C / min, of 130°C to 160°C. Because the melting point is 130°C or higher, sufficient heat resistance can be ensured, and because the melting temperature is 160°C or lower, excellent sealing properties can be guaranteed.

[0060] Of the resins mentioned above (1) to (4), which form the inner sealing layer ( 3To form the resin, a copolymer resin is preferably used that contains at least propylene and ethylene as a copolymerization component and has a melt flow rate (MFR) of 1 g / 10 min to 15 g / 10 min. The MFR is a value measured according to JIS K7210-1999 (Condition M). Because the MFR is 1 g / 10 min or more, extrusion lamination can be easily performed. Because the MFR is 15 g / 10 min or less, the resin's fluidity during sealing is moderate, thus ensuring even better sealing properties.

[0061] The thickness of the inner sealing layer ( 3 The thickness is preferably 10 to 80 μm. Because the thickness is 10 μm or more, sufficient sealing strength can be achieved, and because the thickness is 80 μm or less, sufficient protection against damage to a water vapor barrier from the end surface can be ensured. The inner sealing layer ( 3The seal can be formed from a single layer, as mentioned above, or it can be multilayered, such as by a co-extruded polypropylene film and one obtained by double extrusion lamination of polypropylene. In the latter case, if a highly fluid polypropylene layer is placed on the outside (innermost layer side) of a less fluid polypropylene layer, an extreme reduction in seal thickness due to unusual flow of the polypropylene layer during sealing can be prevented.

[0062] In the molded packaging material ( 1 ), which has the configuration described above, has the adhesive resin layer ( 5 ) an excellent affinity for both the metallic foil and the barrier layer ( 4 ) as well as the inner sealing layer ( 3), which is why the interlayer lamination thickness between the layers can be sufficiently increased. Therefore, a reduction in interlayer lamination thickness caused by the influence of an electrolyte solution can be prevented, and a reduction in interlayer lamination thickness caused by the influence of heat generation and expansion and contraction of the parking material due to repeated charging and discharging can also be prevented, so that sufficient sealing properties can be ensured when the packing material ( 1 ) is formed in a battery container. (Manufacturing process)

[0063] Next, an example of a process for manufacturing the molded packaging material will be presented ( 1 ) the invention with reference to the Fig. 1 and Fig. 2 described.

[0064] First, a biaxially oriented polyethylene terephthalate film is applied as the outer substrate layer ( 2 ) with an area of ​​the metallic foil ( 4 ) as the barrier layer with the adhesive ( 11 ) for example, by means of a dry lamination process.

[0065] For the metallic foil ( 4 ) a metallic foil in which at least the inner surface (the surface onto which a treatment fluid used in the subsequent process is applied) ( 4A ) is / was subjected to a chemical transformation treatment, is used. It can also be the metallic foil ( 4 ), in which both surfaces are / were subjected to a chemical transformation treatment.

[0066] On the other surface (inside surface) ( 4A ) the metallic foil ( 4 ) the inner sealing layer ( 3 ) by means of the adhesive resin view (5 ), which has formed good adhesion with both the metallic foil and the bonding-side resin of the inner sealing layer.

[0067] Here, the formation of the inner adhesive resin layer ( 5 ) and the inner sealing layer ( 3 ) for example, by creating and preparing a film ( 20 ), which has a multi-layer configuration in which the adhesive resin layer ( 5 ) and the inner sealing layer ( 3 ) previously laminated using a T-form tooling process or a blow molding process, arranging the film on the surface that has been chemically transformed, the metallic foil ( 4 ), and then passing it through a hot roller ( 22 ), which is heated to 130°C to 220°C. By passing the resulting substance in such a way that the biaxially oriented polyethylene terephthalate ( 2 )-side on the side of the hot roller (22 ) is located, a laminate is used as the form packaging material ( 1 ) receive ( Fig. 2).

[0068] The material of the surface of the hot roller ( 22 ) is not particularly restricted and, for example, ordinary materials such as stainless steel can be used.

[0069] From the molded packaging material ( 1 According to the invention, a packaging container body for a battery container, for food, for pharmaceuticals, and the like is produced by forming (curving, deep drawing, and the like) into numerous shapes, such as a rectangular parallelepiped shape with a large form height. In the battery container, the food packaging container, or the pharmaceutical packaging container obtained by carrying out such a forming process, it is prevented that the respective contents come into contact with the layer of metallic foil ( 4 ) and the inner adhesive resin layer ( 5) penetrate. Therefore, if it is formed, for example, into a battery container, a reduction in lamination strength caused by the influence of an electrolyte solution can be prevented, and a reduction in lamination strength caused by the influence of heat generation and the expansion and contraction of the packing material due to repeated charging and discharging can be prevented, so that sufficient sealing performance can be maintained over a long period of time. Examples

[0070] Next, specific examples of the invention will be described, although the invention is not limited to these examples. (Example 1)

[0071] A chemical conversion treatment liquid containing polyacrylic acid, a trivalent chromium compound, water, and alcohol was applied to both surfaces of an approximately 40 μm thick aluminum foil (substrate layer) ( 4 ) applied, the aluminum foil was dried at 180°C, and then the chemical conversion treatment was carried out such that the chromium adhesion quantity was 10 mg / m² 2 amounts.

[0072] Then a 12 μm thick biaxially oriented polyethylene terephthalate film (outer surface-substrate layer) was applied ( 2 ) to a surface of the aluminum foil ( 4 ) dry-laminated with a two-component, hardening-type urethane adhesive (outer surface-substrate layer).

[0073] Furthermore, a maleic acid-modified polypropylene resin ( 5) (Inner surface adhesive resin layer), which has adhesion to both the metallic foil and the propylene, and a statistical ethylene-propylene copolymer resin, which has a melting point of 140°C and an MFR of 7 g / 10 min, as a laminate film ( 20 ) on the other surface of the aluminum foil is extruded and prepared using a T-shaped die process so that the maleic acid-modified polypropylene resin layer ( 5 ) 7 μm and the statistical ethylene-propylene copolymer resin layer ( 3 ) 28 μm.

[0074] Subsequently, the laminate film ( 20 ) on the chemically transformed surface ( 4a ) the aluminum foil ( 4 ) arranged, and then by a hot roller ( 22 ), which is heated to 150°C, happens as described in the Fig. 2 is shown, which creates a molded packaging material ( 1). In this process, the heat treatment was carried out with the biaxially oriented polyethylene terephthalate film side facing the side of the hot roller heated to 150°C. The biaxially oriented polyethylene terephthalate film used here was one that MB + TB = 560 MPa and |MB – TB| ≤ 25 MPa fulfilled if the tensile breaking load in the direction M of the biaxially oriented polyethylene terephthalate film is defined as “MB”, and the tensile breaking load in the direction T of the biaxially oriented polyethylene terephthalate film is defined as “TB”.

[0075] The materials, compositions, physical properties, components and similar items of the outer substrate layer, the inner adhesive resin layer and the sealing layer are as shown in Table 1.

[0076] The following abbreviations are used in Table 1. Oriented PET: biaxially oriented polyethylene terephthalate film Oriented Ny: biaxially oriented polyamide(6-nylon) film m-PP: Maleic anhydride-modified polypropylene (Modified polypropylene resin obtained by graft polymerization of maleic anhydride with a copolymer of propylene and ethylene) M-PP: Maleic anhydride-modified polypropylene (Modified polypropylene resin obtained by graft polymerization of maleic anhydride with a copolymer of propylene and ethylene) Statistical PP: statistical propylene-ethylene copolymer resin Block PP: Propylene-ethylene block copolymer resin PP: Polypropylene resin Multifunctional isocyanate: Polymer body made of hexamethylene diisocyanate (NCO content of 23.1 wt%) Polyolefin-Polyol Adhesive: Adhesive containing polyolefin polyol (number average molecular weight of 2000 and hydroxyl group value of 50 mgOH / g) and multifunctional isocyanate (manufactured by “Nippon Polyurethane Industry Co., Ltd.” with the product name “Coronate HX”) as a necessary component, toluene / methyl ethyl ketone: 80 / 20 as a solvent, a thermoplastic elastomer (manufactured by “Kraton Polymers Inc.” with the product name “Kraton G-1657”), and an adhesion-promoting agent (manufactured by “Arakawa Chemical Industries, Ltd.” with the product name “Arkon P-90”). (Examples 2 to 4)

[0077] The mold packaging materials were obtained in the same way as in Example 1, except that biaxially oriented polyethylene terephthalate resin films were used as the outer substrate layer biaxially oriented polyethylene terephthalate resin films having an “MB + TB” value of 510, 600 and 630 respectively, and an “|MB – TB|” value of 10, 5 and 2 respectively. (Example 5)

[0078] A molded packaging material was obtained in the same way as in Example 1, however, a maleic acid-modified polypropylene resin, which has a melting point of 160°C and an MFR of 7 g / 10 min, was used as the inner sealing layer ( 3 ) used, and the temperature of the hot roller was set to 170°C. (Example 6)

[0079] A molded packaging material was used. 1obtained in the same way as in Example 1, however, a propylene ethylene copolymer resin having a melting point of 130°C and an MFR of 21 g / 10 min was used as the inner sealing layer, the thickness of the adhesive resin layer was set to 10 μm and the thickness of the sealing layer was set to 70 μm. (Example 7)

[0080] A 12 μm thick biaxially oriented polyethylene terephthalate film was used. 2 dry-laminated on an aluminum foil surface (barrier layer), both surfaces of which were subjected to a chemical conversion treatment in the same manner as in Example 1, using a two-component hardening urethane adhesive.

[0081] Subsequently, a 40 μm thick statistical propylene ethylene copolymer film (with a melting point of 140°C, measured by DSC) was laminated and integrated onto the other surface of the aluminum foil using a sandwich lamination process with a 5 μm thick adhesive resin and an extruded polypropylene resin. This extruded polypropylene resin was produced by extruding a 15 μm thick statistical propylene ethylene copolymer resin layer, which had a melting point of 130°C, using an extrusion die. The laminate was then passed through a heated roller heated to 150°C, resulting in a molded packaging material. During this process, the laminate passed through the heated roller with the side containing the biaxially oriented polyethylene terephthalate film facing the side of the heated roller.The biaxially oriented polyethylene terephthalate film used was the same as the one used in Example 1. (Example 8)

[0082] A 12 μm thick biaxially oriented polyethylene terephthalate film (outer substrate layer) was dry-laminated to a surface of an aluminum foil (barrier layer), both surfaces of which were subjected to a chemical transformation treatment in the same manner as in Example 1, using a two-component hardening urethane adhesive.

[0083] Subsequently, an adhesive, in which 0.9 g of a polymer body of hexamethylene diisocyanate (multifunctional isocyanate compound, NCO content of 23.1 wt%) in a solution containing 15 g of maleic acid-modified polypropylene (modified polypropylene resin obtained by grafting polymerization of maleic anhydride with a copolymer of propylene and ethylene, melting point 77°C, acidity 10 mgKOH / g) in 85 g of a solvent mixture (solvent mixture with methylcyclohexane to methyl ethyl ketone = 8 parts (by mass) to 2 parts (by mass)) was dissolved such that the equivalence ratio [NCO] / [OH] is 1.8, was applied to the other surface of the aluminum foil and then dried at 80°C to form a 3 μm thick inner adhesive resin layer.Then, an 80 μm thick statistical propylene ethylene copolymer film (inner sealing layer) was dry-laminated onto the surface of the dried adhesive resin layer. Apart from the processes described above, the mold packaging material was produced in the same way as in Example 1. (Example 9)

[0084] An adhesive containing polyolefin polyol (number-average molecular weight of 2000 and hydroxyl group value of 50 mgOH / g) and multifunctional isocyanate (manufactured by "Nippon Polyurethane Industry Co., Ltd." with the product name "Coronate HX") as a necessary component, toluene / methyl ethyl ketone: 80 / 20 as a solvent, a thermoplastic elastomer (manufactured by "Kraton Polymers Inc" with the product name "Kraton G-1657") and an adhesion-promoting agent (manufactured by "Arakawa Chemical Industries, Ltd." with the product name "Arkon P-90") was applied and dried to form a 3 μm thick adhesive resin layer onto a chemically treated aluminum foil, both surfaces of which were subjected to the chemical transformation treatment.

[0085] Then an 80 μm thick, non-oriented film ( 3) comprising three layers: a statistical propylene-ethylene copolymer, block polypropylene, and a statistical propylene-ethylene copolymer (inner seal layer), as shown in Table 1, dry-laminated onto the dried adhesive resin layer surface. Apart from the processes described above, a molded packaging material was obtained in the same manner as in Example 1. (Comparison examples 1 and 2)

[0086] Molded packaging materials were obtained in the same way as in Example 8, however, the biaxially oriented polyethylene terephthalate film of the outer substrate layer used had “MB + TB” values ​​of 430 and 730 respectively, and |MB – TB| values ​​of 55 and 40 respectively. (Comparative example 3)

[0087] A molded packing material was obtained in the same way as in Example 8, however, a 15 μm thick biaxially oriented nylon-6 film (MB + TB = 470 MPa, |MB – TB| = 60 MPa) was used as the heat-resistant resin of the outer substrate layer.

[0088] The melting point mentioned in the description of the above examples and comparison examples is a melting point measured at a temperature rise rate of 20°C / min using an automatic dynamic differential calorimeter manufactured by "Shimadzu Corp." (product number: DSC-60A).

[0089] The tensile breaking load is a value measured using a TENSILON RTA-100 manufactured by "Orientec Co., Ltd." at a drawing speed of 100 mm / min, a sample width of 15 mm and a distance between the chucks of 50 mm.

[0090] Each molded packaging material obtained as described above was tested for performance based on the following test procedures. The results are shown in Table 1. <form-eigenschaften-testverfahren>

[0091] The molded packaging materials were formed into a rectangular parallelepiped shape with a length of 55 mm, a width of 35 mm and a depth of 8 mm using a molding machine manufactured by “Amanda Co., Ltd.” (product number TP-25C-X2), and the mold properties were evaluated based on the following evaluation criteria. (Evaluation criteria) “⌾” No holes or cracks were created. “Δ” Holes were created in a small area, but essentially hardly any holes were created. “x” Holes and cracks were created in bending areas. <Laminierungsstärke-Testverfahren>

[0092] The form packaging materials were cut to a width of 15 mm to form test samples, and the lamination thickness (lamination thickness of the inner adhesive resin layer and the inner sealing layer) of the test samples was measured using a tensile strength testing machine in an atmosphere at 80°. (Evaluation criteria) “⌾” The lamination thickness is 15 N / 15 mm width or more. “o” The lamination thickness is 3 N / 15 mm width or more and less than 5 N / 15 mm width. “x” The lamination thickness is less than 3 N / 15 mm width. <Elektrolytlösung-Widerstandsfähigkeit-Testverfahren>

[0093] The mold packaging materials were cut to a width of 15 mm to form test samples, and a solution containing lithium hexafluorophosphate dissolved in a solvent mixture in which ethylene carbonate and diethylene carbonate are mixed in a volume ratio of 1:1, resulting in a concentration of 1 mol / L, along with the test samples, were placed in a wide-mouth bottle made of polytetrafluoroethylene resin. The bottle was stored in an oven at 85°C for one week. The test samples were then removed, and the inner adhesive resin layer and the inner sealing layer were separated at their junction to measure the lamination strength (adhesion strength) between the layers. (Evaluation criteria) “⌾” With regard to the measured adhesion strength, the retention rate is 90% or more based on the initial adhesion strength. “o” With regard to the measured adhesion strength, the retention rate is 60% or more and less than 90% based on the initial adhesion strength. “Δ” With regard to the measured adhesion strength, the retention rate is 30% or more and less than 60% based on the initial adhesion strength. “x” With regard to the measured bond strength, the retention rate is less than 30% based on the initial bond strength (including a case where an intermediate layer separation occurs during immersion). <Elektrolytlösung-Anhaften-Aussehen-Bewertung>

[0094] The form packaging materials were cut to 10 cm × 10 cm, and 1 cm was used. 3 A solution in which lithium hexafluorophosphate is dissolved in a solvent mixture in which ethylene carbonate and diethylene carbonate are mixed in a volume ratio of 1:1, such that a concentration of 1 mol / L is present, was applied dropwise to the outermost surface of the mold packaging materials, and then the appearance was assessed when the area of ​​a section to which the liquid droplets adhered was rubbed back and forth ten times using a rubbing device in which cotton is wound around a weight with a diameter of 1 cm and which has a weight of 1 kilogram together with the cotton. “⌾” The appearance did not change even when the section was rubbed back and forth ten times. “Δ” The appearance changed when the section was rubbed back and forth five times. “x” The appearance changed when the section was rubbed back and forth once. <versiegelungsleistungs-testverfahren>

[0095] A seal separation test was performed under conditions of 25°C and 80°C using a TENSILON RTA-100 manufactured by Orientale Co., Ltd. and a constant temperature bath TCF-III1-B manufactured by Baldwin, Inc., and the sealing performance was then evaluated. Regarding the sealing conditions, sealing was performed for each molded packaging material with a sealing width of 5 mm, a sealing pressure of 0.3 MPa, a sealing time of 1 second, and a sealing temperature of 160°C and 180°C (both times surface heat). (Sealing performance evaluation criteria) “⌾” Those that have a strength of 30 N / 15 mm or more in both cases where sealing was performed at 160°C and the sealing separation test was performed at 25°C, and where sealing was performed at 180°C and the sealing separation test was performed at 80°C. “o” Those who achieved a strength of 25 N / 15 mm or more and less than 30 N / 15 mm in the two cases where sealing was performed at 160°C and the sealing separation test was performed at 25°C, and where sealing was performed at 180°C and the sealing separation test was performed at 80°C. “x” Those who do not meet the above criteria (poor sealing performance).

[0096] It is clear from the performance evaluation results in Table 1 that the mold test confirmed that the mold packaging materials of Examples 1–9 of the invention do not develop holes or cracks and that their molding properties are excellent. It was also confirmed that the packaging materials initially have sufficient interlayer lamination thickness and also exhibit excellent electrolyte solution resistance, electrolyte solution adhesion, appearance, and sealing performance.

[0097] On the other hand, when the biaxially oriented polyethylene terephthalate films of Comparative Examples 1 and 2, in which the tensile strengths in the MD direction and the TD direction and the difference thereto deviate from the ranges required according to the present invention, were used, and when the biaxially oriented nylon 6 film was used for the outer substrate layer of Comparative Example 3, the molded packing materials have poorer molding properties and are also worse in terms of electrolyte solution resistance and electrolyte solution adhesion appearance performance.

[0098] The present application claims priority from the unexamined Japanese patent application publication No. 2011-72538, filed on March 29, 2011, the entire disclosure of which forms part of the present application. Industrial applicability

[0099] The molded packaging material according to the invention is suitable for use as a container material for batteries, such as lithium-ion polymer secondary batteries for personal notebook computers, mobile phones, in-vehicles and stationary power sources, and is also suitable for use as packaging material for food, pharmaceuticals and the like. Reference symbol list 1 Form-Packing material 2 Outer substrate layer (heat-resistant resin layer) 3 Inner sealing layer (thermoplastic resin layer) 4 metallic foil (barrier layer) 5 Inner resin layer 11 Adhesive layer 22 Hot rolling

Claims

[1] Mold packaging material ( 1 ), exhibiting an outer substrate layer ( 2 ) having a heat-resistant resin, an inner sealing layer ( 3 ) comprising a thermoplastic resin, and a metallic foil ( 4 ) as a barrier layer provided between the layers, where the substrate layer ( 2 ) has a biaxially oriented polyethylene terephthalate film, and the film satisfies the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa, expression (II) where MB is a tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film, and TB is a tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film. [2] Mold packaging material ( 1 ), exhibiting an outer substrate layer (2 ) having a heat-resistant resin, an inner sealing layer ( 3 ) comprising a thermoplastic resin, and a metallic foil ( 4 ) as a barrier layer provided between the layers, including at least one inner surface ( 4a ) the metallic foil layer ( 4 ) is subjected to a chemical conversion treatment, whereby an inner adhesive resin layer ( 5 ), the adhesion with both the metallic foil as the barrier layer and the resin of the inner sealing layer ( 3 ) exhibits, is laminated onto the surface that has been treated with chemical transformation, and furthermore the inner sealing layer is bonded by means of the adhesive resin layer ( 5 ) is laminated, where the outer substrate layer ( 2) has a biaxially oriented polyethylene terephthalate film, and the film satisfies the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa, expression (II) where MB is a tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film, and TB is a tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film. [3] Mold packaging material ( 1 ) according to claim 2, wherein the inner adhesive resin layer ( 5 ) an adhesive comprising a polyolefin resin having a carboxyl group and a multifunctional isocyanate compound. [4] Mold packaging material ( 1 ) according to claim 3, wherein an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin is 1.0 to 10.

0. [5] Mold packaging material ( 1 ) according to claim 3, wherein the melt mass flow rate (MFR) of the polyolefin resin having a carboxyl group, measured at 130°C, is 5 to 40 g / 10 min. [6] Mold packaging material ( 1 ) according to claim 2, wherein the inner adhesive resin layer ( 5 ) contains an adhesive that includes polyolefin polyol and a multifunctional isocyanate hardener. [7] Mold packaging material ( 1 ) according to claim 6, wherein the inner adhesive resin layer ( 5 ) furthermore contains a thermoplastic elastomer and / or a tackifier. [8] Mold packaging material ( 1 ) according to any one of claims 1 to 7, wherein the inner sealing layer ( 3 ) a propylene homopolymer or a copolymer containing at least propylene and ethylene as a copolymerization component. [9] Mold packaging material ( 1) according to claim 8, wherein the inner sealing layer ( 3 ) the polymer or copolymer, each having a melting point of 130°C to 160°C and a melt mass flow rate of 1 to 25 g / 10 min. [10] Battery container produced by deep drawing or doming the mold packaging material ( 1 ) according to any one of claims 1 to 9. [11] Mold packaging material ( 1 ) according to any one of claims 1 to 9, which is used as packaging material for food or pharmaceuticals. [12] Method for producing a molded packaging material ( 1 ), exhibiting a step of exposing at least one surface ( 4a ) a metallic foil ( 4 ) for a barrier layer in a chemical conversion treatment, one step of joining a biaxially oriented polyethylene terephthalate film to the other surface of the metallic foil ( 4) using an external adhesive to bond an external substrate layer ( 2 ) to form, one step in forming an inner adhesive resin layer ( 5 ), the adhesive strength with both, the metallic foil ( 4 ) as the barrier layer and a resin of an inner sealing layer ( 3 ), has, on that surface ( 4a ) the metal foil ( 4 ), which was chemically transformed, a step of laminating and forming the sealing layer ( 3 ), which contains a thermoplastic resin, on the inner adhesive resin layer ( 5 ), and a step of heat-treating a laminate produced by the above steps, using a hot roller ( 22 ), which is heated to 130°C to 220°C, whereby the outer substrate layer ( 2 ) on one side of the hot roller ( 22 ) is located where a biaxially oriented polyethylene terephthalate film is used, the film fulfills the following expressions (I) and (II): 500 MPa ≤ MB + TB ≤ 700 MPa, Printout (I) |MB – TB| ≤ 30 MPa, expression (II) where MB is a tensile breaking load in one direction M of the biaxially oriented polyethylene terephthalate film, and TB is a tensile breaking load in one direction T of the biaxially oriented polyethylene terephthalate film. [13] Method for producing a molded packaging material ( 1 ) according to claim 12, wherein a resin containing a propylene homopolymer or a copolymer resin containing at least propylene and ethylene as a copolymerization component, each having a melting point of 130°C to 160°C and a melt mass flow rate of 1 to 25 g / 10 min, is the thermoplastic resin of the sealing layer ( 3 ) is used. [14] Method for producing a molded packaging material ( 1) according to claim 12 or 13, wherein the inner adhesive resin layer ( 5 ) is formed by applying and drying an adhesive resin containing a polyolefin resin with a carboxyl group and a multifunctional isocyanate compound, and having an equivalence ratio [NCO] / [OH] of an isocyanate group of the multifunctional isocyanate compound to a hydroxyl group forming the carboxyl group of the polyolefin resin of 1.0 to 10.

0. [15] Method for producing a molded packaging material ( 1 ) according to claim 12 or 13, wherein the inner adhesive resin layer ( 5 ) is formed with an adhesive composition containing polyolefin polyol and a multifunctional isocyanate hardener, and further comprising a thermoplastic elastomer and / or a tackifier.