JPWO2018079681A1 - Packaging material for battery, method for manufacturing the same, battery and method for manufacturing the same - Google Patents

Abstract

Provided is a battery packaging material with excellent printability. It is a packaging material for batteries which consists of a layered product provided with a base material layer, a barrier layer, and a heat fusion bonding resin layer in this order from the outside, and the above-mentioned packaging material for batteries is provided with a print receiving layer in the outside surface. A packaging material for a battery, wherein the print receptive layer contains an amide based additive.

Description

  The present invention relates to a battery packaging material, a method of manufacturing the same, a battery and a method of manufacturing the same.

  Conventionally, various types of batteries have been developed, but in all batteries, 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 packaging for batteries, but in recent years, various shapes are required for batteries as the performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc. is improved. Needs to be thinner and lighter. However, in the case of metal battery packaging materials that have been widely used in the past, it is difficult to follow the diversification of the shape, and there is also a drawback that there is a limit to weight reduction.

  Therefore, as a packaging material for a battery that can be easily processed into various shapes and that can realize thinning and weight reduction, a film-like material in which a base material layer, an adhesive layer, a barrier layer, and a thermally adhesive resin layer are sequentially laminated A laminate has been proposed (see, for example, Patent Document 1). In such a film-like battery packaging material, the battery element can be sealed by heat-sealable resin layers facing each other and heat-sealing the peripheral portion by heat sealing.

  In various packaging materials formed by the above laminates, the ink is printed on the surface of the substrate layer to form a bar code, a handle, characters and the like, and adhesion is performed on the printed substrate layer. The method of printing on a packaging material is widely adopted by the method of laminating an agent and metal foil. However, when such a printing surface is present between the base material layer and the barrier layer, the adhesion between the base material layer and the barrier layer is reduced, and delamination tends to occur between the layers. In particular, since the battery to which the battery packaging material is applied requires high safety, the adhesive and the metal layer are laminated on the base layer printed on the surface of such base layer and printed. Methods are avoided in battery packaging materials. Therefore, conventionally, in the case of forming a print such as a bar code on the battery packaging material, generally, a method of sticking a seal on which the print is formed on the surface of the base material layer is employed.

JP 2008-287971 A

  However, when the seal on which the print is formed is attached 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 by printing ink on the surface of the base material layer of the battery packaging material in consideration of the recent trend of thinning and reducing the weight of the battery packaging material in recent years. did.

  As a method of printing by direct ink printing on the surface of the base material layer of the battery packaging material, for example, pad printing (also referred to as tampo printing) and inkjet printing are known. Pad printing is the following printing method. First, the ink is poured into the concave portion of the flat plate in which the pattern to be printed is etched. Next, the silicon pad is pressed from above the recess to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to a print target to form a print on the print target. Such pad printing is easy to print on the surface of the battery packaging material after molding because the ink is transferred to the printing object using an elastic silicon pad or the like, and the battery element is a battery packaging material. After sealing, it has the advantage of being able to print on the battery. Moreover, it has the same advantage also in inkjet printing.

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

  Moreover, in the battery packaging material, in order to increase the volumetric energy density, generally, a recess is formed by cold forming, and the storage volume of the battery element is increased. 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 precipitates, and as a result, a short circuit occurs. Since it is likely to be, packaging materials for batteries are required to have even better formability.

  Under such circumstances, the present invention has as its main object (first object) to provide a battery packaging material having excellent printability, and in addition to excellent printability, it has excellent formability. It is another object of the present invention to provide a battery packaging material having the same. 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, the present invention provides the invention of the aspects listed below.
Item 1. What is claimed is: 1. A battery packaging material comprising a laminate comprising, in order from the outside, at least a base material layer, a barrier layer, and a heat fusible resin layer,
The battery packaging material has a print receptive layer on its outer surface,
The packaging material for a battery, wherein the print receptive layer contains an amide based additive.
Item 2. The packaging material for a battery according to Item 1, wherein the amide-based additive is erucic acid amide.
Item 3. 3. The packaging material for a battery 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. The packaging material for a battery according to any one of Items 1 to 3, wherein the print receptive layer is formed on the entire outer surface of the packaging material for a battery.
Item 5. The packaging material for a battery according to any one of Items 1 to 4, wherein a print layer is provided on the outer surface of the print receptive layer.
Item 6. The battery packaging material according to any one of Items 1 to 5, wherein the thickness of the print receptive layer is in the range of 0.001 μm to 50 μm.
Item 7. The packaging material for a battery 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. The packaging material for a battery according to any one of Items 1 to 7, wherein the print receptive layer contains a resin containing 80% by mass or more of an acrylic resin, and the amide-based additive.
Item 9. Item 9. A battery, wherein a battery element including at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of Items 1 to 8.
Item 10. A method for producing a battery packaging material comprising a laminate including, in order from the outside, a print receptive layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order,
And a laminating step of laminating the print receptive layer, the base layer, the barrier layer, and the heat-fusible resin layer to obtain a laminate.
The method for producing a battery packaging material, wherein the print receptive layer is provided on the outer surface of the battery packaging material, and the print receptive layer contains an amide-based additive.
Item 11. Item 11. The method for producing a battery packaging material according to item 10, further comprising the step of forming a print layer on the surface of the print receptive layer.
Item 12. Item 9. A method for producing a battery, comprising the step of housing a battery element provided with at least a positive electrode, a negative electrode, and an electrolyte in a package formed of 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 the step of forming a print layer on the surface of the print receptive 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 the present invention, it is possible to provide a method for producing the battery packaging material, a battery using the battery packaging material, and a method for producing the battery.

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, from the outside, at least a base layer, a barrier layer, and a heat fusible resin layer in this order, and the outer surface of the battery packaging material has a print receptive layer. The printing receptive layer is characterized by containing an amide based additive. Hereinafter, the battery packaging material of the present invention will be described in detail.

  In addition, in this specification, the numerical range shown by "-" means "more than" and "less than" about a numerical range. 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, as shown in FIG. 1, the print receptive layer 6, the base material layer 1, the barrier layer 3 and the heat fusible resin layer 4 from the outside. It consists of a laminated body provided in this order. In the battery packaging material of the present invention, the print receptive layer 6 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. That is, when assembling the battery, the battery element is sealed by sealing the battery element by thermally fusing the heat-fusible resin layers 4 located on the peripheral edge of the battery element.

  The battery packaging material of the present invention has an adhesive layer 2 as necessary between the base layer 1 and the barrier layer 3 for the purpose of enhancing the adhesiveness, as shown in FIG. 2, for example. 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 needed for the purpose of enhancing the adhesiveness thereof. In addition, a surface coating layer (not shown) or the like may be provided on the outer side of the base material layer 1 (the side opposite to the heat-fusible resin layer 4) as necessary. When the surface covering layer is provided, the surface covering layer is located between the base layer 1 and the print receptive layer 6.

  As described later, the print receptive layer 6 may be formed on at least a part of the outer surface (the surface opposite to the barrier layer 3) of the substrate layer 1. That is, the print receptive layer 6 may be formed on the entire surface of the outer surface of the substrate 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 surface on the substrate layer side (outside surface) is preferably about 0.50 or less, more preferably about 0.26 or less, and about 0.18 The following is more preferable, and it is particularly preferable that it is about 0.13 or less. In addition, a kinetic friction coefficient means the value measured by the following method.

(Measurement of dynamic friction coefficient)
Two pieces of the battery packaging material are cut into a rectangular shape of 200 mm × 80 mm to make a test sample. Based on JIS K 7125: 1999, measurement of film-to-film and using a commercially available measuring device to measure the dynamic friction coefficient, the bottom surface is elastic with a contact area of 40 cm ² (square with a side length of 63 mm) Using a slide piece with a total weight of 200 g covered with a felt and at a speed of 100 mm / min, the base layer sides of the test sample are overlapped to measure the dynamic friction coefficient. The measurement environment is a temperature of 24 ° C. and a relative humidity of 50%. Also, keep the sample and the sliding piece in intimate contact so as not to slip. The sliding piece is pulled at a speed of 100 mm / min, the dynamic friction (N) between two samples is measured, and the dynamic friction coefficient is calculated by dividing it by the normal force (1.96 N) of the sliding slip. Do. The coefficient of kinetic friction is determined from the average value up to the first 30 mm after the relative displacement between contact surfaces is initiated, disregarding the static friction peak. 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 it is preferably about 160 μm from the viewpoint of exhibiting high formability while making the total thickness of the laminate as thin as possible. The following may more preferably be about 35 to 155 μm, and 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, for example, 160 μm or less, according to the present invention, excellent formability can be exhibited. Therefore, the battery packaging material of the present invention can contribute to the improvement of the energy density of the battery.

2. Each Layer Forming a Packaging Material for a Battery [Base Material Layer 1]
In the battery packaging material of the present invention, the base material layer 1 is a layer which is located outside the barrier layer 3 and functions as a support of the battery packaging material. About the raw material which forms the base material layer 1, it does not restrict | limit in particular that it is what is provided with insulation. As a material for forming the base material layer 1, for example, polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyether imide, polyimide, and a mixture or copolymer of these, etc. It 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, copolymer polyester having ethylene terephthalate as a main unit of repeating unit, and butylene terephthalate as a repeating unit Copolymer polyester etc. which made the main are mentioned. Further, as a copolymerized polyester having ethylene terephthalate as the main component of the repeating unit, specifically, a copolymer polyester in which ethylene terephthalate is polymerized as the main component of the repeating unit with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) , Polyethylene (terephthalate / decane dicarboxylate) and the like. Further, as a copolymerized polyester having butylene terephthalate as the main component of the repeating unit, specifically, a copolymer polyester in which butylene terephthalate is polymerized with butylene isophthalate as the main component of the repeating unit (hereinafter, polybutylene (terephthalate / isophthalate) And polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used alone or in combination of two or more. Polyester has an advantage that it is excellent in electrolytic solution resistance and is less likely to cause whitening or the like due to adhesion of the electrolytic solution, and is suitably used as a forming material of the base material layer 1.

  Further, as polyamides, specifically, aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, copolymers of nylon 6 and nylon 66, etc .; terephthalic acid and / or isophthalic acid Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide such as nylon 6I, nylon 6T, nylon 6IT, nylon 6 I 6T (I is isophthalic acid, T represents terephthalic acid) containing structural units derived from An aromatic polyamide such as pamide (MXD6); an alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM 6); and a copolymer of a lactam component and an isocyanate component such as 4,4'-diphenylmethane diisocyanate. Polyamide, copolymerization Polyester amide copolymer and polyether ester amide copolymer is a copolymer of a polyamide and a polyester and polyalkylene ether glycol; copolymers thereof, and the like. These polyamides may be used alone or in combination of two or more. The stretched polyamide film is excellent in stretchability, can prevent the occurrence of whitening due to resin cracking of the base material layer 1 at the time of molding, and is suitably used as a forming material of 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, is suitably used as the substrate layer 1 because its heat resistance is improved by orientation crystallization. Further, the base material layer 1 may be formed by coating the above-described material on the barrier layer 3.

  Among these, from the viewpoint of exhibiting high moldability, preferably nylon, polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, particularly preferably biaxially stretched nylon as a resin film for forming the substrate layer 1. It can be mentioned.

  The base material layer 1 can also be laminated with at least one of a resin film and a coating of different materials in order to improve the pinhole resistance and the insulation property of the battery package. Specifically, a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a biaxially oriented polyester and a biaxially oriented nylon are laminated, and the like can be mentioned. When the base material layer 1 has a multilayer structure, each resin film may be bonded via an adhesive, or may be directly laminated without using an adhesive. In the case of bonding without using an adhesive, for example, a method of bonding in a hot-melted state such as coextrusion lamination method, sandwich lamination method, thermal lamination method and the like can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a 2 liquid curing adhesive, and may be a 1 liquid curing adhesive. Furthermore, the adhesion mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, an ionizing radiation curing type such as ultraviolet light (UV) or electron beam (EB). It may be. As components of adhesives, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin A resin, a polyimide resin, an amino resin, rubber, and a silicone resin are mentioned.

  The water repellant may be contained in the base material layer of the packaging material for batteries. For example, a polyamide resin film such as nylon is widely used, and the polyamide resin film generally contains ethylenebisoleic acid amide, ethylenebisstearic acid amide or the like as a water repellent. By containing a water repellent, the wettability of the molten resin to water can be adjusted during the production of the film, and appropriate irregularities (surface roughness) can be formed on the surface of the raw film, and the raw film Even after the stretching of the above, the asperity shape remains, and it is possible to obtain a polyamide resin film in which the slipperiness of the surface is adjusted. However, when the substrate layer contains a water repellent, the water repellent is applied to the surface of the substrate layer by applying heat in a baking process or the like after the battery element such as the electrolyte is sealed in the battery packaging material. When the ink is bled out and printed on the surface of the base material layer by pad printing etc., the ink is repelled on the surface of the base material layer, the ink becomes difficult to be fixed, and there is a problem that the missing part where the ink is not formed tends to occur. .

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

  The content of the water repellent contained in the base material layer 1 is not particularly limited, but preferably about 200 to 1500 ppm, more preferably about 300 to 1200 ppm. In the present invention, the water repellent content contained in the base material layer 1 is the water repellent agent present on the inside and the surface of the base material layer (for example, fatty acids such as ethylenebisstearic acid amide and ethylenebisoleic acid amide) Amide)). The content of the water repellent contained in the base material layer 1 of the battery packaging material is such that after removing the base material layer 1 from the battery packaging material and dissolving the base material layer 1 in hexafluoroisopropyl alcohol, dimethylethane is added In addition, solvent precipitation can be performed, and the resin component can be separated to prepare an extraction solution of a water repellent, and the extraction solution can be quantified by GC-MS analysis.

  The thickness of the base material layer 1 may be, for example, about 10 to 50 μm, preferably about 12 to 30 μm.

[Printing receptive layer 6]
In the battery packaging material of the present invention, the print receptive layer 6 containing the 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 layer 1 side). The print receptive layer 6 may be formed on the entire surface of the outer surface of the battery packaging material, or may be formed on a part thereof. From the viewpoint of further enhancing the formability of the battery packaging material, the print receptive layer 6 is preferably formed on the entire outer surface of the battery packaging material. When the location printed on the outer surface of the battery packaging material is predetermined, the print receptive layer 6 is preferably formed on a part of the outer surface. When the print receptive layer 6 is formed on a part of the outer surface, the area of the print receptive layer 6 occupied on the outer surface is considered from the viewpoint of providing a battery packaging material having both excellent printability and excellent formability. The proportion 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, when the present inventors examined printing directly on the outside surface instead of sticking the seal to the outside of the battery packaging material as in the prior art, when the ink is printed on the outside surface, the outside surface is It became clear that the ink was repelled in the case of (3), the ink was difficult to be fixed, and there was a case where a missing portion where the ink could not be formed. In particular, the printability tends to be insufficient when printing by pad printing.

  On the other hand, in the battery packaging material of the present invention, since the print receptive 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 receptive layer 6), the ink is less likely to be repelled, and the ink can be suitably printed on the outside of the battery packaging material. In particular, when the ink is printed by pad printing, the ink may be repelled on the outer surface and printing defects may occur, but the battery packaging material of the present invention forms the print receptive layer 6 even in such a case. As a result, the ink is difficult to be repelled, and it is particularly suitable as a battery packaging material in which printing and the like are formed on the outer surface by pad printing. Furthermore, the inclusion of the amide-based additive in the print receptive layer 6 is also excellent in the formability of the battery packaging material.

  The material constituting the print receptive layer 6 is not particularly limited as long as it is a surface on which the ink is not easily repelled. The print receptive layer 6 is formed of, for example, a resin composition containing an amide based additive and a resin. Although it does not restrict | limit especially as resin, For example, a thermoplastic resin, a thermosetting resin, ionizing radiation curable resin etc. are mentioned.

  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-acrylate resin, nitrifying cotton resin, etc. may be mentioned. Among these, acrylic resins are preferable from the viewpoint of improving the printability and the formability of the ink on the outer surface of the battery packaging material.

  The thermosetting resin is not particularly limited. 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 resin Resin, amide functional copolymer, urethane resin etc. are mentioned. Among these, a urethane resin is preferable from the viewpoint of improving the printability and the formability of the ink on the outer surface of the battery packaging material. Further, among the urethane resins, polyester urethane resins are more preferable from the same viewpoint.

  Furthermore, from the viewpoint of further improving the adhesion to the tape after improving the printability and the formability of the ink on the outer surface of the battery packaging material, the resin constituting the print receptive layer 6 contains an acrylic resin. It is preferable that the ratio of an acrylic resin is 80 mass% or more. More specifically, in the resin constituting the print receptive 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, it is particularly preferable that the print receptive layer 6 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 above-mentioned amide based additive. When the battery using the battery packaging material is fixed by a tape or the like, the tape may be adhered to the print receptive layer 6 to fix the battery to a housing or the like. In such a case, the battery can be suitably fixed using a tape because the adhesion of the print receptive layer 6 to the tape is excellent. In addition, as a tape, a commercially available adhesive tape etc. are used, for example.

  An ionizing radiation curable resin is a resin which is crosslinked and cured by irradiation with ionizing radiation, specifically, a prepolymer, an oligomer, having a polymerizable unsaturated bond or an epoxy group in the molecule, And a mixture of at least one of monomers and the like as appropriate. Here, ionizing radiation means an electromagnetic wave or charged particle beam having energy quantum capable of polymerizing or crosslinking molecules, and generally ultraviolet (UV) or electron beam (EB) is used, but in addition, X It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Known ionizing radiation curable resins can be used.

  As the above-mentioned monomer used as an ionizing radiation curable resin, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specific examples of multifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di Meta) 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 ( Meta) 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 ( Meta) 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 Hexa (meth) acrylate etc. are mentioned. These monomers may be used alone or in combination of two or more.

  Further, as the above-mentioned oligomer used as the ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, two or more polymerizable unsaturated bonds in the molecule A (bifunctional or higher) polyfunctional (meth) acrylate oligomer is preferred. As a polyfunctional (meth) acrylate oligomer, for example, polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And polybutadiene (meth) acrylate, silicone (meth) acrylate, and oligomers having a cationically polymerizable functional group in the molecule (eg, novolak epoxy resin, bisphenol 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 at the terminal or side chain, for example, polycarbonate polyol (meth) 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 is obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylates can be obtained by radical copolymerization of silicone macromonomers with (meth) acrylate monomers. Urethane (meth) acrylate is obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol, a polyester polyol, a caprolactone type polyol, a polycarbonate polyol, and a polyisocyanate compound with (meth) acrylic acid. it can. The epoxy (meth) acrylate can be obtained, for example, by reacting (esterification) of (meth) acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin. Further, it is also possible to use a carboxyl-modified epoxy (meth) acrylate in which this epoxy (meth) acrylate is partially modified with a dibasic carboxylic acid anhydride. Polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyvalent alcohol with (meth) acrylic acid, or into polyvalent carboxylic acid It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. Polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of a polybutadiene oligomer. The 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 singly or in combination of two or more.

  Specific examples of the amide-based additive include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic 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, and N-stearyl erucic acid amide. In addition, specific examples of methylolamide include methylol stearic acid amide and the like. Specific examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylene bisstearin An acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl sebacic acid amide etc. are mentioned. Specific examples of the unsaturated fatty acid bisamide include ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide Etc. Specific examples of fatty acid ester amides include stearoamidoethyl stearate and the like. Moreover, m-xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, N, N'-distearyl isophthalic acid amide etc. are mentioned as a specific example of aromatic-type bisamide. Among these, erucic acid amide is preferable from the viewpoint of improving the printability and the formability of the ink on the outer surface of the battery packaging material. The amide-based additive may be used alone or in combination of two or more.

  The content of the amide-based additive in the print receptive layer 6 is not particularly limited, but from the viewpoint of improving the printability of the ink on the outer surface of the battery packaging material, and from the viewpoint of improving the printability and formability of the ink. From this, preferably 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, particularly preferably 3.0 to About 4.0 mass% is mentioned.

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

  The print receptive layer 6 may contain inorganic particles. The inorganic particles are not particularly limited, and, 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. Are preferably mentioned, and silica particles are preferred. The inorganic particles may be used alone or in combination of two or more. Further, the print receptive layer 6 may contain the additive exemplified in the surface coating layer described later.

  The print receptive layer 6 can be formed, for example, by a method of applying the resin composition constituting the above-described print receptive layer 6 on the substrate layer 1 by a known printing method or the like.

  The thickness of the print receptive layer 6 is not particularly limited, but preferably about 0.001 μm or more, more preferably about 0.005 μm or more, and still more preferably about 0.01 μm or more. 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. Furthermore, it may be about 0.1 μm or less and about 0.05 μm or less. The thickness of the print receptive 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, the ink can be suitably printed on the surface of the print receptive layer 6. That is, in the present invention, the battery packaging material in which the ink is printed on the outer surface (surface of the print receptive layer 6) of the battery packaging material is the ink printed on the surface of the print receptive layer 6 (cured product of ink, Dry matter etc. are exposed. The printed ink can, for example, form a print such as a bar code, a pattern, characters and the like. The ink used for printing is not particularly limited, and any known ink can be used. For example, a photocurable ink which is cured by irradiation with ultraviolet light can be used.

  In the battery packaging material of the present invention, the wetting tension of the surface of the print receptive 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 receptive layer by the wetting reagent according to the JIS standard is measured. The test method conforms to "JIS K 6768 1999 Plastic-film and sheet-wet tension test method". Using the mixed solution for the wet tension test, apply the reagent contained in the spherical absorbent cotton in a line about 5 cm on the surface of the print receptive layer, and judge whether the liquid film is broken after 2 seconds, it is not broken Wet tension (mN / m) is measured. The measurement of the wetting tension is performed in an environment of 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 substrate layer 1 and the barrier layer 3 as needed in order to firmly bond the substrate layer 1 and the barrier layer 3.

  The adhesive layer 2 is formed of an adhesive capable of adhering the base layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-part curable adhesive, or may be a one-part curable adhesive. Furthermore, the adhesion mechanism of the adhesive used to form 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 heat pressure type, and the like.

  Specific examples of the adhesive component 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, copolyester, etc .; Adhesives; polyurethane adhesives; epoxy resins; phenolic resins; polyamide resins such as nylon 6, nylon 66, nylon 12, copolymerized polyamides, etc .; polyolefin resins such as polyolefins, carboxylic acid modified polyolefins, metal modified polyolefins etc. Polyvinyl acetate resins; cellulose adhesives; (meth) acrylic resins; polyimide resins; polycarbonates; amino resins such as urea resins and melamine resins; chloroprene rubber, nitrile rubber, styrene Rubbers such as butadiene rubber, silicone-based resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane adhesive is preferably mentioned.

  The adhesive layer 2 may also contain a colorant. When the adhesive layer 2 contains a coloring agent, the battery packaging material can be colored. As the colorant, known ones such as pigments and dyes can be used. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.

  For example, as a specific example of the inorganic pigment, preferably, carbon black, titanium oxide and the like can be mentioned. Moreover, as a specific example of the pigment of an organic type, Preferably an azo pigment, a phthalocyanine pigment, a condensation polycyclic pigment etc. are mentioned. 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, etc. Examples of phthalocyanine pigments include copper phthalocyanine pigments. And blue pigments and green pigments as metal-free phthalocyanine pigments, and examples of condensed polycyclic pigments include dioxazine violet and quinacridone violet. In addition, as pigments, pearl pigments, fluorescent pigments and the like can be used.

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

  The average particle diameter of the pigment is not particularly limited, and for example, 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 by laser diffraction / scattering type particle diameter 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 may be, for example, about 5 to 60% by mass.

  The thickness of the adhesive layer 2 is not particularly limited as long as it exhibits the function as an adhesive layer, and for example, about 1 to 10 μm, preferably about 2 to 5 μm.

[Color layer]
The colored layer is a layer provided as needed between the base material layer 1 and the adhesive layer 2 (not shown). 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 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 one type of colorant may be used, or two or more types may be mixed and used.

  As a specific example of the coloring agent contained in a colored layer, the same thing as what was illustrated in the column of [adhesive layer 2] is illustrated.

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function to prevent water vapor, oxygen, light and the like from invading the inside of the battery, in addition to the strength improvement of the battery packaging material. The barrier layer 3 can be formed of a metal foil, a metal deposition film, an inorganic oxide deposition film, a carbon-containing inorganic oxide deposition film, a film provided with these deposition layers, or the like, and is a layer formed of metal Is preferred. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium steel etc. are mentioned, Preferably aluminum is mentioned. The barrier layer 3 is preferably formed of a metal foil, more preferably an aluminum alloy foil or a stainless steel foil.

  From the viewpoint of preventing the occurrence 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 A8021 H-O, JIS H4160: It is more preferable to form by soft aluminum alloy foil, such as 1994 A8079 H-O, JIS H4000: 2014 A8021 P-O, JIS H 4000: 2014 A8079 P-O).

  Moreover, as stainless steel foil, austenitic stainless steel foil, ferritic stainless steel foil, etc. are mentioned. The stainless steel foil is preferably made of austenitic stainless steel.

  Specific examples of austenitic stainless steels that constitute stainless steel foil include SUS304, SUS301, SUS316L, etc. Among these, SUS304 is particularly preferable.

  The thickness of the barrier layer 3 is not particularly limited as long as it exhibits a function as a barrier layer such as water vapor, but 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, further preferably about 40 μm or less, the lower limit is preferably about 10 μm or more, and the thickness range is about 10 to 100 μm, about 10 to 80 μm, Preferably, it can be about 10 to 50 μm and 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, still more preferably about 30 μm or less Particularly preferably, the thickness is about 25 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, more preferably About 10 to 30 μm, and more preferably about 15 to 25 μm.

  In addition, it is preferable that at least one surface, preferably both surfaces, of the barrier layer 3 be subjected to chemical conversion treatment in order to stabilize adhesion, to prevent dissolution or corrosion, and the like. Here, the chemical conversion treatment means a treatment for forming an acid resistant film on the surface of the barrier layer. When the acid resistant film is formed on the surface of the barrier layer 3 of the present invention, the barrier layer 3 contains the acid resistant film. As the chemical conversion treatment, for example, chromate chromate using a chromate compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromate acetyl acetate, chromium chloride, potassium chromium sulfate, etc. Treatment; Phosphoric acid chromate treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid, etc .; Aminated phenol having repeating units represented by the following general formulas (1) to (4) The chromate process etc. which used the polymer are mentioned. In the aminated phenol polymer, repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. It is also good.

In the 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. In addition, R ¹ and R ² are the same or different and each independently represent 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 and an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Also, examples of the hydroxyalkyl group represented by X, R ¹ and R ² include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3- C1-C4 linear or branched with one hydroxyl group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group etc. substituted An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and the hydroxyalkyl group represented by X, R ¹ and R ² may be identical to or different from each other. 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 repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and about 1 to 20,000. More preferable.

  In addition, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a coating in which fine particles of aluminum oxide, titanium oxide, cerium oxide, metal oxide such as tin oxide, or barium sulfate are dispersed in phosphoric acid is coated; A method of forming an acid resistant film on the surface of the barrier layer 3 can be mentioned by carrying out the baking treatment at 150 ° C. or higher. In addition, on the acid resistant film, a resin layer may be further formed by crosslinking the cationic polymer with a crosslinking agent. Here, as the cationic polymer, for example, polyethylene imine, an ionic polymer complex composed of polyethylene imine and a polymer having a carboxylic acid, primary amine graft acrylic resin obtained by graft polymerizing a primary amine on an acrylic main skeleton, polyallylamine Or derivatives thereof, aminophenol and the like. As these cationic polymers, only 1 type may be used and you may use combining 2 or more types. Moreover, as a crosslinking agent, the compound which has an at least 1 sort (s) of functional group chosen from the group which consists of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent etc. are mentioned, for example. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

Moreover, as a method of specifically providing an acid resistant coating, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method as one example. Degreasing treatment by a known treatment method such as acid activation method, and then the surface to be degreased is treated with Cr (chromium) phosphate, Ti (titanium) phosphate, Zr (zirconium) phosphate, Zn phosphate ( Treatment solution (aqueous solution) mainly composed of metal salts of phosphoric acid such as zinc salts and mixtures of these metal salts, or treatments mainly composed of nonmetallic metal salts of phosphoric acid and mixtures of these nonmetallic salts Roll coating method, gravure printing method, immersion treatment liquid (aqueous solution) or a treatment liquid (aqueous solution) consisting of a mixture of these with an aqueous synthetic resin such as acrylic resin, phenol resin or polyurethane resin, etc. 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 It becomes an acid-resistant film consisting of aluminum oxide), AlF _x (aluminum fluoride), etc. and is treated with a phosphoric acid Zn (zinc) salt-based treatment solution, Zn ₂ PO ₄ · 4H ₂ O (zinc phosphate hydrate) ), AlPO ₄ (aluminum phosphate), Al ₂ O ₃ (aluminum oxide), Al (OH) _x (aluminum hydroxide), AlF _x (aluminum fluoride) and the like.

  Moreover, as another example of the specific method of providing an acid resistant film, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid resistant film can be formed by degreasing treatment by a known treatment method such as activation method and then applying known anodizing treatment to the degreasing treatment surface.

  In addition, as another example of the acid resistant coating, a coating of a phosphorus compound (for example, a phosphate type) or a chromium compound (for example, a chromic acid type) can be mentioned. Examples of phosphates include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate and chromium phosphate. Examples of chromic acid include chromium chromate.

  In addition, as another example of the acid resistant coating, at the time of embossing by forming an acid resistant coating such as a phosphorus compound (such as phosphate), a chromium compound (such as chromate), a fluoride or a triazine thiol compound Dissolution of aluminum surface, corrosion, in particular dissolution and corrosion of aluminum oxide present on the surface of aluminum, by the prevention of delamination between aluminum and substrate layer, hydrogen fluoride generated by the reaction between electrolyte and water And improve the adhesion (wettability) of the aluminum surface, prevent delamination of the substrate layer and aluminum during heat sealing, and in the case of the emboss type, remove the substrate layer and aluminum during press molding. It shows the effect of preventing lamination. Among the substances forming the acid resistant film, an aqueous solution composed of a phenolic resin, a chromium fluoride (3) compound, and a phosphoric acid three component is applied on the aluminum surface, and the dry baking treatment is good.

  The acid resistant film further comprises a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, wherein the phosphoric acid or phosphate is any of the above. 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid resistant coating be 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 said anionic polymer is a copolymer which has poly (meth) acrylic acid or its salt, or (meth) acrylic acid or its salt as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which consists of a compound which has a functional group in any one of an isocyanate group, glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

  Moreover, it is preferable that the said phosphoric acid or phosphate is condensed phosphoric acid or condensed phosphate.

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

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

  Moreover, as a specific example of an acid resistant film, a phosphate type film, a chromate type film, a fluoride type film, a triazine thiol compound film, etc. are mentioned. The acid resistant coating may be one of these or a combination of two or more. Furthermore, as an acid-resistant film, after degreasing the surface of the aluminum alloy foil on the chemical conversion treatment, a treatment liquid comprising a mixture of a metal salt of phosphoric acid and an aqueous synthetic resin, or a mixture of a nonmetallic phosphate and an aqueous synthetic resin It may be formed of a treatment liquid comprising

The analysis of the composition of the acid-resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry. Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry, for example, secondary ions consisting of Ce, P and O (for example, at least one of Ce ₂ PO ₄ ⁺ , CePO ₄ ^−, etc. And peaks derived from secondary ions (for example, at least one of CrPO ₂ ⁺ , CrPO ₄ ^{− and the} like) consisting of Cr, P and O, for example.

The amount of the acid resistant coating formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but, for example, in the case of performing the above-mentioned chromate treatment, a chromic acid compound is contained 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, of the phosphorus compound in terms of phosphorus, and the aminated phenolic polymer is preferable. It is desirable that the content is about 0 to 200 mg, preferably about 5.0 to 150 mg.

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

  In the chemical conversion treatment, the temperature of the barrier layer is 70 after the solution containing the compound used for forming the acid resistant coating is applied to the surface of the barrier layer by the bar coating method, roll coating method, gravure coating method, immersion method or the like. 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 subjected in advance to a degreasing treatment by an alkaline immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like. By performing the degreasing treatment in this manner, the chemical conversion treatment on the surface of the barrier layer can be performed more efficiently.

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

The resin component used for the heat fusible resin layer 4 is not particularly limited as long as heat fusible is possible, 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 contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the heat-fusible resin layer 4 may contain a polyolefin skeleton, for example, by 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 denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene And polypropylenes such as random copolymers of propylene and ethylene (for example, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and as the olefin which is a constituent monomer of the cyclic polyolefin, for example, ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, etc. Can be mentioned. Moreover, as a cyclic monomer which is a constituent monomer of the cyclic polyolefin, for example, cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, etc. may be mentioned. Among these polyolefins, preferred are cyclic alkenes, more preferably norbornene.

  The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as a 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, itaconic anhydride, etc. or anhydrides thereof.

  The acid-modified cyclic polyolefin is prepared by copolymerizing part of the monomers constituting the cyclic polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof, or α, β- to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be carboxylic acid modified is the same as described above. Moreover, as a carboxylic acid used for modification | denaturation, it is the same as that used for modification | denaturation of the said polyolefin.

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

  The heat fusible resin layer 4 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types 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 of the same or different resin components.

  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 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 optionally provided between the barrier layer 3 and the heat-fusible resin layer 4 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 adhering the barrier layer 3 and the heat fusible resin layer 4. As resin used for formation of adhesion layer 5, the thing of the adhesion mechanism, the kind of adhesive agent component, etc. can be used for the adhesive agent illustrated by adhesive agent layer 2, and the like. Moreover, as resin used for formation of the contact bonding layer 5, polyolefin resin, such as polyolefin mentioned above-mentioned heat-fusion resin layer 4, cyclic polyolefin, carboxylic acid modified polyolefin, carboxylic acid modified cyclic polyolefin, can also be used. . As the polyolefin, a carboxylic acid-modified polyolefin is preferable, and a carboxylic acid-modified polypropylene is particularly preferable, from the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4. That is, the resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. It is possible to analyze that the resin constituting the adhesive layer 5 contains a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography-mass spectrometry, etc., and there is no particular limitation on the analysis method. 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 denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  The adhesive layer 5 preferably contains an acid-modified polyolefin from the viewpoint of improving the adhesion between the barrier layer 3 (or the acid resistant coating) and the heat-fusible resin layer 4. The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component such as a 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, itaconic anhydride, or anhydrides thereof. Moreover, as the polyolefin to be modified, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc .; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (e.g., random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

  Among the acid-modified polyolefins in the adhesive layer 5, in particular, maleic anhydride-modified polyolefin, and more preferably maleic anhydride-modified polypropylene are 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 cures the resin composition containing the acid-modified polyolefin and the curing agent. It is more preferable that it is a thing. As the acid-modified polyolefin, preferably, those described above can be exemplified.

  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. Particularly preferred 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 and a compound having an epoxy group. The adhesive layer 5 preferably contains at least one selected from the group consisting of a urethane resin, an ester resin, and an epoxy resin, and more preferably contains a urethane resin and an epoxy resin. As ester resin, an amide ester resin is preferable, for example. Amide ester resins are generally formed by the reaction of carboxyl groups with 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 a non-reacted substance 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 non-reacted substance 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-fusion resin layer 4 and the adhesive layer 5, the adhesive layer 5 is an oxygen atom, a heterocyclic ring, CNN bond, It is preferable that it is 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. As a curing agent which has a heterocyclic ring, the curing agent which has an oxazoline group, the curing agent which has an epoxy group, etc. are mentioned, for example. Moreover, as a curing agent having a C = N bond, a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like can be mentioned. Moreover, as a curing agent which has a COC bond, the curing agent which has an oxazoline group, the curing agent which has an epoxy group, a urethane resin etc. are mentioned. That the adhesive layer 5 is a cured product of a resin composition containing these curing agents is, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF) SIMS), X-ray photoelectron spectroscopy (XPS), etc.

  The compound having an isocyanate group is not particularly limited, but from the viewpoint of effectively enhancing the adhesion between the acid-resistant film and the adhesive layer 5, a polyfunctional isocyanate compound is preferably 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 polymerizing or nucleating these. And mixtures thereof, and copolymers with other polymers.

  The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, and preferably 0.5 to 40% by mass, in the resin composition constituting the adhesive layer 5. More preferably, it is in the range of degree.

  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 acryl main chain. Further, as a commercially available product, for example, Epocross series manufactured by Nippon Shokubai Co., Ltd. can be mentioned.

  The proportion 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 to be in the range of Thereby, the adhesion between the barrier layer 3 (or the acid resistant film) and the adhesive layer 5 can be effectively enhanced.

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

  Specific examples of the epoxy resin include glycidyl ether derivative of trimethylolpropane, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like. The epoxy resin may be used alone or in combination of two or more.

  The proportion 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. It is more preferable that Thereby, the adhesion between the barrier layer 3 (or the acid resistant film) and the adhesive layer 5 can be effectively enhanced.

  In the present invention, curing of the 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 in the present invention, and the acid-modified polyolefin. When it is a substance, an acid-modified polyolefin functions as a main agent, and a compound having an isocyanate group, a compound having an oxazoline group, and an 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, still more preferably about 5 μm or less, and the lower limit may be about 0.1 μm or more and about 0.5 μm or more. As a range of the thickness concerned, preferably, about 0.1-30 micrometers, about 0.1-20 micrometers, about 0.1-5 micrometers, about 0.5-30 micrometers, about 0.5-20 micrometers, 0.5 There is 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 a carbodiimide type | system | group hardening | curing agent, the polycarbodiimide compound which has a carbodiimide group 2 or more at least is preferable.

  From the viewpoint of, for example, enhancing the adhesion between the barrier layer 3 and the thermally fusible resin layer 4 by the adhesive layer 5, the curing agent may be composed of two or more types 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, and 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 the function as an adhesive layer, but if the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 1 to 10 μm, more preferably 1 to 4 There is about 5 μm. Further, in the case of using the resin exemplified for the heat fusible resin layer 4, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. In the case of a cured product of an acid-modified polyolefin and a curing agent, it is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. 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 as needed) for the purpose of improving designability, electrolytic solution resistance, abrasion resistance, moldability, etc. If necessary, a surface coating layer may be provided on the side opposite to (3). The surface coating layer is provided between the substrate layer 1 and the print receptive layer 6. When the print receptive layer 6 is provided on the entire outer surface of the base layer 1, the surface coating layer may not be provided between the base layer 1 and the print receptive layer 6. In addition, when the print receptive layer 6 is provided on a part of the outer side of the substrate layer 1, the design property and the electrolyte resistance can be obtained by providing a surface coating layer on the portion where the print receptive layer 6 is not provided. Properties, abrasion resistance, formability, etc. 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. Among these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface covering layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, an additive may be blended in the surface coating layer. The additive to be added may function, for example, as a matting agent, and the surface coating layer may function as a matte layer.

  Examples of the additive include fine particles having a particle diameter 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 spheres, fibers, plates, indeterminate shapes, and balloons. As an additive, specifically, talc, silica, graphite, kaolin, montmorrroid, 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 point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These additives may be used alone or in combination of two or more. Among these additives, preferred are silica, barium sulfate and titanium oxide from the viewpoint of dispersion stability, cost and the like. In addition, the surface may be subjected to various surface treatments such as insulation treatment, high dispersion treatment, and the like.

  Although it does not restrict | limit especially as a method to form a surface coating layer, For example, the method of apply | coating 2-part curable resin which forms a surface coating layer on the surface of the outer side of the base material layer 1 is mentioned. In the case of blending the additive, the additive may be added to and mixed with the two-component curable resin and then applied.

  The thickness of the surface coating layer is not particularly limited as long as the above-described function as the surface coating layer is exhibited, and for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. Method for Producing Battery Packaging Material The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate obtained by laminating each layer of a predetermined composition is obtained. The method for producing the battery packaging material includes, for example, a laminating step of laminating at least the print receptive layer, the base material layer, the barrier layer, and the heat fusible resin layer from the outside to obtain a laminate. In the laminating step, a method of laminating a print receptive layer containing an amide-based additive on the outer surface of the battery packaging material may be mentioned. That is, it comprises a laminating step of laminating a print receptive layer, a base material layer, a barrier layer, and a heat fusible resin layer to obtain a laminate, and the print receptive layer is formed on the outer surface of the battery packaging material. The provided printing receptive layer includes a method including an amide based additive. In addition, the method for producing a battery packaging material may further include the step of forming a print layer on the surface of the print receptive layer.

  As an example of the manufacturing method of the packaging material for batteries of this invention, it is as follows. First, a laminate (hereinafter sometimes referred to as “laminate A”) in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are sequentially laminated is formed. Specifically, the laminate A is formed by gravure coating an adhesive used for forming the adhesive layer 2 on the base layer 1 or on the barrier layer 3 whose surface has been subjected to a chemical conversion treatment if necessary. It can carry out by the dry lamination method which makes the said barrier layer 3 or the base material layer 1 laminate, and hardens the adhesive layer 2 after applying and drying by application methods, such as a roll coating method.

  The print receptive layer 6 may be laminated on the outer surface before laminating the base material layer 1 and the metal layer 3 or may be laminated on the outer surface after laminating the base material layer 1 and the metal layer 3 Good. In addition, the print receptive 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 in this order on the barrier layer 3 of the laminate A. For example, (1) a method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 by coextrusion on the barrier layer 3 of the laminate A (co-extrusion laminating method), (2) separately, the adhesive layer 5 To form a laminate in which the heat-fusion resin layer 4 is laminated, and laminating it on the barrier layer 3 of the laminate A by thermal lamination method, (3) bonding on the barrier layer 3 of the laminate A An adhesive for forming the layer 5 is extruded or solution coated, laminated by drying or baking at a high temperature, etc., and the heat fusible resin layer 4 previously formed into a sheet on the adhesive layer 5 is formed. Method of laminating by thermal laminating method, (4) Bonding while pouring the melted adhesive layer 5 between the barrier layer 3 of the laminate A and the heat-fusible resin layer 4 previously formed into a sheet Affix the laminate A and the heat fusible resin layer 4 through the layer 5 The method (sandwich lamination method), and the like to match.

  In the case of providing a surface covering layer, the surface covering layer is laminated on the surface of the base layer 1 opposite to the barrier layer 3. The surface coating layer can be formed, for example, by applying the above-mentioned resin 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 layer 1 and the step of laminating the surface coating layer on the surface of the base layer 1 is 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 covering layer / base material layer 1 / optional 1 / adhesive layer 2 optionally provided / the surface optionally formed a chemical conversion treated barrier layer 3 / optional A laminated body comprising the adhesive layer 5 / thermal adhesive resin layer 4 to be provided is formed, but in order to strengthen the adhesion of the adhesive layer 2 or the adhesive layer 5, the heat roll contact type or hot air type is further used. It may be subjected to heat treatment such as near infrared type or far infrared type. As conditions of such heat processing, about 1 to 5 minutes are mentioned, for example at about 150-250 degreeC.

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

  As a method of forming a printing layer on the surface of the printing receptive layer 6, for example, the printing layer can be formed by printing ink on the surface of the printing receptive layer 6. The printing method is not particularly limited, and pad printing, inkjet printing, thermal transfer printing, laser printing, ink transfer printing, hot stamp printing and the like can be mentioned. Among these, pad printing is preferable when printing is performed on the battery packaging material after molding. The battery packaging material obtained by the manufacturing method of the present invention preferably has the ink on the outer surface of the battery packaging material even by pad printing in which the ink is easily repelled because the print receptive layer 6 is formed on the outer surface. It can print. Therefore, printing of, for example, a barcode, a handle, characters, etc. can be suitably formed on at least a part of the outer surface. The ink used for printing is as described above.

4. Applications of Battery Packaging Material The battery packaging material of the present invention is used for a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the battery element provided with 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 make a battery. In the production of the battery of the present invention, a print layer may be formed in advance on the outer surface of the battery packaging material for containing the battery element. In addition, after the battery element is accommodated, a print layer can be formed on the surface of the print receptive layer. The battery element may be accommodated using a battery packaging material in which a print layer is formed in advance, and a print layer may be further formed on the surface of the print receptive layer.

  Specifically, a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is a battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward. The battery is covered by forming flanges (areas in which the heat fusible resin layers are in contact with each other) on the periphery of the element, and heat sealing the heat fusible resin layers of the flanges to seal them. A battery using a packaging material is provided. When the battery element is housed in a 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) Then, form a package.

  Since the battery packaging material of the present invention is used in the battery of the present invention, the battery packaging material is molded, and the ink is suitably printed on the outer surface of the battery after the battery element is sealed. be able to. That is, in the battery of the present invention, since the print receptive layer 6 is provided 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 the ink is easily repelled. For example, printing of a bar code, a handle, characters or 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, lithium ion battery, lithium ion polymer battery, lead storage battery, nickel hydrogen storage battery, nickel cadmium storage battery, nickel Iron storage batteries, nickel-zinc storage batteries, silver oxide-zinc storage batteries, metal air batteries, multivalent cation batteries, capacitors, capacitors and the like can be mentioned. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are mentioned as a suitable application object of the packaging material for batteries of the present invention.

  Hereinafter, the present invention will be described in detail by way of 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 the base material layer (15 micrometers in thickness) which consists of nylon resin, the barrier layer which consists of aluminum alloy foil (35 micrometers in thickness) which performed the chemical conversion treatment on both surfaces was laminated by the dry lamination method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum alloy foil to form an adhesive layer (3 μm in thickness) on the barrier layer. Then, the adhesive layer on the barrier layer and the base layer were dry laminated to form a laminate of base layer / adhesive layer / barrier layer. The chemical conversion treatment of the aluminum alloy foil used as the barrier layer is carried out by using a treatment liquid consisting 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). It apply | coated on both surfaces of aluminum alloy foil by the coating method, and it carried out by baking for 20 seconds on the conditions which become the film | membrane temperature 180 degreeC or more. Next, by coextruding 20 μm of carboxylic acid-modified polypropylene (arranged on the barrier layer side) and 15 μm of random polypropylene (innermost layer) on the barrier layer of the laminate, the adhesive layer / thermoadhesive resin layer on the barrier layer Was stacked.

  Next, the resin (polyester urethane resin or acrylic resin) described in Table 1 and the amide-based additive (erucic acid amide, contents described in Table 1) are provided on the entire surface of the base layer side of each obtained laminate. The paint containing layer was used to form a 1 .mu.m thick print receptive layer to obtain a battery packaging material. In Comparative Examples 1 and 2, no amide additive was added to the print receptive layer.

<Measurement of wetting tension>
The determination of the wetting tension (mN / m) of the print receptive layer by the wetting reagent based on JIS standard was carried out for the purpose of comparative verification of the printability of each of the packaging materials for batteries obtained above. The test method was based on "JIS K 6768 1999 plastic film and sheet-wet tension test method". Using a mixed solution for wetting tension test manufactured by Nacalai Tesque, apply the reagent contained in spherical absorbent cotton linearly to the surface of the print receptive layer for about 5 cm, and whether or not the liquid film is broken after 2 seconds It judged and the wetting tension (mN / m) when the liquid film did not tear was measured. The measurement of the wetting tension (mN / m) was performed in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The results are shown in Table 1.

<Measurement of dynamic coefficient of friction>
Two pieces of each of the battery packaging materials obtained above were cut into a rectangular shape of 200 mm × 80 mm to prepare test samples. The measuring instrument used model COF2-2N made by Imada Co., Ltd. Based on JIS K 7125: 1999, measurement of 8.1 film-to-film, a sliding piece with a contact area of 40 cm ² (square with a side length of 63 mm) and a total weight of 200 g covered with elastic felt at the bottom The dynamic friction coefficient was measured by superposing the base layer side surfaces of the test sample on each other at 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%. In addition, the sample and the sliding piece were brought into close contact with each other so as not to slip. The sliding piece is pulled at a speed of 100 mm / min, the dynamic friction (N) between two samples is measured, and the dynamic friction coefficient is calculated by dividing it by the normal force (1.96 N) of the sliding slip. did. The coefficient of kinetic friction was determined from the average value up to the first 30 mm after the relative displacement between contact surfaces was initiated, ignoring the static friction peak. The load cell was directly connected to the sliding piece.

<Printability evaluation>
Pad printing was performed on the print receptive layer of each of the battery packaging materials obtained above, and the printability was evaluated. The pad printer used SPACE PAD 6GX made by Mishima Co., Ltd., and the ink used UV ink PJU-A black made by Navitas Co., Ltd. In addition, ultraviolet light was irradiated for 30 seconds from a distance of 10 cm at an ultraviolet wavelength of 254 nm with a handy UV lamp SUV-4 manufactured by As One to cure the ink. The printed surface after curing was observed with an optical microscope and evaluated according to the following criteria. The printability was measured in an environment at a temperature of 24 ° C. and a relative humidity of 50%. The results are shown in Table 1. In the following criteria, “%” of print omission indicates the ratio of the area of the omission to the printing area formed on the print receptive layer.
5: There is no print omission 4: The print omission is 2.5% or less 3: The print omission is over 2.5%, 5.0% or less 2: The print omission is 5.0% More than 10% or less 1: The print omission is more than 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 produced. Each test sample is a male mold having a 55 mm × 32 mm rectangular convex portion at 25 ° C. (The surface is a surface roughness standard piece for comparison in JIS B 0659-1: 2002 Annex 1 (Reference). The maximum height roughness (nominal value of Rz) specified in Table 2 of Table 1. is a female mold having a corner R: 2.0 mm, a ridgeline R: 1.0 mm) and a corresponding recess (The surface has a maximum height roughness (nominal value of Rz) specified in Table 2 of JIS B 0659-1: 2002 Annex 1 (Reference) Comparative surface roughness standard piece is 3.2 μm. Using an R 2.0 mm and a ridge line R 1.0 mm, cold forming (one-step drawing) was performed at 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 so as to be positioned so that the heat fusible resin layer side was positioned on the male mold side. The clearance between male and female molds was 0.3 mm. About the sample after shaping | molding, light was irradiated with a penlight in a dark room, and it was confirmed whether the pinhole or the crack had arisen in aluminum foil by transmission of light. The case where no pinhole was generated in all of the 30 test samples after molding was evaluated as good (A), and the case where even one pinhole was generated was evaluated as defective (C) . In addition, also in the case where the forming depth was set to 6.0 mm, 6.5 mm, and 7.0 mm, the formability was similarly evaluated. The results are shown in Table 1.

  From the results shown in Table 1, it is composed of a laminate comprising in this order from the outside at least a substrate layer, a barrier layer, and a heat-fusible resin layer in this order, and a print receptive layer is provided on the outer surface, The battery packaging material of Examples 1 to 16 in which the print receptive layer contains an amide-based additive is found to have both excellent printability and formability.

Examples 17 to 23
<Manufacture of battery packaging materials>
On the base material layer (15 micrometers in thickness) which consists of nylon resin, the barrier layer which consists of aluminum alloy foil (35 micrometers in thickness) which performed the chemical conversion treatment on both surfaces was laminated by the dry lamination method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum alloy foil to form an adhesive layer (3 μm in thickness) on the barrier layer. Then, the adhesive layer on the barrier layer and the base layer were dry laminated to form a laminate of base layer / adhesive layer / barrier layer. The chemical conversion treatment of the aluminum alloy foil used as the barrier layer is carried out by using a treatment liquid consisting 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). It apply | coated on both surfaces of aluminum alloy foil by the coating method, and it carried out by baking for 20 seconds on the conditions which become the film | membrane temperature 180 degreeC or more. Next, by coextruding 20 μm of carboxylic acid-modified polypropylene (arranged on the barrier layer side) and 15 μm of random polypropylene (innermost layer) on the barrier layer of the laminate, the adhesive layer / thermoadhesive resin layer on the barrier layer Was stacked.

  Next, the resin described in Table 2 (a resin containing a polyester urethane resin and an acrylic resin in a ratio described in Table 2) and an amide based additive (all on the surface on the base material layer side of each obtained laminate) A paint receptive layer having a thickness of 1 μm was formed using a paint containing erucic acid amide and the content described in Table 2 to obtain a packaging material for a battery.

  About the packaging material for batteries obtained by Examples 17-23 similarly to Examples 1-16 and Comparative Examples 1-2, the measurement of the wetting tension of a printing receiving layer, the dynamic friction coefficient of the surface by the side of a substrate layer Were evaluated, the printability was evaluated, and the moldability was evaluated. The results are shown in Table 2. Table 2 also shows the results of the aforementioned Example 14 and Example 6.

(Evaluation of tape adhesion)
The tape adhesion of the print receptive layer of each of the battery packaging materials 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 wide and 175 mm long, and is double-sided tape 20 on an acrylic plate 10 of 15 mm wide, 175 mm long and 2 mm thick. On the surface of the print receptive layer of the battery packaging material 30 attached and fixed, the double-sided tape 40 (tesa (registered trademark 70415) manufactured by TesaSE) having a width of 5 mm and a length of 125 mm was attached. Furthermore, an aluminum foil 50 (8079 material) with a thickness of 40 μm cut out with a width of 15 mm and a length of 300 mm from the double-sided adhesive tape 40 is overlapped, and JIS-Z0237: 2009 adhesive tape · adhesive sheet 10.2.4 of the test method The battery packaging material 30, the double-sided tape 40, and the aluminum foil 50 were crimped using the crimping apparatus described. In an environment with a temperature of 24 ° C. and a relative humidity of 50% RH, the mass of the roller of the pressure bonding apparatus reciprocates twice at a speed of 2 kg and 10 mm / sec. After crimping with a roller and storing for 1 hour at a temperature of 24 ° C. and a relative humidity of 50% RH, the aluminum foil 50 attached to the double-sided tape 40 is folded back at 180 ° at the end of the double-sided tape 40, and the above-mentioned battery packaging material Is fixed at the top and bottom of the tensile tester, the peel angle of 180 °, the distance between chucks 200 mm, the speed of 50 mm / min, the temperature 24 ° C., the relative humidity 50 A tensile test was conducted in an environment of% RH to evaluate the adhesion of the tape. At this time, the double-sided tape 40 was peeled off in a state of being in close contact with the aluminum foil 50 side, peeling did not occur between the acrylic plate 10 and the battery packaging material 30, and was peeled 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 based on the criteria shown below. The results are shown in Table 2.
A: Peeling strength 5 N / 5 mm or more B: Peeling strength 3 N / 5 mm or more, less than 5 N / 5 mm C: Peeling strength 3 N / 5 mm

DESCRIPTION OF SYMBOLS 1 base material layer 2 adhesive bond layer 3 barrier layer 4 heat sealing | fusion resin layer 5 adhesive layer 6 printing receptive layer

Claims (13)

What is claimed is: 1. A battery packaging material comprising a laminate comprising, in order from the outside, at least a base material layer, a barrier layer, and a heat fusible resin layer,
The battery packaging material has a print receptive layer on its outer surface,
The packaging material for a battery, wherein the print receptive layer contains an amide based additive.   The packaging material for a battery according to claim 1, wherein the amide-based additive is erucic acid amide.   The battery packaging material according to claim 1, wherein a 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.   The battery packaging material according to any one of claims 1 to 3, wherein the print receptive 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, wherein a print layer is provided on the outer surface of the print receptive layer.   The battery packaging material according to any one of claims 1 to 5, wherein the thickness of the print receptive layer is in the 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 receptive layer contains a resin containing 80% by mass or more of an acrylic resin, and the amide-based additive.   A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of claims 1 to 8. A method for producing a battery packaging material comprising a laminate including, in order from the outside, a print receptive layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order,
And a laminating step of laminating the print receptive layer, the base layer, the barrier layer, and the heat-fusible resin layer to obtain a laminate.
The method for producing a battery packaging material, wherein the print receptive layer is provided on the outer surface of the battery packaging material, and the print receptive 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 on the surface of the said printing receptive layer.   A method of manufacturing a battery, comprising the step of housing a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the battery packaging material according to any one of claims 1 to 8.   The method for producing a battery according to claim 12, further comprising the step of forming a print layer on the surface of the print receptive layer.

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