JP2019160799A - Battery packaging material, method for manufacturing the same, battery, and method of manufacturing the same - Google Patents

Abstract

To provide battery packaging material having excellent printing suitability.SOLUTION: Battery packaging material comprises a laminated body comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order from the outside. The battery packaging material includes a print receiving layer on an outer surface thereof, and the print receiving layer includes an amide-based additive.SELECTED DRAWING: None

Description

  The present invention relates to a battery packaging material, a manufacturing method thereof, a battery, and a manufacturing method thereof.

  Conventionally, various types of batteries have been developed. In any battery, a packaging material is an indispensable member for sealing battery elements such as electrodes and electrolytes. 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, as a battery packaging material that can be easily processed into various shapes and can be made thinner and lighter, a film-like structure in which a base layer / adhesive layer / barrier layer / heat-sealable resin layer are sequentially laminated. A laminated body 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 heat-fusible resin layers to face each other and heat-sealing the peripheral edge portion by heat sealing.

  In various packaging materials formed by the laminates as described above, ink is printed on the surface of the base material layer to form barcodes, patterns, characters, etc., and then bonded onto the base material layer on the printed side A method of printing on a packaging material by a method of laminating an agent and a metal foil is widely adopted. However, when such a printing surface exists between the base material layer and the barrier layer, the adhesion between the base material layer and the barrier layer is lowered, and delamination is likely to occur between the layers. In particular, since high safety is required for a battery to which a battery packaging material is applied, an adhesive and a metal layer are laminated on the base material layer on the printed side. This method is avoided in battery packaging materials. Therefore, conventionally, when printing a barcode or the like on a battery packaging material, a method of sticking a seal on which a print is formed on the surface of a base material layer is generally employed.

JP 2008-287971 A

  However, when the seal on which the print is formed is affixed to the surface of the base material layer, the thickness and weight of the battery packaging material increase. Therefore, the present inventors considered a method of printing directly on the surface of the base material layer of the battery packaging material in consideration of the trend of further thinning and weight reduction for the battery packaging material in recent years. did.

  As a method for printing directly on the surface of the base material layer of the battery packaging material by ink printing, for example, pad printing (also referred to as tampo printing) or ink jet printing is known. Pad printing is a printing method as follows. First, ink is poured into a concave portion of a flat plate in which a pattern to be printed is etched. Next, the silicon pad is pressed from above the concave portion to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to the object to be printed to form a print on the object to be printed. In such pad printing, the ink is transferred to the object to be printed using an elastic silicon pad or the like. Therefore, it is easy to print on the surface of the battery packaging material after molding, and the battery element is made of the battery packaging material. After sealing, the battery can be printed. In addition, ink jet printing has similar advantages.

  However, when the present inventors examined, when ink was printed on the surface of a conventionally used base material layer formed of a polyamide resin or a polyester resin, the ink was repelled on the surface of the base material layer, It was found that the ink is difficult to fix, and there may be a missing portion where the ink is not formed. In particular, it has been clarified that printability tends to be insufficient when printing is performed by pad printing.

  Moreover, in battery packaging materials, in order to increase volume energy density, generally, recesses are formed by cold forming to increase the capacity of battery elements. In recent years, it has been required to further increase the storage volume by deep drawing. However, when pinholes or cracks occur in the battery packaging material at the time of molding, the electrolytic solution penetrates into the aluminum alloy foil layer to form metal deposits, resulting in a short circuit. For this reason, the battery packaging material is required to have more excellent moldability.

  Under such circumstances, the main object of the present invention is to provide a battery packaging material with excellent printability (first object), and in addition to excellent printability, excellent moldability. It is also an object (second object) to provide a battery packaging material provided with the above. Furthermore, another object of the present invention is to provide a method for producing the battery packaging material, a battery using the battery packaging material, and a method for producing the battery.

That is, this invention provides the invention of the aspect hung up below.
Item 1. From the outside, a battery packaging material consisting of a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The battery packaging material has a print receiving layer on its outer surface,
The printing receiving layer is a battery packaging material containing an amide-based additive.
Item 2. Item 4. The battery packaging material according to Item 1, wherein the amide-based additive is erucic acid amide.
Item 3. Item 3. The battery packaging material according to Item 1 or 2, wherein the content of the amide-based additive in the print receiving layer is 0.3% by mass or more and 6.0% by mass or less.
Item 4. Item 4. The battery packaging material according to any one of Items 1 to 3, wherein the print receiving layer is formed on the entire outer surface of the battery packaging material.
Item 5. Item 5. The battery packaging material according to any one of Items 1 to 4, further comprising a printing layer on an outer surface of the printing receiving layer.
Item 6. Item 6. The battery packaging material according to any one of Items 1 to 5, wherein the thickness of the print receiving layer is in the range of 0.001 μm to 50 μm.
Item 7. Item 7. The battery packaging material according to any one of Items 1 to 6, wherein the base material layer is formed of at least one of a polyamide resin and a polyester resin.
Item 8. Item 8. The battery packaging material according to any one of Items 1 to 7, wherein the print receiving layer contains a resin containing 80% by mass or more of an acrylic resin and the amide-based additive.
Item 9. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package body formed of the battery packaging material according to any one of Items 1 to 8.
Item 10. From the outside, at least a printing receiving layer, a base material layer, a barrier layer, and a method for producing a battery packaging material comprising a laminate comprising a heat-fusible resin layer in this order,
Comprising a laminating step of laminating the print receiving layer, the base material layer, the barrier layer, and the heat-fusible resin layer to obtain a laminate,
The printing receiving layer is provided on an outer surface of the battery packaging material, and the printing receiving layer contains an amide-based additive.
Item 11. Item 11. The method for producing a battery packaging material according to Item 10, further comprising a step of forming a printing layer on the surface of the printing receiving layer.
Item 12. Item 9. A method for producing a battery, comprising a step of housing a battery element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed by the battery packaging material according to any one of Items 1 to 8.
Item 13. Item 13. The method for producing a battery according to Item 12, further comprising a step of forming a printing layer on the surface of the printing receiving layer.

  ADVANTAGE OF THE INVENTION According to this invention, the packaging material for batteries provided with the outstanding printability can be provided. Furthermore, according to this invention, the manufacturing method of the said packaging material for batteries, the battery using the said packaging material for batteries, and the manufacturing method of a battery can be provided.

It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram for demonstrating the evaluation method of tape adhesiveness. It is a schematic diagram for demonstrating the evaluation method of tape adhesiveness.

  The battery packaging material of the present invention comprises a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order from the outside, and a print receiving layer is provided on the outer surface of the battery packaging material. And the print receiving layer includes an amide-based additive. Hereinafter, the battery packaging material of the present invention will be described in detail.

  In the present specification, for the numerical range, the numerical range indicated by “to” means “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.

1. Laminated structure of battery packaging material The battery packaging material of the present invention comprises, for example, a print receiving layer 6, a substrate layer 1, a barrier layer 3, and a heat-fusible resin layer 4 from the outside as shown in FIG. It consists of a laminated body provided in this order. In the battery packaging material of the present invention, the print receiving layer 6 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. That is, when the battery is assembled, the battery element is sealed by heat-sealing the heat-fusible resin layers 4 positioned at the periphery of the battery element to seal the battery element.

  For example, as shown in FIG. 2, the battery packaging material of the present invention has an adhesive layer 2 between the base material layer 1 and the barrier layer 3 for the purpose of enhancing the adhesion between them. It may be. For example, as shown in FIG. 3, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4 as necessary for the purpose of enhancing the adhesion. Moreover, a surface coating layer (not shown) or the like may be provided on the outside of the base material layer 1 (on the side opposite to the heat-fusible resin layer 4) as necessary. When the surface coating layer is provided, the surface coating layer is located between the base material layer 1 and the print receiving layer 6.

  As will be described later, the print receiving layer 6 may be formed on at least a part of the outer surface of the base material layer 1 (the surface opposite to the barrier layer 3). That is, the print receiving layer 6 may be formed on the entire outer surface of the base material layer 1 or may be formed on a part thereof.

  In the battery packaging material of the present invention, the dynamic friction coefficient of the base layer side surface (outer surface) is preferably about 0.50 or less, more preferably about 0.26 or less, and about 0.18. More preferably, it is more preferably about 0.13 or less. The dynamic friction coefficient means a value measured by the following method.

(Measurement of dynamic friction coefficient)
Two battery packaging materials are cut out into a rectangular shape of 200 mm × 80 mm to obtain test samples. Based on the measurement of 8.1 film-to-film of JIS K7125: 1999, using a commercially available measuring machine that measures the dynamic friction coefficient, the contact area is 40 cm ² (square with a side length of 63 mm) and the bottom surface is elastic. A sliding piece having a total mass of 200 g covered with a certain felt is used, and the substrate layer side of the test sample is overlapped with each other under the condition of a speed of 100 mm / min, and the dynamic friction coefficient is measured. The measurement environment is a temperature of 24 ° C. and a relative humidity of 50%. Also, keep the sample and sliding piece in close contact so that they do not slide. Pull the sliding piece at a speed of 100 mm / min, measure the dynamic friction force (N) between the two samples, and divide by the normal force (1.96 N) of the sliding piece of the dynamic friction force to calculate the dynamic friction coefficient To do. The dynamic friction coefficient is obtained from the average value up to the first 30 mm after starting the relative displacement motion between the contact surfaces, ignoring the peak of the static friction force. The load cell is directly connected to the sliding piece.

  The total thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but is preferably about 160 μm from the viewpoint of exhibiting high moldability while reducing the total thickness of the laminate as much as possible. Hereinafter, more preferably about 35 to 155 μm, and still more preferably about 45 to 155 μm. Even when the thickness of the laminate constituting the battery packaging material of the present invention is as thin as 160 μm or less, for example, the present invention can exhibit excellent moldability. For this reason, the packaging material for batteries of this invention can contribute to the improvement of the energy density of a battery.

2. Each layer forming the battery packaging material [base material layer 1]
In the battery packaging material of the present invention, the base material layer 1 is positioned outside the barrier layer 3 and functions as a support for the battery packaging material. 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 resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and a mixture or copolymer thereof. Can be mentioned. Among these, polyester and polyamide are preferable from the viewpoint of exhibiting high moldability.

  Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, butylene terephthalate as a repeating unit. Examples thereof include a copolymer polyester mainly used. 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 polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, and polymetaxylylene azide Polyamide containing aromatics such as Pamide (MXD6); Alicyclic polyamides such as Polyaminomethylcyclohexyl Adipamide (PACM6); and Lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate are copolymerized Polyamide, copolymerization Examples thereof include polyesteramide copolymers and polyetheresteramide copolymers, which are copolymers of lyamide and polyester or polyalkylene ether glycol; these copolymers. 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. Moreover, the base material layer 1 may be formed by coating the above-mentioned material on the barrier layer 3.

  Among these, as a resin film for forming the base material layer 1, nylon, polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, and particularly preferably biaxially stretched nylon are used from the viewpoint of exhibiting high moldability. Can be mentioned.

  The base material layer 1 can also be laminated with at least one of resin films and coatings 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 lamination method, a sandwich lamination method, or a thermal lamination method can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive. Furthermore, the bonding mechanism of the adhesive is not particularly limited, and any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, an ionizing radiation curable type such as an ultraviolet ray (UV) or an electron beam (EB), etc. There may be. As an adhesive component, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin Resins, polyimide resins, amino resins, rubbers, and silicon resins can be used.

  The base material layer of the battery packaging material may contain a water repellent. For example, a polyamide resin film such as nylon is widely used, and the polyamide resin film generally contains ethylene bisoleic acid amide, ethylene bis stearic acid amide or the like as a water repellent. By including a water repellent, the wettability of the molten resin to water can be adjusted during film production, and moderate unevenness (surface roughness) can be formed on the surface of the original film. This stretched shape remains even after stretching, and a polyamide resin film having a controlled surface slipperiness can be obtained. However, when the water repellent is contained in the base material layer, heat is applied in the baking process after the battery element such as the electrolyte is sealed in the battery packaging material, so that the water repellent is applied to the surface of the base material layer. When ink is printed on the surface of the base material layer by bleed-out and pad printing or the like, the ink is repelled on the surface of the base material layer, making it difficult to fix the ink, and a problem that a missing portion where no ink is formed is likely to occur. .

  On the other hand, in the battery packaging material of the present invention, since the print receiving layer 6 is provided on the surface of the base material layer 1, the battery packaging material can be used even when the base material layer 1 contains a water repellent. The outer surface of the material can exhibit excellent ink printability.

  Although it does not restrict | limit especially as content of the water repellent contained in the base material layer 1, Preferably it is about 200-1500 ppm, More preferably, about 300-1200 ppm is mentioned. In the present invention, the content of the water repellent contained in the base material layer 1 is the water repellent (such as ethylene bis stearamide, ethylene bis oleate amide, etc.) present in the base layer. Amide). The content of the water repellent contained in the base material layer 1 of the battery packaging material is determined by removing the base material layer 1 from the battery packaging material, dissolving the base material layer 1 in hexafluoroisopropyl alcohol, and then adding dimethylethane. In addition, solvent precipitation is performed, the resin component is separated to prepare an extraction solution of a water repellent, and the extraction solution can be quantified by GC-MS analysis.

  As thickness of the base material layer 1, about 10-50 micrometers, for example, Preferably about 12-30 micrometers is mentioned.

[Print receiving layer 6]
In the battery packaging material of the present invention, the print receiving layer 6 containing an amide-based additive is provided on at least a part of the outer surface of the battery packaging material (that is, the surface on the base material layer 1 side). The print receiving layer 6 may be formed on the entire outer surface of the battery packaging material or may be formed on a part thereof. From the viewpoint of further improving the moldability of the battery packaging material, the print receiving layer 6 is preferably formed on the entire outer surface of the battery packaging material. When the location to be printed on the outer surface of the battery packaging material is predetermined, the print receiving layer 6 is preferably formed on a part of the outer surface. In the case where the print receiving layer 6 is formed on a part of the outer surface, the area of the print receiving layer 6 occupying the outer surface from the viewpoint of a battery packaging material having both excellent printability and excellent moldability. The ratio is preferably about 50% or more, more preferably about 80% or more, still more preferably about 90% or more, and particularly preferably about 99% or more.

  As described above, instead of pasting a seal on the outside of the battery packaging material as in the prior art, the present inventors examined printing directly on the outside surface. It was revealed that the ink was repelled and the ink was difficult to be fixed, and a part where the ink was not formed may occur. In particular, there was a tendency for printability to be insufficient when printing by pad printing.

  On the other hand, in the battery packaging material of the present invention, since the print receiving layer 6 containing the amide-based additive is provided on at least a part of the outer surface, the outer surface of the battery packaging material (print receiving layer) 6), the ink is difficult to be repelled, and the ink can be suitably printed on the outside of the battery packaging material. In particular, when ink is printed by pad printing, the ink may be repelled on the outer surface and printing defects may occur. However, in such a case, the print receiving layer 6 is formed in the battery packaging material of the present invention. Therefore, the ink is not easily repelled, and is particularly suitable as a battery packaging material in which printing is formed on the outer surface by pad printing. Furthermore, since the amide-based additive is contained in the print receiving layer 6, the moldability of the battery packaging material is also excellent.

  The material constituting the print receiving layer 6 is not particularly limited as long as it has a surface on which ink is hard to be repelled. The print receiving layer 6 is formed of, for example, a resin composition containing an amide-based additive and a resin. The resin is not particularly limited, and examples thereof include a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin.

  The thermoplastic resin is not particularly limited, and acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; acrylonitrile-butadiene-styrene resins (ABS resin); acrylonitrile-styrene-acrylic ester resin, nitrified cotton resin, etc. are mentioned. Among these, an acrylic resin is preferable from the viewpoint of improving the printability and formability of the ink on the outer surface of the battery packaging material.

  The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic. Examples include resins, amide functional copolymers, and urethane resins. Among these, urethane resin is preferable from the viewpoint of improving the printability and moldability of the ink on the outer surface of the battery packaging material. Among urethane resins, polyester urethane resins are more preferable from the same viewpoint.

  Furthermore, from the viewpoint of improving the printability and moldability of the ink on the outer surface of the battery packaging material and further improving the adhesion to the tape, the resin constituting the print receiving layer 6 contains an acrylic resin. It is preferable that the ratio of the acrylic resin is 80% by mass or more. More specifically, in the resin constituting the print receiving layer 6, it is particularly preferable that the acrylic resin is about 80 to 100% by mass and the polyester urethane resin is about 0 to 20% by mass. That is, the print receiving layer 6 particularly preferably contains a resin containing about 80 to 100% by mass of an acrylic resin and about 0 to 20% by mass of a polyester urethane resin and the amide additive. When a battery using a battery packaging material is fixed with a tape or the like, the tape may be adhered to the print receiving layer 6 to fix the battery to a housing or the like. In such a case, since the adhesion of the print receiving layer 6 to the tape is excellent, the battery can be suitably fixed using the tape. In addition, as a tape, a commercially available adhesive tape etc. are used, for example.

  The ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, the polymer has a polymerizable unsaturated bond or an epoxy group, a prepolymer, an oligomer, And those obtained by appropriately mixing at least one of monomers and the like. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. A well-known thing can be used as ionizing radiation-curable resin.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, a polycarbonate urethane (meth) acrylate which is a urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane oligomer obtained by the reaction of polyether polyol, polyester polyol, caprolactone-based polyol or polycarbonate polyol and a polyisocyanate compound. it can. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth) acrylate oligomer, polycarbonate (meth) acrylate, urethane (meth) acrylate, and the like are particularly preferable. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the amide-based additive include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like. Specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc. Specific examples of the fatty acid ester amide include stearoamidoethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide, and the like. Among these, erucic acid amide is preferable from the viewpoint of improving the printability and formability of the ink on the outer surface of the battery packaging material. An amide type additive may be used individually by 1 type, and may be used in combination of 2 or more types.

  The content of the amide-based additive in the print receiving layer 6 is not particularly limited, but the viewpoint of improving the printability of ink on the outer surface of the battery packaging material, and the viewpoint of improving the printability and moldability of the ink To about 0.3 to 6.0% by mass, more preferably about 0.3 to 5.0% by mass, still more preferably about 2.0 to 4.0% by mass, and particularly preferably about 3.0 to About 4.0 mass% is mentioned.

  The content of the amide-based additive in the print receiving layer 6 can be quantified based on the intensity peak obtained by scraping the print receiving layer 6 from the battery packaging material and subjecting it to gas chromatography.

  The print receiving layer 6 may contain inorganic particles. The inorganic particles are not particularly limited. For example, silica particles (colloidal silica, fumed silica, precipitated silica, etc.), barium sulfate particles, aluminum hydroxide particles, alumina particles, zirconia particles, titania particles, zinc oxide particles, etc. The metal oxide particles are preferably mentioned, and silica particles are preferred. An inorganic particle may be used individually by 1 type, and may be used in combination of 2 or more types. Further, the print receiving layer 6 may contain the additives exemplified in the surface coating layer described later.

  The print receiving layer 6 can be formed by, for example, a method of applying the resin composition constituting the print receiving layer 6 described above onto the base material layer 1 by a known printing method or the like.

  The thickness of the print receiving layer 6 is not particularly limited, but is preferably about 0.001 μm or more, more preferably about 0.005 μm or more, and further preferably about 0.01 μm or more. Further, the thickness is preferably about 50 μm or less, more preferably about 40 μm or less, and still more preferably about 5 μm or less. Further, it may be about 0.1 μm or less and about 0.05 μm or less. The thickness of the print receiving layer 6 can be measured by observing the cross section with a scanning electron microscope (SEM).

  In the battery packaging material of the present invention, ink can be suitably printed on the surface of the print receiving layer 6. That is, in the present invention, the battery packaging material in which the ink is printed on the outer surface of the battery packaging material (the surface of the print receiving layer 6) is the ink printed on the surface of the print receiving layer 6 (cured product of ink, Dry material etc. are exposed. The printed ink can form, for example, printing of barcodes, patterns, characters, and the like. The ink used for printing is not particularly limited, and a known ink can be used. For example, a photocurable ink that is cured by irradiation with ultraviolet rays or the like can be used.

  In the battery packaging material of the present invention, the wetting tension on the surface of the print receiving layer 6 is preferably about 33 mN / m or more, and more preferably about 35 mN / m or more. In addition, the said wetting tension means the value measured by the following method.

(Measurement of wetting tension)
The wetting tension (mN / m) of the print receiving layer with a wetting reagent conforming to JIS standards is measured. The test method conforms to “JIS K6768 1999 plastic-film and sheet-wetting tension test method”. Using the wet tension test mixture, apply the reagent contained in the spherical absorbent cotton to the surface of the print receiving layer in a line of about 5 cm, and determine whether the liquid film is broken after 2 seconds. The wetting tension (mN / m) is measured. The wetting tension is measured in an environment with a temperature of 23 ° C. and a relative humidity of 50%.

[Adhesive layer 2]
In the battery packaging material of the present invention, the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as necessary in order to firmly bond them.

  The adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 3 together. The adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive. Furthermore, the bonding 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, a hot pressure type, and the like.

  Specific examples of adhesive components that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester; polyethers Polyurethane adhesive; epoxy resin; phenolic resin; polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin resin such as polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin , Polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; polycarbonate; amino resin such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene Rubbers such as butadiene rubber, silicone-based resins. These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive is preferable.

  Moreover, the adhesive layer 2 may contain a colorant. When the adhesive layer 2 includes a colorant, the battery packaging material can be colored. As the colorant, known ones such as pigments and dyes can be used. Moreover, only 1 type may be used for a coloring agent, and 2 or more types may be mixed and used for it.

  For example, specific examples of inorganic pigments preferably include carbon black and titanium oxide. Specific examples of organic pigments preferably include azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Examples of azo pigments include soluble pigments such as watching red and force-min 6C; insoluble azo pigments such as monoazo yellow, disazo yellow, pyrazolone orange, pyrazolone red, and permanent red, and phthalocyanine pigments include copper phthalocyanine pigments. And blue pigments and green pigments as metal-free phthalocyanine pigments, and condensed polycyclic pigments include dioxazine violet and quinacridone violet. As the pigment, a pearl pigment, a fluorescent pigment, or the like can be used.

  Among the colorants, for example, carbon black is preferable in order to make the appearance of the battery packaging material black.

  The average particle diameter of the pigment is not particularly limited, and examples thereof include about 0.05 to 5 μm, preferably about 0.08 to 2 μm. In addition, let the average particle diameter of a pigment be the median diameter measured with the laser diffraction / scattering type particle size distribution measuring apparatus.

  The content of the pigment in the adhesive layer 2 is not particularly limited as long as the battery packaging material is colored, and examples thereof include about 5 to 60% by mass.

  Although it will not restrict | limit especially if the thickness of the adhesive bond layer 2 exhibits the function as an adhesive layer, For example, about 1-10 micrometers, Preferably about 2-5 micrometers is mentioned.

[Colored layer]
The colored layer is a layer provided as necessary between the base material layer 1 and the adhesive layer 2 (illustration is omitted). By providing the colored layer, the battery packaging material can be colored.

  The colored layer can be formed, for example, by applying an ink containing a colorant to the surface of the base material layer 1 or the surface of the barrier layer 3. As the colorant, known ones such as pigments and dyes can be used. Moreover, only 1 type may be used for a coloring agent, and 2 or more types may be mixed and used for it.

  Specific examples of the colorant contained in the colored layer are the same as those exemplified in the column of [Adhesive layer 2].

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function of preventing water vapor, oxygen, light and the like from entering the battery, in addition to improving the strength of the battery packaging material. The barrier layer 3 can be formed of a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited layers, or the like, and is a layer formed of metal. Preferably there is. Specific examples of the metal constituting the barrier layer 3 include aluminum, stainless steel, titanium steel, and preferably aluminum. The barrier layer 3 is preferably formed of a metal foil, and more preferably formed of an aluminum alloy foil or a stainless steel foil.

  From the viewpoint of preventing the generation of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: (1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like, more preferably formed of a soft aluminum alloy foil.

  Examples of the stainless steel foil include austenitic stainless steel foil and ferritic stainless steel foil. The stainless steel foil is preferably made of austenitic stainless steel.

  Specific examples of the austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, SUS316L, etc. Among them, SUS304 is particularly preferable.

  The thickness of the barrier layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor. From the viewpoint of reducing the thickness of the battery packaging material, for example, the upper limit is about 100 μm or less, preferably about 85 μm or less, more preferably about 50 μm or less, more preferably about 40 μm or less, and the lower limit is preferably about 10 μm or more. The thickness ranges are about 10 to 100 μm, about 10 to 80 μm, Preferably, it can be about 10 to 50 μm or about 10 to 40 μm. When the barrier layer 3 is made of stainless steel foil, the thickness of the stainless steel foil is preferably about 85 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, and further preferably about 30 μm or less. The lower limit is about 10 μm or more, and the preferable thickness range is about 10 to 85 μm, about 10 to 50 μm, more preferably about 10 to 40 μm, and more preferably. About 10-30 micrometers is mentioned, More preferably, about 15-25 micrometers is mentioned.

  The barrier layer 3 is preferably subjected to chemical conversion treatment on at least one surface, preferably both surfaces, for stabilization of adhesion, prevention of dissolution and corrosion, and the like. Here, the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer. When an acid resistant film is formed on the surface of the barrier layer 3 of the present invention, the barrier layer 3 includes an acid resistant film. As the chemical conversion treatment, for example, chromate chromate using chromic acid compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc. 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 the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be included singly or in any combination of two or more. Also good.

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 hydroxyl 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, for example, preferably about 500 to 1,000,000, and preferably about 1,000 to 20,000. More preferred.

  Further, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein. A method of forming an acid-resistant film on the surface of the barrier layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned. Further, a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the acid resistant film. 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, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

In addition, as a method for specifically providing an acid-resistant film, for example, as an example, at least the surface on the inner layer side of the aluminum alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method. , Degreasing treatment is performed by a known treatment method such as an acid activation method, and then a Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, Zn phosphate ( Zinc) Treatment liquid (aqueous solution) mainly composed of metal phosphates such as salts and mixtures of these metal salts, or treatment mainly composed of non-metal phosphates and mixtures of these non-metal salts A liquid (aqueous solution) or a treatment liquid (aqueous solution) composed of a mixture of these with an aqueous synthetic resin such as an acrylic resin, a phenolic resin, or a polyurethane resin, roll coating, gravure printing, immersion By coating in a known coating method etc., it is possible to form the acid-resistant coating. For example, when treated with a Cr (chromium) phosphate-based treatment solution, CrPO ₄ (chromium phosphate), AlPO ₄ (aluminum phosphate), Al ₂ O ₃ (aluminum oxide), Al (OH) _x (water Zn ₂ PO ₄ · 4H ₂ O (zinc phosphate hydrate) when treated with an acid-resistant film made of aluminum oxide), AlF _x (aluminum fluoride), etc. ), AlPO ₄ (aluminum phosphate), Al ₂ O ₃ (aluminum oxide), Al (OH) _x (aluminum hydroxide), AlF _x (aluminum fluoride), and the like.

  In addition, as another example of a specific method for providing an acid-resistant film, for example, at least the surface on the inner layer side of the aluminum alloy foil is first subjected to an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid-resistant film can be formed by performing a degreasing process by a known processing method such as an activation method and then performing a known anodizing process on the degreasing surface.

  Moreover, as another example of an acid-resistant film | membrane, the film | membrane of a phosphorus compound (for example, phosphate type) and a chromium compound (for example, chromic acid type) is mentioned. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate. Examples of the chromic acid system include chromium chromate.

  In addition, as another example of an acid-resistant film, by forming an acid-resistant film such as a phosphorus compound (phosphate, etc.), a chromium compound (chromate, etc.), a fluoride, a triazine thiol compound, etc., during emboss molding Prevention of delamination between aluminum and base material layer, and dissolution and corrosion of aluminum surface, especially aluminum oxide existing on the surface of aluminum, due to hydrogen fluoride generated by reaction between electrolyte and moisture In addition, the adhesion (wetting) of the aluminum surface is improved, the delamination between the base material layer and aluminum during heat sealing is prevented, and in the embossed type, the delamination between the base material layer and aluminum during press molding is performed. Shows the effect of preventing lamination. Among substances that form an acid-resistant film, an aqueous solution composed of three components of a phenolic resin, a chromium fluoride (3) compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.

  The acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is 1-100 mass parts may be mix | blended with respect to 100 mass parts of cerium oxides. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.

  Furthermore, it is preferable that the anionic polymer is poly (meth) acrylic acid or a salt thereof, or a copolymer having (meth) acrylic acid or a salt thereof as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

  The phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.

  As the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatment may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds. Among the chemical conversion treatments, chromic acid chromate treatment, chromate treatment combining a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are preferable.

  Specific examples of the acid resistant film include those containing at least one of phosphate, chromate, fluoride, and triazine thiol. An acid resistant film containing a cerium compound is also preferable. As the cerium compound, cerium oxide is preferable.

  Specific examples of the acid-resistant film include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film. As an acid-resistant film, one of these may be used, or a plurality of combinations may be used. Furthermore, as an acid-resistant film, after degreasing the chemical conversion surface of the aluminum alloy foil, a treatment liquid comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed of a treatment liquid consisting of

The composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry. By analyzing the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry, for example, at least one secondary ion composed of Ce, P and O (for example, Ce ₂ PO ₄ ⁺ , CePO ₄ ^−, etc.) ) Or a peak derived from a secondary ion composed of Cr, P, and O (for example, at least one kind of CrPO ₂ ⁺ , CrPO ₄ ^−, etc.) is detected.

The amount of the acid-resistant film to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited. For example, if the above chromate treatment is performed, a chromic acid compound is present per 1 m ² of the surface of the barrier layer 3. About 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of chromium, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and 1. It is desirable that it is contained in a proportion of about 0 to 200 mg, preferably about 5.0 to 150 mg.

  The thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 20 μm, more preferably 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesion strength with the aluminum alloy foil and the heat-fusible resin layer. About 1 to 50 nm. The thickness of the acid-resistant film can be measured by observation with a transmission electron microscope, or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron energy loss spectroscopy.

  In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc., and then the temperature of the barrier layer is 70. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer, the barrier layer 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 chemical conversion process on the surface of the barrier layer.

[Heat-fusion resin layer 4]
In the battery packaging material of the present invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that heat-fuses the heat-fusible resin layers and seals the battery element when the battery is assembled.

The resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-sealed, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the resin constituting the heat-fusible resin layer 4 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the resin constituting the heat-fusible resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  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 Polypropylenes such as random copolymers of (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers 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, cyclic alkene is preferable, and norbornene is more preferable.

  The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.

  The 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- It is 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 polyolefin.

  Among these resin components, polyolefins such as polypropylene and carboxylic acid-modified polyolefins are preferable; polypropylenes and acid-modified polypropylenes are more preferable.

  The heat-fusible resin 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 heat-fusible resin layer 4 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 heat-fusible resin layer 4 is not particularly limited as long as it exhibits the function as the heat-fusible resin layer, but is preferably about 60 μm or less, more preferably about 15 to 40 μm.

[Adhesive layer 5]
In the battery packaging material of the present invention, the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 as necessary in order to firmly bond the barrier layer 3 and the heat-fusible resin layer 4.

The adhesive layer 5 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4. As the resin used for forming the adhesive layer 5, the adhesive mechanism, the kind of the adhesive component, and the like can be the same as the adhesive exemplified in the adhesive layer 2. Further, as the resin used for forming the adhesive layer 5, polyolefin resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin exemplified in the above-mentioned heat-fusible resin layer 4 can also be used. . From the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4, the polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene. That is, the resin constituting the adhesive layer 5 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the resin constituting the adhesive layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  From the viewpoint of improving the adhesion between the barrier layer 3 (or acid resistant film) and the heat-fusible resin layer 4, the adhesive layer 5 preferably contains an acid-modified polyolefin. The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. Polyolefins to be modified include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymers (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  In the adhesive layer 5, among the acid-modified polyolefins, maleic anhydride-modified polyolefins, and further maleic anhydride-modified polypropylene are particularly preferable.

  Furthermore, from the viewpoint of making the battery packaging material excellent in shape stability after molding while reducing the thickness of the battery packaging material, the adhesive layer 5 is a cured resin composition containing an acid-modified polyolefin and a curing agent. More preferably, it is a product. Preferred examples of the acid-modified polyolefin include those described above.

  The adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. The resin composition is preferably a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. The adhesive layer 5 preferably contains at least one selected from the group consisting of urethane resins, ester resins, and epoxy resins, and more preferably contains urethane resins and epoxy resins. As the ester resin, for example, an amide ester resin is preferable. Amide ester resins are generally formed by the reaction of carboxyl groups and oxazoline groups. The adhesive layer 5 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin. In the case where an unreacted product of a curing agent such as a compound having an isocyanate group, a compound having an oxazoline group, or an epoxy resin remains in the adhesive layer 5, the presence of the unreacted material is, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.

  Further, from the viewpoint of further improving the adhesion between the barrier layer 3 (or acid-resistant film), the heat-fusible resin layer 4 and the adhesive layer 5, the adhesive layer 5 includes an oxygen atom, a heterocyclic ring, a C = N bond, and It is preferably a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of C—O—C bonds. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group and a curing agent having an epoxy group. Examples of the curing agent having a C═N bond include a curing agent having an oxazoline group and a curing agent having an isocyanate group. In addition, examples of the curing agent having a C—O—C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and a urethane resin. The adhesive layer 5 is a cured product of a resin composition containing these curing agents, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF) -SIMS) and X-ray photoelectron spectroscopy (XPS).

  Although it does not restrict | limit especially as a compound which has an isocyanate group, From a viewpoint of improving the adhesiveness of an acid-resistant membrane | film | coat and the contact bonding layer 5 effectively, Preferably a polyfunctional isocyanate compound is mentioned. The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerization and nurate of these. And a mixture thereof and a copolymer with another polymer.

  As content of the compound which has an isocyanate group in the contact bonding layer 5, it is preferable to exist in the range of about 0.1-50 mass% in the resin composition which comprises the contact bonding layer 5, and 0.5-40 mass% More preferably, it is in the range of about.

  The compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the compound having an oxazoline group include those having a polystyrene main chain and those having an acrylic main chain. Moreover, as a commercial item, the Epocross series by Nippon Shokubai Co., Ltd. etc. are mentioned, for example.

  The ratio of the compound having an oxazoline group in the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, and about 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. It is more preferable that it is in the range. Thereby, the adhesiveness of the barrier layer 3 (or acid-resistant film | membrane) and the contact bonding layer 5 can be improved effectively.

  The epoxy resin is not particularly limited as long as it is a resin capable of forming a crosslinked structure with an epoxy group present in the molecule, and a known epoxy resin can be used. As a weight average molecular weight of an epoxy resin, Preferably it is about 50-2000, More preferably, it is about 100-1000, More preferably, about 200-800 is mentioned. In the present invention, the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.

  Specific examples of the epoxy resin include trimethylolpropane glycidyl ether derivative, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  The ratio of the epoxy resin in the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, and in the range of about 0.5 to 40% by mass in the resin composition constituting the adhesive layer 5. More preferably. Thereby, the adhesiveness of the barrier layer 3 (or acid-resistant film | membrane) and the contact bonding layer 5 can be improved effectively.

  In the present invention, the adhesive layer 5 is a cured resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin. When it is a product, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin each function as a curing agent.

  The thickness of the adhesive layer 5 is preferably about 30 μm or less, more preferably about 20 μm or less, more preferably about 5 μm or less, and the lower limit is about 0.1 μm or more, about 0.5 μm or more, The thickness ranges are preferably about 0.1 to 30 μm, about 0.1 to 20 μm, about 0.1 to 5 μm, about 0.5 to 30 μm, about 0.5 to 20 μm, 0.5 to For example, about 5 μm.

  The carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N═C═N—). As the carbodiimide curing agent, a polycarbodiimide compound having at least two carbodiimide groups is preferable.

  From the viewpoint of improving the adhesion between the barrier layer 3 and the heat-fusible resin layer 4 by the adhesive layer 5, the curing agent may be composed of two or more kinds of compounds.

  The content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.

  The thickness of the adhesive layer 5 is not particularly limited as long as it exhibits a function as an adhesive layer. However, if the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 1 to 10 μm, more preferably 1 to 1 μm. For example, about 5 μm. Moreover, when using resin illustrated by the heat-fusible resin layer 4, Preferably it is about 2-50 micrometers, More preferably, about 10-40 micrometers is mentioned. Moreover, if it is a hardened | cured material of acid-modified polyolefin and a hardening | curing agent, Preferably it is about 30 micrometers or less, More preferably, it is about 0.1-20 micrometers, More preferably, about 0.5-5 micrometers is mentioned. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.

[Surface coating layer]
In the battery packaging material of the present invention, the outer side of the base material layer 1 (the barrier layer of the base material layer 1) is optionally used for the purpose of improving design properties, electrolytic solution resistance, scratch resistance, moldability, and the like. If necessary, a surface coating layer may be provided on the side opposite to (3). The surface coating layer is provided between the base material layer 1 and the print receiving layer 6. When the print receiving layer 6 is provided on the entire surface outside the base material layer 1, it is not necessary to provide a surface coating layer between the base material layer 1 and the print receiving layer 6. Further, when the print receiving layer 6 is provided on a part of the outer side of the base material layer 1, by providing a surface coating layer in a portion where the print receiving layer 6 is not provided, the design property and the anti-electrolytic solution Property, scratch resistance, moldability and the like may be improved.

  The surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin for forming the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix | blend an additive with a surface coating layer. The additive to be added may function as, for example, a matting agent, and the surface coating layer may function as a mat layer.

  Examples of the additive include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. Further, the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an indeterminate shape, and a balloon shape. Specific additives include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, 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 | fusing point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold | metal | money, aluminum, copper, nickel etc. are mentioned. These additives may be used individually by 1 type, and may be used in combination of 2 or more type. Among these additives, silica, barium sulfate, and titanium oxide are preferably used from the viewpoints of dispersion stability and cost. In addition, the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment.

  The method for forming the surface coating layer is not particularly limited, and examples thereof include a method in which a two-component curable resin for forming the surface coating layer is applied to the outer surface of the base material layer 1. When blending the additive, the additive may be added to the two-component curable resin, mixed, and then applied.

  Although it will not restrict | limit especially if said function as a surface coating layer is exhibited as a thickness of a surface coating layer, For example, about 0.5-10 micrometers, Preferably it is about 1-5 micrometers.

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. As a method for producing a battery packaging material, for example, a layering step is provided in which a laminate is obtained by laminating at least a print receiving layer, a base material layer, a barrier layer, and a heat-fusible resin layer from the outside. In the laminating step, there is a method of laminating a print receiving layer containing an amide-based additive on the outer surface of the battery packaging material. That is, it comprises a laminating step of laminating a print receiving layer, a base material layer, a barrier layer, and a heat-fusible resin layer to obtain a laminate, and the print receiving layer is provided on the outer surface of the battery packaging material. A method in which the print receiving layer includes an amide-based additive is provided. Moreover, in the manufacturing method of the packaging material for batteries, the process of forming a printing layer on the surface of a printing receiving layer may be further provided.

  An example of the method for producing the battery packaging material of the present invention is as follows. First, a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order (hereinafter also referred to as “laminate A”) is formed. Specifically, the laminate A is formed by applying an adhesive used for forming the adhesive layer 2 on the base layer 1 or the barrier layer 3 whose surface is subjected to a chemical conversion treatment, if necessary, a gravure coating method, After applying and drying by a coating method such as a roll coating method, the barrier layer 3 or the base material layer 1 can be laminated and the adhesive layer 2 can be cured by a dry laminating method.

  The print receiving layer 6 may be laminated on the outer surface before the substrate layer 1 and the metal layer 3 are laminated, or may be laminated on the outer surface after the substrate layer 1 and the metal layer 3 are laminated. Good. The print receiving layer 6 may be laminated on the outer surface after the heat-fusible resin layer 4 is formed.

  Next, the adhesive layer 5 and the heat-fusible resin layer 4 are laminated on the barrier layer 3 of the laminate A in this order. For example, (1) a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate A by coextrusion (coextrusion laminating method), (2) a separate adhesive layer 5 And a layered product of the heat-fusible resin layer 4 and a method of laminating the layered product on the barrier layer 3 of the layered product A by a thermal laminating method. (3) Adhering to the barrier layer 3 of the layered product A An adhesive for forming the layer 5 is formed by extrusion or solution coating, and is laminated at a high temperature by drying or baking, and the heat-fusible resin layer 4 previously formed into a sheet on the adhesive layer 5 is formed. (4) Adhesion while pouring a molten adhesive layer 5 between the barrier layer 3 of the laminate A and the heat-fusible resin layer 4 previously formed into a sheet shape. Laminate A and heat-fusible resin layer 4 are pasted through layer 5 The method (sandwich lamination method), and the like to match.

  When the surface coating layer is provided, the surface coating layer is laminated on the surface of the base material layer 1 opposite to the barrier layer 3. The surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1. The order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited. For example, after the surface coating layer is formed on the surface of the base material layer 1, the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.

  As described above, the surface coating layer / base material layer 1 provided as necessary / adhesive layer 2 provided as necessary / barrier layer 3 whose surface is subjected to chemical conversion treatment as needed / as needed A laminate composed of the adhesive layer 5 / the heat-fusible resin layer 4 to be provided is formed. In order to strengthen the adhesiveness of the adhesive layer 2 or the adhesive layer 5, further, a hot roll contact type, a hot air type It may be subjected to a heat treatment such as a near infrared type or a far infrared type. Examples of such heat treatment conditions include, for example, about 150 to 250 ° C. and about 1 to 5 minutes.

  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.

  As a method for forming a print layer on the surface of the print receiving layer 6, for example, the print layer can be formed by printing ink on the surface of the print receiving layer 6. The printing method is not particularly limited, and includes pad printing, ink jet printing, thermal transfer printing, laser printing, ink transfer printing, hot stamp printing, and the like. Among these, pad printing is preferable when printing is performed on the battery packaging material after molding. In the battery packaging material obtained by the production method of the present invention, the print receiving layer 6 is formed on the outer surface, so that the ink can be suitably applied to the outer surface of the battery packaging material even by pad printing in which ink is easily repelled. Printing can be performed. Therefore, for example, a barcode, a pattern, a character, or the like can be suitably formed on at least a part of the outer surface. The ink used for printing is as described above.

4). Application of Battery Packaging Material The battery packaging material of the present invention is used in a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a battery element including at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to obtain a battery. In the production of the battery of the present invention, a printing layer may be formed in advance on the outer surface of the battery packaging material that houses the battery element. Further, after the battery element is accommodated, a printing layer can be formed on the surface of the printing receiving layer. Note that a battery packaging material in which a printing layer is formed in advance may be used to accommodate the battery element, and a printing layer may be further formed on the surface of the printing receiving layer.

  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. By covering the periphery of the element so that a flange portion (region where the heat-fusible resin layers are in contact with each other) can be formed, and heat-sealing the heat-fusible resin layers of the flange portion to seal the battery A battery using the packaging material is provided. When the battery element is housed in the package formed of the battery packaging material of the present invention, the heat-fusible resin portion of the battery packaging material of the present invention is on the inner side (surface in contact with the battery element). Thus, a package is formed.

  Since the battery packaging material of the present invention is used in the battery of the present invention, the ink is suitably printed on the outer surface of the battery after the battery packaging material is molded and the battery element is sealed. be able to. That is, since the battery of the present invention has the print receiving layer 6 on the outer surface, the ink can be suitably printed on the outer surface of the battery packaging material even by pad printing in which ink is easily repelled. For example, barcodes, patterns, characters, and the like can be suitably formed on at least a part of the outer surface of the battery.

  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 storage battery, a nickel-hydrogen storage battery, a nickel-cadmium storage battery, a nickel- Examples include iron storage batteries, nickel / zinc storage batteries, silver oxide / zinc storage batteries, metal-air batteries, multivalent 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.

Examples 1-16 and Comparative Examples 1-2
<Manufacture of battery packaging materials>
On a base material layer (thickness 15 μm) made of nylon resin, a barrier layer made of aluminum alloy foil (thickness 35 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum alloy foil, and an adhesive layer (thickness 3 μm) was formed on the barrier layer. Next, the adhesive layer and the base material layer on the barrier layer were dry-laminated to form a base material layer / adhesive layer / barrier layer laminate. In addition, the chemical conversion treatment of the aluminum alloy foil used as the barrier layer is performed by rolling a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry weight). The coating was applied to both surfaces of the aluminum alloy foil and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher. Next, 20 μm of carboxylic acid-modified polypropylene (arranged on the barrier layer side) and 15 μm of random polypropylene (innermost layer) are coextruded on the barrier layer of the laminate, whereby an adhesive layer / thermoadhesive resin layer is formed on the barrier layer. Were laminated.

  Next, the resin (polyester urethane resin or acrylic resin) described in Table 1 and an amide-based additive (erucic acid amide, content described in Table 1) are formed on the entire surface of the obtained laminate on the base layer side. A print-receiving layer having a thickness of 1 μm was formed using a coating material containing a quantity of 1) to obtain a battery packaging material. In Comparative Examples 1 and 2, an amide additive was not added to the print receiving layer.

<Measurement of wetting tension>
For the purpose of comparing and verifying the printability of the battery packaging materials obtained above, the wetting tension (mN / m) of the print receiving layer with a wetting reagent in accordance with JIS standards was determined. The test method was in accordance with “JIS K6768 1999 plastic-film and sheet-wetting tension test method”. Using a liquid mixture for wet tension test manufactured by Nacalai Tesque, apply the reagent contained in spherical absorbent cotton to the surface of the print receiving layer in a line of about 5 cm. Determination was made, and the wetting tension (mN / m) when the liquid film was not torn was measured. The wetting tension (mN / m) was measured in an environment at a temperature of 23 ° C. and a relative humidity of 50%. The results are shown in Table 1.

<Measurement of dynamic friction coefficient>
Each of the battery packaging materials obtained above was cut into two rectangular shapes of 200 mm × 80 mm to obtain test samples. The measuring machine used was model COF2-2N manufactured by Imada Corporation. According to JIS K7125: 1999 8.1 film-to-film measurement, a sliding piece having a contact area of 40 cm ² (a square with a side length of 63 mm) and a bottom covered with elastic felt is 200 g in total. Used, the dynamic friction coefficient was measured by superimposing the base material layer side surfaces of the test sample on the condition of a speed of 100 mm / min. The results are shown in Table 1. The measurement environment is a temperature of 24 ° C. and a relative humidity of 50%. Also, the sample and the sliding piece were brought into close contact with each other so as not to slip. Pull the sliding piece at a speed of 100 mm / min, measure the dynamic friction force (N) between the two samples, and divide by the normal force (1.96 N) of the sliding piece of the dynamic friction force to calculate the dynamic friction coefficient did. The dynamic friction coefficient was determined from the average value up to the first 30 mm after starting the relative displacement motion between the contact surfaces, ignoring the peak of the static friction force. The load cell was directly connected to the sliding piece.

<Printability evaluation>
Pad printing was performed on the print receiving layer of each battery packaging material obtained above, and the printability was evaluated. The pad printer used was SPACE PAD 6GX manufactured by Mishima Co., Ltd., and the ink used was UV ink PJU-A black manufactured by Navitas Co., Ltd. Also, the ink was cured by irradiating with UV light for 30 seconds from a distance of 10 cm at an ultraviolet wavelength of 254 nm with an As One handy UV lamp SUV-4. The printed surface after curing was observed with an optical microscope and evaluated according to the following criteria. The printability measurement was performed in an environment with a temperature of 24 ° C. and a relative humidity of 50%. The results are shown in Table 1. In the following criteria, “%” of missing prints represents the ratio of the missing area to the printed area formed in the print receiving layer.
5: No missing print 4: Print missing is 2.5% or less 3: Print missing is more than 2.5%, 5.0% or less 2: Print missing is 5.0% Over 10% or less 1: Print missing is over 10%

<Evaluation of formability>
Each battery packaging material obtained above was cut into a rectangular shape of 80 mm × 120 mm, and 30 test samples were prepared. Each test sample was male type having a rectangular convex part of 55 mm × 32 mm in an environment of 25 ° C. (surface is JIS B 0659-1: 2002 Annex 1 (reference) Comparative surface roughness standard piece The maximum height roughness (nominal value of Rz) specified in Table 2 is 1.6 μm, corner R: 2.0 mm, ridge line R: 1.0 mm, and a female mold having a recess corresponding thereto. (The surface has JIS B 0659-1: 2002 Annex 1 (reference). The maximum height roughness (nominal value of Rz) defined in Table 2 of the comparative surface roughness standard piece is 3.2 μm. R2.0 mm, ridgeline R1.0 mm), and cold forming (retraction one-step forming) with a pressing pressure of 0.16 MPa and a forming depth of 5.5 mm. At this time, the test sample was placed on the female mold and molded so that the heat-fusible resin layer side was positioned on the male mold side. The clearance between the male mold and the female mold was 0.3 mm. About the sample after shaping | molding, light was irradiated with the penlight in the dark room, and it was confirmed whether the pinhole and the crack had arisen in aluminum foil by permeation | transmission of light. A case where no pinholes occurred in all 30 test samples after molding was evaluated as a good product (A), and a case where even one pinhole was generated was evaluated as a defective product (C). . Further, the moldability was evaluated in the same manner when the molding depth was 6.0 mm, 6.5 mm, and 7.0 mm. The results are shown in Table 1.

  From the results shown in Table 1, from the outside, it comprises a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order, provided with a print receiving layer on the outer surface, and It can be seen that the battery packaging materials of Examples 1 to 16 in which the print receiving layer contains an amide-based additive have excellent printability and moldability.

Examples 17-23
<Manufacture of battery packaging materials>
On a base material layer (thickness 15 μm) made of nylon resin, a barrier layer made of aluminum alloy foil (thickness 35 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum alloy foil, and an adhesive layer (thickness 3 μm) was formed on the barrier layer. Next, the adhesive layer and the base material layer on the barrier layer were dry-laminated to form a base material layer / adhesive layer / barrier layer laminate. In addition, the chemical conversion treatment of the aluminum alloy foil used as the barrier layer is performed by rolling a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry weight). The coating was applied to both surfaces of the aluminum alloy foil and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher. Next, 20 μm of carboxylic acid-modified polypropylene (arranged on the barrier layer side) and 15 μm of random polypropylene (innermost layer) are coextruded on the barrier layer of the laminate, whereby an adhesive layer / thermoadhesive resin layer is formed on the barrier layer. Were laminated.

  Next, the resin described in Table 2 (resin containing a polyester urethane resin and an acrylic resin in the ratio described in Table 2) and an amide-based additive ( A print-receiving layer having a thickness of 1 μm was formed using a paint containing erucic acid amide (contents shown in Table 2) to obtain a battery packaging material.

  In the same manner as in Examples 1 to 16 and Comparative Examples 1 and 2, for each battery packaging material obtained in Examples 17 to 23, measurement of the wetting tension of the print receiving layer, the dynamic friction coefficient of the substrate layer side surface Measurement, printability evaluation, and moldability evaluation. The results are shown in Table 2. Table 2 also shows the results of Example 14 and Example 6 described above.

(Evaluation of tape adhesion)
The tape adhesion of the print receiving layer of each battery packaging material obtained in Examples 17 to 23 and Examples 6 and 14 was evaluated by the following method. The results are shown in Table 2. As shown in FIGS. 4 and 5, each battery packaging material 30 obtained above is cut out in a size of 15 mm in width and 175 mm in length, and the acrylic plate 10 having a width of 15 mm, a length of 175 mm, and a thickness of 2 mm is coated with a double-sided tape 20. The double-sided tape 40 having a width of 5 mm and a length of 125 mm (tesa (registered trademark 70415) manufactured by TesaSE) was attached to the surface of the print receiving layer of the battery packaging material 30 that was attached and fixed. Furthermore, an aluminum foil 50 (8079 material) having a thickness of 15 mm and a length of 300 mm cut out from the double-sided tape 40 and a thickness of 40 μm is stacked, and the JIS-Z0237: 2009 pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet test method is 10.2.4. The battery packaging material 30, the double-sided tape 40, and the aluminum foil 50 were crimped using the described crimping apparatus. Note that, in an environment of a temperature of 24 ° C. and a relative humidity of 50% RH, the mass of the roller of the crimping device reciprocates twice at a speed of 2 kg and 10 mm / sec. After being pressed with a roller and stored at a temperature of 24 ° C. and a relative humidity of 50% RH for 1 hour, the aluminum foil 50 attached to the double-sided tape 40 is folded back to 180 ° at the end of the double-sided tape 40, and the above-described battery packaging material Acrylic plate 10 fixed with aluminum foil 50 folded at 180 ° is fixed at the top and bottom of a tensile testing machine, 180 ° peeling angle, 200 mm distance between chucks, speed of 50 mm / min, temperature 24 ° C., relative humidity 50 A tensile test was performed in an environment of% RH to evaluate the adhesion of the tape. At this time, the double-sided tape 40 was peeled in a state of being in close contact with the aluminum foil 50 side, and no peeling between the acrylic plate 10 and the battery packaging material 30 occurred, and the peeling was performed between the battery packaging material 30 and the double-sided tape 40. The obtained peel strength was calculated as an average value excluding the first 25 mm and the last 20 mm of the measurement, and the tape adhesion was evaluated according to the following criteria. The results are shown in Table 2.
A: Peel strength 5N / 5mm or more B: Peel strength 3N / 5mm or more, less than 5N / 5mm C: Peel strength 3N / 5mm or less

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-fusible resin layer 5 Adhesive layer 6 Print receiving layer

Claims (13)

From the outside, a battery packaging material consisting of a laminate comprising at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The battery packaging material has a print receiving layer on its outer surface,
The printing receiving layer is a battery packaging material containing an amide-based additive.   The battery packaging material according to claim 1, wherein the amide-based additive is erucic acid amide.   The battery packaging material according to claim 1 or 2, wherein a content of the amide-based additive in the print receiving layer is 0.3 mass% or more and 6.0 mass% or less.   The battery packaging material according to any one of claims 1 to 3, wherein the print receiving layer is formed on the entire outer surface of the battery packaging material.   The battery packaging material according to any one of claims 1 to 4, further comprising a printing layer on an outer surface of the printing receiving layer.   The battery packaging material according to any one of claims 1 to 5, wherein a thickness of the print receiving layer is in a range of 0.001 µm to 50 µm.   The battery packaging material according to any one of claims 1 to 6, wherein the base material layer is formed of at least one of a polyamide resin and a polyester resin.   The battery packaging material according to any one of claims 1 to 7, wherein the print receiving layer contains a resin containing 80% by mass or more of an acrylic resin and the amide-based additive.   A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is accommodated in a package formed by the battery packaging material according to claim 1. From the outside, at least a printing receiving layer, a base material layer, a barrier layer, and a method for producing a battery packaging material comprising a laminate comprising a heat-fusible resin layer in this order,
Comprising a laminating step of laminating the print receiving layer, the base material layer, the barrier layer, and the heat-fusible resin layer to obtain a laminate,
The printing receiving layer is provided on an outer surface of the battery packaging material, and the printing receiving layer contains an amide-based additive.   The manufacturing method of the packaging material for batteries of Claim 10 further equipped with the process of forming a printing layer in the surface of the said printing receiving layer.   A method for producing a battery, comprising a step of accommodating a battery element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the battery packaging material according to claim 1.   The battery manufacturing method according to claim 12, further comprising a step of forming a print layer on a surface of the print receiving layer.