JP2016072156A - Battery packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery packaging material in which a change amount of thickness of a metal foil layer through a molding process can be checked by a nondestructive method.SOLUTION: The battery packaging material comprises a laminate having at least a base layer, an adhesive layer, a metal foil layer, and a sealant layer, in this order. The laminate includes at least one layer functioning as a fluorescence layer containing a fluorescent substance having no absorption in a visible light region. When at least either the base layer or the adhesive layer contains the fluorescent substance, the layer containing the fluorescent substance of the two layers functions as a fluorescence layer. When a resin layer containing the fluorescent substance is formed on an opposite side of the base layer to the adhesive layer, the resin layer functions as a fluorescence layer.SELECTED DRAWING: None

Description

  The present invention relates to a battery packaging material capable of confirming a change in thickness of a metal foil layer before and after molding by a nondestructive method.

  Conventionally, various types of batteries have been developed, and packaging materials are indispensable members for sealing battery elements such as electrodes and electrolytes in all batteries. Conventionally, metal packaging materials have been widely used as battery packaging, but in recent years, with the increasing performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., batteries are required to have various shapes. At the same time, there is a demand for reduction in thickness and weight. However, metal battery packaging materials that have been widely used in the past have the disadvantages that it is difficult to follow the diversification of shapes and that there is a limit to weight reduction.

  Therefore, in recent years, a film-like laminate in which a base material layer / adhesive layer / barrier layer / sealant layer are sequentially laminated as a battery packaging material that can be easily processed into various shapes and can be reduced in thickness and weight. Has been proposed (see, for example, Patent Document 1). Such a film-shaped battery packaging material is formed so that the battery element can be sealed by causing the sealant layers to face each other and heat-sealing the peripheral portion by heat sealing.

  In conventional film-like battery packaging materials, the barrier layer has a function of preventing the entry of water vapor, oxygen, light, etc. into the battery, in addition to improving the strength of the packaging material, and metal foil is often used. ing.

  In recent years, there has been an increasing demand for smaller and thinner batteries, and there is a demand for further thinning of film-like battery packaging materials so as to follow the demand. Furthermore, there is no time for encouraging further improvements in battery performance, and accordingly, an increase in battery capacity is required. Film-like battery packaging material is processed into a predetermined shape by deep drawing or the like to seal the battery element. Therefore, to improve battery capacity, the formability of film-like battery packaging material is improved. To increase the molding depth (elongation during molding).

  When the battery packaging material is formed by such deep drawing or the like, for example, when the thickness of the metal foil layer is thinly stretched to about 20 μm or less, pinholes are easily generated in the metal foil layer. .

JP 2001-202927 A

As described above, battery packaging materials are desired to have a thinner thickness and an increased molding depth, but when the thickness of the metal foil layer is reduced by molding, pinholes are generated in the metal foil layer. It becomes easy. Therefore, in a battery packaging material with a small thickness, it is desired to confirm whether or not the thickness of the metal foil layer has become too thin after molding. However, in the battery packaging material after molding, in order to confirm the thickness of the metal foil layer at each position, conventionally, the battery packaging material is cut in the stacking direction, The method of measuring thickness had to be adopted. In such an inspection by destruction, only a small part of the product can be inspected. Therefore, when the molding depth is increased while reducing the thickness of the battery packaging material, the metal foil layer is generated to such an extent that pinholes are generated. There is a possibility that the molded body of the battery packaging material having a reduced thickness will be used for the production of the battery. Under such circumstances, the present inventors examined a method for grasping the thickness of the metal foil layer nondestructively.
The main object of the present invention is to provide a battery packaging material in which the amount of change in the thickness of the metal foil layer before and after molding can be confirmed by a non-destructive method.

  The inventors of the present invention have intensively studied to solve the above problems. As a result, it comprises a laminate having at least a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order, and the laminate becomes a fluorescent light emitting layer containing a fluorescent material that does not absorb in the visible light region. When at least one layer is provided and at least one of the base material layer and the adhesive layer contains the fluorescent material, the layer containing the fluorescent material among these layers becomes a fluorescent light emitting layer, and the base material When the resin layer containing the fluorescent material is formed on the opposite side of the adhesive layer of the layer, the resin layer becomes a fluorescent light-emitting layer, so that the thickness of the metal foil layer before and after molding can be obtained by a non-destructive method. It was found that the amount of change can be confirmed. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the invention of the aspect hung up below.
Item 1. It consists of a laminate having at least a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent material that does not absorb in the visible light region,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the said fluorescent substance is formed in the opposite side to the said contact bonding layer of the said base material layer, the said resin layer is a packaging material for batteries used as a fluorescence light emitting layer.
Item 2. Item 6. The battery packaging material according to Item 1, wherein the phosphor is a phosphor that emits fluorescence by absorbing light irradiated by black light.
Item 3. The laminate has a resin layer containing the fluorescent material,
Item 3. The battery packaging material according to Item 1 or 2, wherein the resin layer has a thickness of 1 to 10 µm.
Item 4. Item 4. The battery packaging material according to any one of Items 1 to 3, wherein the metal foil layer is an aluminum foil.
Item 5. The manufacturing method of the molded object of the packaging material for batteries including following process (1)-(4).
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold Molding step for obtaining a molded body by molding into a shape conforming to step (3): irradiating black light from the base material layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent substance. Step Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the luminous efficiency of the fluorescence obtained in the step (3). The measuring method of the variation | change_quantity of the thickness of the metal foil layer before and behind shaping | molding of the molded object of the packaging material for batteries including following process (1)-(4).
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold Molding step for obtaining a molded body by molding into a shape conforming to step (3): irradiating black light from the base material layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent substance. Step Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the luminous efficiency of the fluorescence obtained in the step (3). Item 5. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is accommodated in the battery packaging material according to any one of Items 1 to 4.

  The battery packaging material of the present invention comprises a laminate having at least a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order, and the laminate comprises a fluorescent material that does not absorb in the visible light region. When at least one layer to be a fluorescent light emitting layer is included and at least one of the base material layer and the adhesive layer contains the fluorescent material, the layer containing the fluorescent material among these layers is fluorescent light emitting. When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Thereby, in the battery packaging material of this invention, the variation | change_quantity of the thickness of the metal foil layer before and behind shaping | molding can be confirmed by the nondestructive method.

Moreover, the manufacturing method of the molded object of the packaging material for batteries of this invention, and the measuring method of the variation | change_quantity of the thickness of the metal foil layer before and behind the shaping | molding of the said molded object are respectively following process (1)-(4). Including.
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold A molding step for obtaining a molded body by molding into a shape conforming to step (3): a step of irradiating black light from the resin layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent material Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the fluorescence emission efficiency obtained in the step (3).

  According to the method for producing a molded body of battery packaging material of the present invention and the method for measuring the amount of change in the thickness of the metal foil layer before and after molding the molded body, the metal foil layer before and after molding of the battery packaging material, respectively. Since the amount of change in the thickness of the metal foil layer can be grasped, the battery packaging material including the portion where the thickness of the metal foil layer is reduced to a predetermined value (for example, 20 μm) or less can be removed from the product. It is possible to effectively suppress the use of the molded body of the battery packaging material, which is likely to generate, for the production of the battery.

It is a schematic diagram which shows an example of the cross-sectional structure of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-sectional structure of the packaging material for batteries of this invention.

  The battery packaging material of the present invention comprises a laminate having at least a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order, and the laminate comprises a fluorescent material that does not absorb in the visible light region. When at least one layer to be a fluorescent light emitting layer is included and at least one of the base material layer and the adhesive layer contains the fluorescent material, the layer containing the fluorescent material among these layers is fluorescent light emitting. When the resin layer containing the fluorescent substance is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer.

  That is, in the battery packaging material of the present invention, at least one of the resin layer, the base material layer, and the adhesive layer contains a fluorescent material that does not absorb in the visible light region, and the fluorescent material is included. The functioning layer functions as a fluorescent light emitting layer. In the fluorescent light emitting layer, when light having a predetermined wavelength is irradiated onto the fluorescent material, the fluorescent material emits fluorescence by absorbing the light. In the battery packaging material after molding, the fluorescence emission efficiency per unit area increases as the thickness of the fluorescent light emitting layer increases, and the fluorescence emission efficiency per unit area decreases as the thickness decreases. Further, the amount of change in the thickness of the fluorescent light emitting layer due to molding and the amount of change in the thickness of the metal foil layer have a correlation with each other. Therefore, when the battery packaging material is molded at various molding depths, the surface distribution of the fluorescence emission efficiency of the battery packaging material and the thickness of the metal foil layer measured by cutting the battery packaging material in the stacking direction The thickness of the metal foil layer of the battery packaging material before and after molding is measured by measuring the surface distribution of the fluorescence emission efficiency of the battery packaging material after molding. The amount of change can be measured nondestructively. Hereinafter, the battery packaging material of the present invention will be described in detail.

1. Laminated structure of battery packaging material The battery packaging material of the present invention has a laminated structure comprising at least a base material layer 1, an adhesive layer 2, a metal foil layer 3, and a sealant layer 4 in this order. FIG. 1 shows an example in which a base material layer 1, an adhesive layer 2, a metal foil layer 3, and a sealant layer 4 are laminated in this order as an example of a cross-sectional structure of the battery packaging material of the present invention. Moreover, in FIG. 2, the resin layer 5, the base material layer 1, the contact bonding layer 2, the metal foil layer 3, and the sealant layer 4 are laminated | stacked in this order as an example of the cross-sectional structure of the battery packaging material of this invention. Show about.

  The laminate that forms the battery packaging material of the present invention includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent material that does not absorb in the visible light region. In the stacked body, the layer containing the fluorescent substance becomes a fluorescent light emitting layer. Therefore, when at least one of the base material layer 1 and the adhesive layer 2 contains the fluorescent material, the layer containing the fluorescent material among them becomes a fluorescent light emitting layer. Moreover, when the laminated body is provided with the resin layer 5, the resin layer 5 becomes a fluorescence light emitting layer. The number of layers to be the fluorescent light emitting layer may be one layer or two or more layers.

  In the battery packaging material of the present invention, an adhesive layer 6 may be provided on the base material layer 1 side of the sealant layer 4 as necessary for the purpose of improving the adhesiveness of the sealant layer 4.

  When the resin layer 5 is provided in the battery packaging material of the present invention, the resin layer 5 is the outermost layer, and when the resin layer 5 is not provided, the base material layer 1 is the outermost layer. In the battery packaging material of the present invention, the sealant layer 4 is the innermost layer. When assembling the battery, the sealant layers 4 located on the periphery of the battery element are brought into contact with each other and thermally welded to seal the battery element and seal the battery element.

2. Composition of each layer forming battery packaging material [resin layer 5]
In the battery packaging material of the present invention, the resin layer 5 is a layer that is provided on the base material layer 1 as necessary, and is a layer that forms the outermost layer. The resin layer 5 includes a resin and a fluorescent material that does not absorb in the visible light region. The resin forming the resin layer 5 is not particularly limited as long as it has insulating properties. Examples of the material for forming the resin layer 5 include polyester, polyamide, epoxy, acrylic, fluorine resin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and a mixture or copolymer thereof. Specific examples of these materials are the same as those exemplified in the base material layer 1 described later. The raw material which forms the base material layer 1 may be used individually by 1 type, and may be used in combination of 2 or more types.

  The fluorescent substance that does not absorb in the visible light region is not particularly limited as long as it is a substance that absorbs light having a predetermined wavelength and emits fluorescence. As a preferable fluorescent substance, for example, a substance that absorbs light irradiated by black light and emits fluorescence is cited. Although it does not restrict | limit especially as light irradiated by a blacklight, Preferably an ultraviolet-ray is mentioned. That is, the fluorescent material is preferably a fluorescent material that does not absorb in the visible light region and emits fluorescence by absorbing ultraviolet rays. Specific examples of fluorescent substances include photoluminescent materials for all organic compounds including aromatics (those that emit visible light include aromatics having two or more condensed naphthalenes), luminol, naphthalene derivatives, anthracene derivatives, tetracene derivatives, Examples include pyrene derivatives, perylene derivatives, and metal complexes. Specific examples of the metal complex include an aluminum-quinoline complex and a phthalocyanine derivative. A fluorescent substance may be used individually by 1 type, and may be used in combination of 2 or more types. In the battery packaging material of the present invention, since the fluorescent material does not absorb visible light, coloring of the fluorescent light-emitting layer by the fluorescent material can be suppressed in an environment where visible light is irradiated.

  The content of the fluorescent substance in the resin layer 5 is such that the surface distribution of the luminous efficiency of the fluorescence emitted from the fluorescent substance can be measured by irradiating black light from the surface of the resin layer 5 as described later. If there is no particular limitation, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably about 0.5% by mass or more. In addition, as an upper limit of content of a fluorescent substance, about 5 mass% is mentioned.

  In the battery packaging material of the present invention, the resin layer 5 is preferably provided. When the battery packaging material of the present invention has the resin layer 5, at least the resin layer 5 is a fluorescent light emitting layer. In the case where the resin layer 5 is provided, the base material layer 1 and the adhesive layer 2 do not need to contain a fluorescent material, but each may contain a fluorescent material and be a fluorescent light emitting layer together with the resin layer 5.

  The thickness of the resin layer 5 is not particularly limited. For example, even when the base material layer 1 and the adhesive layer 2 do not contain the above fluorescent substance, the metal foil layer 3 before and after molding is formed by a nondestructive method. From the viewpoint of confirming the amount of change in thickness with high accuracy, it is preferably about 1 to 10 μm, more preferably about 3 to 8 μm.

[Base material layer 1]
In the battery packaging material of the present invention, the base material layer 1 is a layer that functions as a base material for the battery packaging material. When the resin layer 5 is not provided, the base material layer 1 is a layer that forms the outermost layer. Moreover, when the base material layer 1 contains said fluorescent substance, the base material layer 1 functions also as a fluorescence light emitting layer.

  The material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy, acrylic, fluororesin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and a mixture or copolymer thereof.

  Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, and repeating units of butylene terephthalate. Copolyester etc. mainly composed of The copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)). Abbreviated), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate). In addition, as a copolymer polyester mainly composed of butylene terephthalate as a repeating unit, specifically, a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit (hereinafter referred to as polybutylene (terephthalate / isophthalate)). For example), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type. Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.

  Specific examples of the polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 6,6; terephthalic acid and / or Or hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide, polymer, such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) containing structural units derived from isophthalic acid Polyamides containing aromatics such as taxylylene adipamide (MXD6); Alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and isocyanate components such as lactam components and 4,4′-diphenylmethane-diisocyanate Copolymerized polyamide, Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polymerized polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like. These polyamides may be used individually by 1 type, and may be used in combination of 2 or more type. The stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.

  The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1.

  Among these, as a resin film which forms the base material layer 1, Preferably nylon and polyester, More preferably, biaxially stretched nylon, biaxially stretched polyester, Most preferably, biaxially stretched polyester is mentioned.

  The base material layer 1 can also be laminated with resin films of different materials in order to improve pinhole resistance and insulation when used as a battery package. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, and a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated. When making the base material layer 1 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as a co-extrusion method, a sand lamination method, or a thermal laminating method can be mentioned.

  The base material layer 1 may contain said fluorescent substance. As described above, when the battery packaging material of the present invention does not have the resin layer 5, at least one of the base material layer 1 and the adhesive layer 2 described later includes a fluorescent material and becomes a fluorescent light emitting layer. On the other hand, when the battery packaging material of the present invention has the resin layer 5, the base material layer 1 may not contain a fluorescent substance.

  When the base material layer 1 contains a fluorescent material, the content of the fluorescent material in the base material layer 1 is not particularly limited as long as the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent material can be measured. , Preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably about 0.5% by mass or more. In addition, as an upper limit of content of a fluorescent substance, about 5 mass% is mentioned.

  Moreover, the base material layer 1 may be made to have low friction in order to improve moldability. In the case of reducing the friction of the base material layer 1, the friction coefficient of the surface is not particularly limited, but for example, 1.0 or less can be mentioned. In order to reduce the friction of the base material layer 1, for example, mat treatment, formation of a thin film layer of a slip agent, a combination thereof, and the like can be given.

  As the matting treatment, a matting agent is added to the base material layer 1 in advance to form irregularities on the surface, a transfer method by heating or pressurizing with an embossing roll, a surface is mechanically dry or wet blasting or filed. The method of ruining is mentioned. Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent is not particularly limited, and examples thereof include a spherical shape, a fiber shape, a plate shape, an indeterminate shape, and a balloon shape. Specific examples of the matting agent include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide. , Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, High melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. The matting agent may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface noodles.

  The slip agent thin film layer can be formed by depositing a slip agent on the surface of the base material layer 1 by bleeding out to form a thin layer, or by laminating the slip agent on the base material layer 1. The slip agent is not particularly limited. For example, fatty acid amide, metal soap, hydrophilic silicone, silicone grafted acrylic, silicone grafted epoxy, silicone grafted polyether, silicone grafted polyester, block silicone Examples thereof include acrylic copolymers, polyglycerol-modified silicone, and paraffin. These slip agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  About the thickness of the base material layer 1, about 10-50 micrometers is mentioned, for example, Preferably about 15-30 micrometers is mentioned.

[Adhesive layer 2]
In the battery packaging material of the present invention, the adhesive layer 2 is a layer disposed on the base material layer 1 in order to impart adhesion to the base material layer 1. That is, the adhesive layer 2 is provided between the base material layer 1, the base material layer 1, and the metal foil layer 3. Further, when the adhesive layer 2 contains the above-described fluorescent material, the adhesive layer 2 also functions as a fluorescent light emitting layer.

  The adhesive layer 2 is formed of an adhesive capable of adhering the base material layer 1 and the metal foil layer 3. The adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive. Also, the adhesive mechanism of the adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

  Specific examples of the resin component of the adhesive that can be used to form the adhesive layer 2 include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester. Resin; Polyether adhesive; Polyurethane adhesive; Epoxy resin; Phenol resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin, acid-modified polyolefin, metal-modified polyolefin, etc. Polyolefin resin; polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; urea resin, melamine resin and other amino resins; chloroprene rubber, nitrile rubber, styrene - rubbers such as butadiene rubber, silicone resin; fluorinated ethylene propylene copolymer, and the like. These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. The combination mode of two or more kinds of adhesive components is not particularly limited. For example, as the adhesive component, a mixed resin of polyamide and acid-modified polyolefin, a mixed resin of polyamide and metal-modified polyolefin, polyamide and polyester, Examples thereof include a mixed resin of polyester and acid-modified polyolefin, and a mixed resin of polyester and metal-modified polyolefin. Among these, extensibility, durability under high humidity conditions, anti-hypertensive action, thermal deterioration-preventing action during heat sealing, etc. are excellent, and a decrease in the lamination strength between the base material layer 1 and the metal layer 2 is suppressed. From the viewpoint of effectively suppressing the occurrence of delamination, a polyurethane two-component curable adhesive; polyamide, polyester, or a blended resin of these with a modified polyolefin is preferable.

  The adhesive layer 2 may be multilayered with different adhesive components. When the adhesive layer 2 is multilayered with different adhesive components, from the viewpoint of improving the lamination strength between the base material layer 1 and the metal foil layer 3, the adhesive component disposed on the base material layer 1 side is used as the base material layer. It is preferable to select a resin excellent in adhesiveness with 1, and select an adhesive component excellent in adhesiveness with the metal foil layer 3 as an adhesive component disposed on the metal foil layer 3 side. When the adhesive layer 2 is multilayered with different adhesive components, specifically, the adhesive component disposed on the metal foil layer 3 side is preferably acid-modified polyolefin, metal-modified polyolefin, polyester and acid-modified polyolefin. And mixed resins, resins containing copolymerized polyesters, and the like.

  The adhesive layer 2 may contain the fluorescent material described above. As described above, when the battery packaging material of the present invention does not have the resin layer 5, at least one of the base material layer 1 and the adhesive layer 2 contains a fluorescent material and becomes a fluorescent light emitting layer. On the other hand, when the battery packaging material of the present invention has the resin layer 5, the adhesive layer 2 may not contain a fluorescent substance.

  When the adhesive layer 2 contains a fluorescent material, the content of the fluorescent material in the adhesive layer 2 is not particularly limited as long as it can measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent material, but is preferably Is 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably about 0.5% by mass or more. In addition, as an upper limit of content of a fluorescent substance, about 5 mass% is mentioned.

  About the thickness of the contact bonding layer 2, about 2-50 micrometers, for example, Preferably about 3-25 micrometers is mentioned.

[Metal foil layer 3]
In the battery packaging material of the present invention, the metal foil layer 3 is a layer that functions as a barrier layer for preventing moisture, oxygen, light, and the like from entering the battery, in addition to improving the strength of the packaging material. Specific examples of the metal forming the metal foil layer 3 include metal foils such as aluminum, stainless steel, and titanium. Among these, aluminum is preferably used. In order to prevent wrinkles and pinholes during the production of the packaging material, soft aluminum, for example, annealed aluminum (JIS A8021P-O) or (JIS A8079P-O) is used as the metal foil layer 3 in the present invention. It is preferable.

  The thickness of the metal foil layer 3 is preferably about 10 to 200 μm, more preferably about 20 to 100 μm, from the viewpoint of reducing the thickness of the battery packaging material and making pinholes less likely to occur by molding. It is done.

  In the battery packaging material of the present invention, the metal foil layer 3 does not have to be subjected to chromate treatment because it has excellent electrolytic solution resistance by providing the sealant layer 4 having a specific composition. When avoiding the use of chromium, which causes environmental pollution, and placing importance on reducing the environmental burden, the metal foil layer 3 that has not been subjected to chromate treatment may be used. May use the metal foil layer 3 subjected to the chromate treatment.

  Examples of chromate treatment include chromate chromate using chromic acid compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, and potassium sulfate chromium. Treatment; Phosphoric acid chromate treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; aminated phenol having a repeating unit represented by the following general formulas (1) to (4) Examples include chromate treatment using a polymer.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. R ¹ and R ² are the same or different and each represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Examples of the hydroxyalkyl group represented by X, R ¹ and R ² include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- C1-C4 straight or branched chain in which one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group is substituted An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and hydroxyalkyl group represented by X, R ¹ and R ² may be the same or different. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is preferably, for example, 500 to 1,000,000, more preferably about 1,000 to 20,000. preferable.

The amount of the acid-resistant film formed on the surface of the metal foil layer 3 in the chromate treatment is not particularly limited. For example, the chromic acid compound is about 0.5 mg to about 0.5 mg in terms of chromium per 1 m ² of the surface of the metal foil layer 3. 50 mg, preferably about 1.0 mg to about 40 mg, phosphorus compound in terms of phosphorus is about 0.5 mg to about 50 mg, preferably about 1.0 mg to about 40 mg, and aminated phenol polymer is about 1 mg to about 200 mg, preferably Is preferably contained at a ratio of about 5.0 mg to 150 mg.

  In the chromate treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal foil layer 3 by a bar coating method, a roll coating method, a gravure coating method, a dipping method or the like, and then the metal foil layer 3 It is performed by heating so that the temperature of is about 70 ° C to 200 ° C. Further, before the chromate treatment is performed on the metal foil layer 3, the metal foil layer 3 may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing process in this manner, it is possible to more efficiently perform the chromate process on the surface of the metal foil layer 3.

  Furthermore, the metal foil layer 3 may be subjected to a chemical conversion treatment that imparts corrosion resistance, if necessary. As a chemical conversion treatment method for imparting corrosion resistance to the metal foil layer 3, specifically, metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles is dispersed in phosphoric acid. A method of forming a corrosion-resistant treatment layer on the surface of the metal layer 3 by coating is performed and baking treatment is performed at 150 ° C. or higher. Further, a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant treatment layer. Here, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned. As these cationic polymers, only one type may be used, or two or more types may be used in combination. Examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent, and the like. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

[Adhesive layer 6]
In the battery packaging material of the present invention, the adhesive layer 6 is a layer provided as necessary between the metal foil layer 3 and the sealant layer 4 in order to firmly adhere the sealant layer 4.

  The adhesive layer 6 is formed of an adhesive that can adhere the metal foil layer 3 and the sealant layer 4. Although there is no restriction | limiting in particular about the composition of the adhesive agent used for formation of the contact bonding layer 6, For example, the resin composition containing a thermosetting resin is mentioned. Specific examples of the thermosetting resin used for the adhesive layer 6 are the same as those exemplified for the adhesive layer 2.

  About the thickness of the contact bonding layer 6, about 1-40 micrometers is mentioned, for example, Preferably about 2-30 micrometers is mentioned.

[Sealant layer 4]
In the battery packaging material of the present invention, the sealant layer 4 corresponds to the innermost layer, and is a layer that seals the battery element by heat-sealing the sealant layers when the battery is assembled.

  The resin component used for the sealant layer 4 is not particularly limited as long as it can be thermally welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

  Specific examples of the polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene Crystalline polypropylene or amorphous polypropylene such as a random copolymer of propylene and ethylene; an ethylene-butene-propylene terpolymer; and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Is mentioned. Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these polyolefins, a cyclic alkene is preferable, and norbornene is more preferable.

  The carboxylic acid-modified polyolefin is a polymer obtained by modifying the polyolefin with a carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

  The carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the α, β-unsaturated carboxylic acid or its anhydride, or α, β with respect to the cyclic polyolefin. -A polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be modified with carboxylic acid is the same as described above. The carboxylic acid used for modification is the same as that used for modification of the acid-modified cycloolefin copolymer.

  Among these resin components, preferably a crystalline or amorphous polyolefin, a cyclic polyolefin, and a blend polymer thereof; more preferably, polyethylene, polypropylene, a copolymer of ethylene and norbornene, and two or more of these The blend polymer of these is mentioned.

  The sealant layer 4 may be formed of one kind of resin component alone, or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the sealant layer may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.

  Further, the thickness of the sealant layer 4 is not particularly limited, but may be about 2 to 2000 μm, preferably about 5 to 1000 μm, and more preferably about 10 to 500 μm.

3. Production method of battery packaging material The production method of the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained. For example, the following first step to first step A method comprising three steps is illustrated:
In a first step of forming a laminate (hereinafter also referred to as “laminate A”) in which the base material layer 1 is laminated on the metal foil layer 3 via the adhesive layer 2, and in the first step A second step of laminating the sealant layer 4 on the surface of the obtained laminate A opposite to the base material layer.

  Specifically, the formation of the laminate A in the first step is performed by using the adhesive in a state in which the base material layer 1 and the metal foil layer 3 are bonded to each other through the adhesive used for forming the adhesive layer 2. This is done by curing. For example, when the laminate A is formed by a dry lamination method, an adhesive used for forming the adhesive layer 2 on the base material layer 1 or the metal foil layer 3 is used as a gravure coating method or a roll coating method. After applying and drying by a coating method such as the above, the metal foil layer 3 or the base material layer 1 may be laminated and heat-treated. The conditions for the heat treatment may be appropriately set according to the type of resin component of the adhesive, etc., for example, 25 to 100 ° C., preferably 30 to 80 ° C., 1 to 10 days, preferably 2 to 7 Day.

  If the adhesive layer 6 is not provided in the second step, the resin component for forming the sealant layer 4 is applied to the surface of the laminate A opposite to the base material layer 1 by a gravure coating method or a roll coating method. What is necessary is just to apply | coat by methods, such as. If the adhesive layer 6 is provided, the second step includes, for example, (1) co-extrusion of the adhesive layer 6 and the sealant layer 4 on the surface of the laminate A opposite to the base material layer 1. (2) Separately, a laminated body in which the adhesive layer 6 and the sealant layer 4 are laminated is formed on the surface of the laminated body A opposite to the base material layer 1. (3) Drying and baking at a high temperature by extrusion or solution coating with an adhesive for forming the adhesive layer 6 on the surface opposite to the base material layer 1 of the laminate A. A method of laminating the sealant layer 4 which has been laminated by a method or the like and previously formed into a sheet on the adhesive layer 6 by a thermal lamination method, (4) a surface of the laminate A opposite to the base material layer 1; Adhesive layer between sealant layer 4 formed into a sheet in advance A method (sand lamination method) of bonding the surface of the laminate A opposite to the base material layer 1 and the sealant layer 4 through the adhesive layer 6 while pouring the adhesive for forming the film in a molten state, etc. Is mentioned.

  Furthermore, when the resin layer 5 is provided, a resin composition containing a resin that forms the resin layer 5 and a fluorescent material is applied onto the base layer 1 by a method such as a gravure coating method or a roll coating method. It may be performed by. The resin layer 5 may be formed after the laminate A is formed and before the sealant layer 4 is laminated, or after the sealant layer 4 is laminated.

  As described above, a laminate having the resin layer 5, the base material layer 1, the adhesive layer 2, the metal foil layer 3, the adhesive layer 6 provided if necessary, and the sealant layer 4 provided in this order as required. Is formed.

  In the battery packaging material of the present invention, each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing (pouching, embossing), etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment may be performed.

4). Method for producing molded body of battery packaging material The method for producing a molded body of battery packaging material of the present invention comprises the following steps (1) to (4).
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold Molding step for obtaining a molded body by molding into a shape conforming to step (3): irradiating black light from the base material layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent substance. Step Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the fluorescence emission efficiency obtained in the step (3).

  The preparation of the battery packaging material in the step (1) can be performed, for example, by adopting the method for producing the battery packaging material. In the method for producing a molded body of a battery packaging material according to the present invention, the above-described fluorescent material that does not absorb in the visible light region as long as it is a fluorescent material that absorbs light irradiated with black light and emits fluorescence. In addition, a fluorescent material having absorption in the visible light region may be used.

  Step (2) is a molding step of obtaining a molded body by molding the battery packaging material into a shape along the mold. In the step (2), a space for accommodating the battery packaging material is formed. The battery packaging material can be molded by a known method such as deep drawing using a molding die.

  In the step (3), from the base material layer 1 side of the molded product obtained by molding the battery packaging material (on the surface of the base material layer 1 or on the surface of the resin layer 5 when the resin layer 5 is provided). A step of measuring the surface distribution of the luminous efficiency of the fluorescence emitted from the fluorescent material by irradiating with black light is performed. Although it does not restrict | limit especially as light irradiated by a blacklight, Preferably an ultraviolet-ray is mentioned. As a specific example of the black light, for example, a light having a wavelength of about 200 to 400 nm and about 2 to 100 W may be used. Further, the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent material by irradiation with black light can be measured by the fluorescence intensity.

  In the step (4), a step of confirming the amount of change in the thickness of the metal foil layer 3 of the molded body of the battery packaging material is performed based on the surface distribution of the fluorescence emission efficiency obtained in the step (3). As described above, in the battery packaging material prepared in step (1), at least one of the resin layer, the base material layer, and the adhesive layer contains a fluorescent substance, and the fluorescent substance is contained. The layer functions as a fluorescent light emitting layer. In the battery packaging material formed in step (2), the fluorescent emission efficiency per unit area measured in step (3) increases as the thickness of the fluorescent light emitting layer increases, and the portion as the thickness decreases. The luminous efficiency of fluorescence per area is reduced. Further, the amount of change in the thickness of the fluorescent light emitting layer due to molding and the amount of change in the thickness of the metal foil layer 3 are correlated with each other. Therefore, when the battery packaging material is molded at various molding depths, the surface distribution of the fluorescence emission efficiency of the battery packaging material and the metal foil layer 3 measured by cutting the battery packaging material in the stacking direction are measured. By recording the relationship with the thickness in advance, based on the surface distribution of the fluorescent luminous efficiency of the molded battery packaging material measured in the step (3), in the step (4), for the battery before and after the molding. The amount of change in the thickness of the metal foil layer 3 of the packaging material can be measured nondestructively. Therefore, in the battery packaging material after molding, for example, the battery packaging material including a portion in which the thickness of the metal foil layer 3 is thinned to a predetermined value (for example, 20 μm) or less can be removed from the product. It is possible to effectively suppress the use of the molded body of the battery packaging material, which is likely to generate, for the production of the battery.

5. Method for measuring the amount of change in the thickness of the metal foil layer before and after forming the molded body of the battery packaging material The method for measuring the amount of change in the thickness of the metal foil layer before and after molding the molded body of the battery packaging material of the present invention is as described above. Including the same steps (1) to (4). By including the said process (1)-(4), it becomes possible to measure the variation | change_quantity of the thickness of the metal foil layer before and behind shaping | molding of the molded object of a battery packaging material nondestructively. Therefore, in the battery packaging material after molding, for example, the battery packaging material including a portion in which the thickness of the metal foil layer 3 is thinned to a predetermined value (for example, 20 μm) or less can be removed from the product. It is possible to effectively suppress the use of the molded body of the battery packaging material, which is likely to generate, for the production of the battery.

6). Application of Battery Packaging Material The battery packaging material of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.

  Specifically, a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed using the battery packaging material of the present invention, with the metal terminals connected to each of the positive electrode and the negative electrode protruding outward. A battery using a battery packaging material is formed by covering the periphery of the element so that a flange portion (a region where the sealant layers are in contact with each other) can be formed, and heat-sealing and sealing the sealant layers of the flange portion. Provided. In addition, when accommodating a battery element using the battery packaging material of the present invention, the battery packaging material of the present invention is used such that the sealant portion is on the inner side (surface in contact with the battery element).

  The battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited. For example, a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery , Nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are suitable applications for the battery packaging material of the present invention.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
<Manufacture of battery packaging materials using an adhesive layer as a fluorescent light emitting layer>
Chemical conversion treatment is performed on both sides of an aluminum foil (thickness 40 μm) as a metal layer, and a nylon film (thickness 25 μm) is used as a base layer on one chemical conversion treatment surface so that the thickness of the adhesive layer is about 3 μm. It bonded together by the dry lamination method through the polyester-type adhesive agent. Each of the adhesives was mixed with a fluorescent agent containing a naphthalene derivative made by Sinloi so as to have the ratio shown in Table 1, and the adhesive layer was used as a fluorescent material layer.
Next, a carboxylic acid-modified polypropylene (23 μm) and polypropylene (23 μm) for forming a sealant layer are coextruded on the chemical conversion treatment surface of the other aluminum foil to form a base layer / adhesive layer / aluminum foil // sealant layer A laminate was obtained.
In addition, all of the chemical conversion treatment of the aluminum foil was performed by applying a roll coating method using an aqueous solution consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid as a treatment liquid, and baking under conditions where the film temperature was 180 ° C. or higher. It was. The amount of chromium applied was 3 mg / m ² (dry weight).

<Formation of battery packaging materials>
Each battery packaging material obtained in Example 1 was cut to prepare a 120 × 80 mm strip, which was used as a test sample. Using a straight mold composed of a 30 × 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold and the above, the thermal adhesive resin layer side is positioned on the male mold side. Place the test sample, set the forming depth to various depths (about 3.5-5.5mm), hold the test sample with presser pressure (surface pressure) of 0.1MPa, cold forming (One-stage drawing).

<Measurement of fluorescence intensity>
At the molding corner of each test sample before and after the above molding, irradiate black light from the base material layer side, measure the surface distribution of the luminous efficiency of the fluorescence emitted from the base material layer side, and before and after molding the test sample. The rate of decrease in fluorescence intensity was calculated. The fluorescence intensity was measured using a fluorescence intensity measuring device manufactured by XBio. The results are shown in Table 1.

<Measurement of remaining thickness ratio of metal foil layer and adhesive layer after molding>
For each test sample before and after the above molding, cut in the thickness direction using a microtome manufactured by Yamato Koki Kogyo, and using a laser microscope manufactured by Keyence, the metal foil layer and the adhesive layer of the molding corner portion of the test sample The thickness was measured, and the remaining thickness ratio of the metal foil layer and the adhesive layer after molding was calculated. The results are shown in Table 1.

<Confirmation of pinhole after molding>
About each test sample after said shaping | molding, the presence or absence of the generation | occurrence | production of the pinhole of a metal layer and a crack was confirmed visually. Regarding the occurrence of pinholes and cracks, about 30 test samples, after the above molding, one where pinholes or cracks were observed at one location was evaluated as having pinholes, and pinholes or cracks were also observed at one location. Those that could not be identified were identified as no pinholes (◯). The results are shown in Table 1.

  From the results shown in Table 1, there is a high correlation between the decrease rate of the emission intensity based on the adhesive layer as the fluorescent light emitting layer and the remaining ratio of the thickness of the metal layer and the adhesive layer (fluorescent light emitting layer) before and after molding. It can be seen that the amount of change in the thickness of the metal foil layer before and after molding can be confirmed by a non-destructive method.

Example 2
<Manufacture of battery packaging materials using a base layer as a fluorescent light emitting layer>
Chemical conversion treatment is performed on both sides of an aluminum foil (thickness 40 μm) as a metal layer, and a nylon film (thickness 25 μm) is used as a base layer on one chemical conversion treatment surface so that the thickness of the adhesive layer is about 3 μm. It bonded together by the dry lamination method through the polyester-type adhesive agent. Each base material layer was mixed with a fluorescent agent containing a naphthalene derivative manufactured by XBio in such a ratio as shown in Table 2, and the base material layer was used as a fluorescent material layer.
Next, a carboxylic acid-modified polypropylene (23 μm) and polypropylene (23 μm) for forming a sealant layer are coextruded on the chemical conversion treatment surface of the other aluminum foil to form a base material layer / adhesive layer / aluminum foil / sealant layer. A laminate was obtained.
In addition, all of the chemical conversion treatment of the aluminum foil was performed by applying a roll coating method using an aqueous solution consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid as a treatment liquid, and baking under conditions where the film temperature was 180 ° C. or higher. It was. The amount of chromium applied was 3 mg / m ² (dry weight).

<Formation of battery packaging materials>
Each battery packaging material obtained in Example 2 was cut, a test sample was produced in the same manner as in Example 1, and molded.

<Measurement of fluorescence intensity>
In the same manner as in Example 1, at the molding corner portion of each test sample before and after molding in Example 2, the surface of the luminous efficiency of the fluorescence emitted from the fluorescent material is measured by irradiating the black light from the base material layer side. The decrease rate of the fluorescence intensity before and after the molding of the test sample was calculated. The results are shown in Table 2.

<Measurement of remaining thickness ratio of metal foil layer and base material layer after molding>
For the test samples before and after molding in Example 2, as in Example 1, the thickness of the metal foil layer and the base material layer at the molding corner of each test sample was measured, and the metal foil layer and base after molding were measured. The thickness residual ratio of the material layer was calculated. The results are shown in Table 2.

<Confirmation of pinhole after molding>
In the same manner as in Example 1, the presence or absence of pin poles was confirmed for each test sample after molding in Example 2. The results are shown in Table 2.

  From the results shown in Table 2, there is a high correlation between the reduction rate of the emission intensity based on the base material layer as the fluorescent light emitting layer and the remaining ratio of the thickness of the metal layer and the base material layer (fluorescent light emitting layer) before and after molding. It can be seen that the amount of change in the thickness of the metal foil layer before and after molding can be confirmed by a non-destructive method.

Example 3
<Manufacture of battery packaging material using a resin layer formed on a base material layer as a fluorescent light emitting layer>
Chemical conversion treatment is performed on both sides of an aluminum foil (thickness 40 μm) as a metal layer, and a nylon film (thickness 25 μm) is used as a base layer on one chemical conversion treatment surface so that the thickness of the adhesive layer is about 3 μm. It bonded together by the dry lamination method through the polyester-type adhesive agent. Next, a resin layer (thickness 5 μm) in which a fluorescent agent containing a naphthalene derivative made by XBio is mixed is formed on the base material layer so as to have the ratio shown in Table 3, respectively. Was used as a fluorescent material layer.
Next, carboxylic acid-modified polypropylene (23 μm) and polypropylene (23 μm) for forming a sealant layer are coextruded on the chemical conversion treatment surface of the other aluminum foil, and resin layer / base material layer / adhesive layer / aluminum foil / sealant layer A laminate comprising:
In addition, all of the chemical conversion treatment of the aluminum foil was performed by applying a roll coating method using an aqueous solution consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid as a treatment liquid, and baking under conditions where the film temperature was 180 ° C. or higher. It was. The amount of chromium applied was 3 mg / m ² (dry weight).

<Formation of battery packaging materials>
Each battery packaging material obtained in Example 3 was cut and each test sample was produced in the same manner as in Example 1 and molded.

<Measurement of fluorescence intensity>
In the same manner as in Example 1, in the molding corner portion of each test sample before and after the molding in Example 3, the black light is irradiated from the resin layer side, and the surface distribution of the luminous efficiency of the fluorescence emitted from the fluorescent material is measured. The decrease rate of the fluorescence intensity before and after molding of the test sample was calculated. The results are shown in Table 3.

<Measurement of remaining thickness ratio of metal foil layer and base material layer after molding>
For each test sample before and after molding in Example 3, in the same manner as in Example 1, the thickness of the metal foil layer and the resin layer at the molding corner portion of the test sample was measured, and the metal foil layer and the resin layer after molding were measured. The thickness residual ratio was calculated. The results are shown in Table 3.

<Confirmation of pinhole after molding>
In the same manner as in Example 1, the presence or absence of pin poles was confirmed for each test sample after molding in Example 3. The results are shown in Table 3.

  From the results shown in Table 3, there is a high correlation between the reduction rate of the emission intensity based on the resin layer as the fluorescent light emitting layer before and after molding and the residual rate of the thickness of the metal layer and the resin layer (fluorescent light emitting layer). It can be seen that the amount of change in the thickness of the metal foil layer before and after molding can be confirmed by a non-destructive method.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesion layer 3 Metal foil layer 4 Sealant layer 5 Resin layer

Claims (7)

It consists of a laminate having at least a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent material that does not absorb in the visible light region,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the said fluorescent substance is formed in the opposite side to the said contact bonding layer of the said base material layer, the said resin layer is a packaging material for batteries used as a fluorescence light emitting layer.   The battery packaging material according to claim 1, wherein the fluorescent material is a fluorescent material that emits fluorescence by absorbing light irradiated by black light. The laminate has a resin layer containing the fluorescent material,
The battery packaging material according to claim 1 or 2, wherein the resin layer has a thickness in the range of 1 to 10 µm.   The battery packaging material according to any one of claims 1 to 3, wherein the metal foil layer is an aluminum foil. The manufacturing method of the molded object of the packaging material for batteries including following process (1)-(4).
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold Molding step for obtaining a molded body by molding into a shape conforming to step (3): irradiating black light from the base material layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent substance. Step Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the fluorescence emission efficiency obtained in the step (3). The measuring method of the variation | change_quantity of the thickness of the metal foil layer before and behind shaping | molding of the molded object of the packaging material for batteries including following process (1)-(4).
Step (1): Step of preparing the following battery packaging material At least, it comprises a laminate having a base material layer, an adhesive layer, a metal foil layer, and a sealant layer in this order,
The laminate includes at least one layer that becomes a fluorescent light-emitting layer containing a fluorescent substance,
When at least one of the base material layer and the adhesive layer contains the fluorescent material, among these layers, the layer containing the fluorescent material becomes a fluorescent light emitting layer,
When the resin layer containing the fluorescent material is formed on the opposite side of the base material layer from the adhesive layer, the resin layer becomes a fluorescent light emitting layer. Step (2): Using the battery packaging material as a mold Molding step for obtaining a molded body by molding into a shape conforming to step (3): irradiating black light from the base material layer side of the molded body to measure the surface distribution of the luminous efficiency of the fluorescence emitted by the fluorescent substance. Step Step (4): A step of confirming the amount of change in the thickness of the metal foil layer of the molded body based on the surface distribution of the fluorescence emission efficiency obtained in the step (3).   The battery by which the battery element provided with the positive electrode, the negative electrode, and electrolyte at least is accommodated in the packaging material for batteries in any one of Claims 1-4.