JP2019029300A - Battery-packaging material, method for manufacturing the same, and battery - Google Patents

Abstract

To provide a battery-packaging material which can suppress the expansion of a battery having a separator including a resin and an inorganic material and enables gentle opening of the battery when the battery is exposed to a high-temperature environment.SOLUTION: A battery-packaging material is arranged for use in a battery including a package body formed from a battery-packaging material, and a battery element having a positive electrode, a negative electrode, an electrolyte and a separator and encased in the package body, provided that the separator includes a resin and an inorganic material, and the battery is one that is opened at a given set temperature of 120°C or under. The battery-packaging material comprises a laminate including at least a base material layer, a barrier layer and a heat-fusable resin layer in this order. On condition that the heat-fusable resin layer is composed of a single layer, the melting peak temperature of the heat-fusable resin layer is 130°C or lower. On condition that the heat-fusable resin layer is composed of a multi-layer, the melting peak temperature of a layer making a surface of the heat-fusable resin layer on a side opposite to the barrier layer is 130°C or lower.SELECTED DRAWING: None

Description

  The present invention relates to a battery packaging material, a method for producing the same, and a battery.

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

  Therefore, in recent years, a film in which a base material layer / adhesive layer / barrier layer / heat-sealable resin layer is sequentially laminated as a battery packaging material that can be easily processed into various shapes and can be thinned and lightened. A layered product has been proposed. Such a film-shaped battery packaging material is formed so that the battery element can be sealed by causing the heat-fusible resin layers to face each other and heat-sealing the peripheral edge portion by heat sealing.

  In recent years, batteries are required to have higher energy density, but ensuring safety is a technical issue. The role of the separator is important in ensuring the safety of the battery, and from the viewpoint of having a battery shutdown function, a polyolefin such as a polyethylene porous film is generally used as the separator. Note that the battery shutdown function is a function of blocking the current when the temperature of the battery rises, thereby blocking the current from running out of the battery.

  With the recent increase in energy density of batteries, separators are also required to have excellent heat resistance. As a method for increasing the heat resistance of the separator, a method of blending an inorganic material into a resin forming the separator is known (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2006-60061

  The heat resistance of the separator can be improved by a method of blending an inorganic material into the resin forming the battery separator. However, when the battery is exposed to a high temperature, the organic solvent used in the electrolytic solution may decompose and generate a combustible gas, which may cause an increase in pressure. In addition, the battery may continuously increase the temperature in the battery due to charging due to overvoltage or discharging with an excessive current, thereby causing a runaway battery reaction. Furthermore, when the battery is exposed to a high temperature environment higher than the melting peak temperature of the resin constituting the separator, the separator melts down, causing a short circuit inside the battery, which may further increase the battery temperature. .

  In a battery using a film-like battery packaging material, such an increase in the pressure or temperature in the battery may cause the battery packaging material to be cleaved and cause ignition due to ejection of combustible gas. Further, if the pressure or temperature rises continuously in the battery and the battery reaction runs out of control when the battery packaging material is excessively expanded, the battery may explode. For this reason, a battery element including a separator, a positive electrode, a negative electrode, and an electrolyte that are improved in heat resistance by blending an inorganic material with a resin is used for a battery that is housed in a package formed of a packaging material. In some battery packaging materials, depending on the application, it is required to suppress the expansion of the battery when exposed to a high-temperature environment and to gently open it at a predetermined temperature.

  For example, a small battery used in a mobile device such as a mobile phone or a notebook computer is always at hand of the user, and the danger is very great if the battery is greatly expanded and then opened explosively. For this reason, in small batteries for mobile use, when exposed to a high temperature environment, the battery is set to be opened gently by suppressing the expansion of the battery at a predetermined temperature (preferably 120 ° C. or less). It is required to be.

  The main object of the present invention is to provide a battery packaging material capable of gently opening a battery by suppressing the expansion of the battery when the battery including a separator containing a resin and an inorganic material is exposed to a high temperature environment. And

  The present inventors have intensively studied to solve the above problems. As a result, a battery packaging material for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator is housed in a packaging body formed of the battery packaging material, The battery includes a resin and an inorganic material, and the battery is opened at a predetermined set temperature of 120 ° C. or less. The battery packaging material includes at least a base material layer, a barrier layer, and a heat-fusible property. When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less, When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. or less. As for the packaging material, the battery is in a high temperature environment (for example, 90 to 1 When exposed to about 0 ° C.) also suppresses the expansion of the battery was found to be able to gently open the battery. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the battery packaging material and battery of the aspect hung up below.
Item 1. A battery packaging material for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator is housed in a packaging body formed of the battery packaging material,
The separator includes a resin and an inorganic material,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
The battery packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. or less. Battery packaging material.
Item 2. Item 4. The battery packaging material according to Item 1, wherein the melting peak temperature of the resin constituting the separator is 130 ° C or higher.
Item 3. When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is lower than the melting peak temperature of the resin constituting the separator,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is the resin constituting the separator. Item 3. The battery packaging material according to Item 1 or 2, wherein the battery packaging material is lower than the melting peak temperature.
Item 4. Item 4. The battery packaging material according to any one of Items 1 to 3, further comprising an adhesive layer between the heat-fusible resin layer and the barrier layer.
Item 5. Item 5. The battery packaging material according to any one of Items 1 to 4, wherein the battery is a battery opened at a predetermined set temperature of 90 ° C or higher and 120 ° C or lower.
Item 6. At least a battery element including a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material is a battery accommodated in a package formed of a battery packaging material,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
The battery packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. or less. battery.
Item 7. Item 7. The battery according to Item 6, wherein the resin constituting the separator has a melting peak temperature of 130 ° C or higher.
Item 8. When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is lower than the melting peak temperature of the resin constituting the separator,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is the resin constituting the separator. Item 8. The battery according to Item 6 or 7, wherein the battery is lower than the melting peak temperature.
Item 9. Item 9. The battery according to any one of Items 6 to 8, further comprising an adhesive layer between the heat-fusible resin layer and the barrier layer.
Item 10. Item 10. The battery according to any one of Items 6 to 9, wherein the battery is a battery opened at a predetermined set temperature of 90 ° C. or higher and 120 ° C. or lower.
Item 11. A battery packaging material manufacturing method for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator including a resin and an inorganic material is housed in a packaging body formed of the battery packaging material. There,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
At least a step of laminating a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer as the heat-fusible resin layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less, and the heat-fusible resin layer Battery having a melting peak temperature of 130 ° C. or lower of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer when the heat-resistant resin layer is a multilayer. Method of manufacturing packaging materials.

  ADVANTAGE OF THE INVENTION According to this invention, when the battery provided with the separator containing resin and an inorganic material is exposed to a high temperature environment, the expansion of a battery can be suppressed and the battery packaging material which can open a battery gently can be provided. .

It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram for demonstrating the method of the opening test of the packaging material for batteries in an Example. It is fu. It is a schematic diagram which shows the position which folds the sample after shaping | molding in an opening test.

  The battery packaging material of the present invention is a battery packaging material for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator is contained in a package formed of the battery packaging material. The separator includes a resin and an inorganic material, the battery is a battery opened at a predetermined set temperature of 120 ° C. or less, and the battery packaging material includes at least a base material layer and a barrier layer And when the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130. When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. It is characterized by being below ℃. Hereinafter, the battery packaging material of the present invention will be described in detail.

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

1. As shown in FIG. 1, the battery packaging material has a laminated structure including at least a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order. In the battery packaging material of the present invention, the base material layer 1 is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer side. That is, at the time of battery assembly, the heat-fusible resin layers 4 positioned at the periphery of the battery element are thermally welded to seal the battery element, thereby sealing the battery element.

  As shown in FIGS. 2 and 3, the battery packaging material of the present invention has an adhesive layer 2 between the base material layer 1 and the barrier layer 3 for the purpose of enhancing the adhesiveness as necessary. It may be provided. In addition, as shown in FIG. 3, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-fusible resin layer 4 as necessary for the purpose of enhancing these adhesive properties. In addition, for the purpose of improving design properties, electrolytic solution resistance, scratch resistance, moldability, etc., if necessary, outside the base material layer 1 (on the side opposite to the barrier layer 3 of the base material layer 1), A surface coating layer (not shown) may be provided.

  The battery packaging material of the present invention is used for a battery containing a resin and an inorganic material (for example, inorganic particles) in a separator. In such a battery, since the heat resistance of the separator is enhanced, the battery is designed to operate even in a high temperature environment. However, as described above, even in a battery in which the heat resistance of the separator is increased, there is a possibility that a problem such as the battery packaging material being cleaved due to an increase in pressure or temperature in the battery may occur. Therefore, battery packaging materials with improved heat resistance by blending an inorganic material with the resin that forms the separator can be opened gently, even when exposed to high-temperature environments, with the battery expanding. Is required. In particular, for example, a small battery used in a mobile device such as a mobile phone or a notebook personal computer is always at hand of the user, and the danger is very great if the battery is greatly expanded and then opened explosively. For this reason, small batteries for mobile use, etc. should be set so that they are gently opened when exposed to a predetermined high-temperature environment (preferably 120 ° C or lower). Is required.

  In the present invention, the gentle opening means that, for example, after the battery is heated and reaches a set temperature, it is not flammable after the battery greatly expands, but it is flammable before the battery expands greatly. It means that gas escapes gently and opens.

  The battery packaging material of the present invention is a battery that is opened at a predetermined set temperature of 120 ° C. or lower. More specifically, when the battery is heated to a predetermined set temperature of 120 ° C. or less, the battery packaging material is not opened until the set temperature is reached, and after the set temperature is reached, the battery packaging material is not opened. It is used for batteries set to be opened. Further, when the heat-fusible resin layer 4 is a single layer, the melting peak temperature of the heat-fusible resin layer 4 is 130 ° C. or less, and the heat-fusible resin layer 4 is a multilayer. The melting peak temperature of the layer constituting the surface opposite to the barrier layer 3 of the heat-fusible resin layer 4 is 130 ° C. or less (that is, the barrier of the heat-fusible resin layer 4 Because the melting peak temperature of the innermost layer constituting the surface opposite to the layer 3 is set to 130 ° C. or lower), a battery in which an inorganic material is blended with the resin forming the separator has a predetermined high temperature environment ( When it is exposed to 120 ° C. or less, the expansion of the battery can be suppressed, leading to a gentle opening.

  In the present invention, the melting peak temperature is measured by a differential scanning calorimeter (DSC).

  Since the battery packaging material of the present invention has such a gentle opening property, the melting peak temperature of the resin constituting the separator is 130 ° C or higher, more preferably 140 ° C or higher, more preferably 130 to 150 ° C. It can be suitably used for a battery excellent in heat resistance set to a degree, and further to 140 to 150 ° C. In addition, from the viewpoint of suppressing battery expansion and gently opening the battery, when the heat-fusible resin layer 4 is a single layer, the melting peak temperature of the heat-fusible resin layer constitutes the separator. When the heat-fusible resin layer 4 is lower than the melting peak temperature of the resin, and the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer, The melting peak temperature is preferably lower than the melting peak temperature of the resin constituting the separator.

  In the present invention, the set temperature at which the battery reaches opening is not particularly limited as long as it is 120 ° C. or lower, and is set to an appropriate temperature according to the use of the battery. The upper limit of the set temperature is about 120 ° C. or lower, or about 110 ° C. or lower, or about 100 ° C. or lower, and the lower limit is preferably about 90 ° C. or higher, more preferably about 95 ° C. or higher. Moreover, as a preferable range of set temperature which leads to opening, for example, about 90-120 degreeC, about 90-110 degreeC, about 90-100 degreeC, about 95-120 degreeC, about 95-110 degreeC, about 95-100 degreeC Is mentioned.

  The separator provided in the battery in which the battery packaging material of the present invention is used is not particularly limited as long as it contains an inorganic material. As described above, the melting peak temperature of the resin forming the separator is 130 ° C. or higher. It is desirable to have excellent heat resistance. Specific examples of the separator include a polyolefin porous film in which an inorganic material is blended. Such a separator is publicly known, and examples thereof include those disclosed in Patent Document 1 described above.

  Specific examples of polyolefin constituting the separator include, for example, polymers of polyolefins such as polyethylene (PE), polypropylene (PP), polybutene-1, poly-4-methylpentene, and ethylene-propylene copolymer. And a copolymer of an olefin hydrocarbon such as an ethylene-tetrafluoroethylene copolymer and another monomer. Polyolefin may be used individually by 1 type and may be used in combination of 2 or more types.

  As the inorganic material, any of synthetic products and natural products can be used without particular limitation. The natural product is not particularly limited. Burcellin, Amesite, Keriaite, Freponite, Blindriaite, biotite, phlogopite, iron mica, eastite, siderophyllite tetraferri iron mica, scale mica, polylithionite, muscovite, celadon stone, iron celadon Stone, Iron Alumino Ceradon Stone, Alumino Ceradon Stone, Tobe Mica, Soda Mica, Clint Knight, Kinoshita, Bite Mica, Ananda Stone, Pearl Mica, Clinochlore, Chamosite, Penantite, Nimite, Baylicroa, Dongbasite Cookeite, and the like Sudoaito. An inorganic material may be used individually by 1 type, and may be used in combination of 2 or more types.

  The content of the resin in the separator is not particularly limited, but is preferably about 35 to 96% by mass from the viewpoint of excellent heat resistance such that the melting peak temperature of the resin forming the separator is 130 ° C. or higher. More preferably, about 50-95 mass% is mentioned. Further, the content of the inorganic material in the separator is not particularly limited, but it is preferably 4 to 65 from the viewpoint of excellent heat resistance such that the resin forming the separator has a melting peak temperature of 130 ° C. or higher. About mass%, More preferably, about 5-50 mass% is mentioned.

  The thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but when the battery in which the inorganic material is blended with the resin forming the separator is exposed to a high temperature environment while reducing the thickness. However, from the viewpoint of suppressing the expansion of the battery and leading to gentle opening, the upper limit is preferably about 250 μm or less, more preferably about 200 μm or less, more preferably about 180 μm or less, and the lower limit is preferably About 60 micrometers or more are mentioned. Moreover, as a range of the thickness of a laminated body, Preferably, about 60-250 micrometers, about 60-200 micrometers, about 60-180 micrometers is mentioned.

2. Each layer forming the battery packaging material [base material layer 1]
In the battery packaging material of the present invention, the base material layer 1 is a layer located on the outermost layer side. The material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, polycarbonate, and a mixture or copolymer thereof. Is mentioned. Among these, it is preferable that the base material layer 1 has at least one layer among the layer formed with polyester and the layer formed with polyamide.

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

  Specific examples of polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, and polymetaxylylene azide Polyamide containing aromatics such as Pamide (MXD6); Alicyclic polyamides such as Polyaminomethylcyclohexyl Adipamide (PACM6); and Lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate are copolymerized Polyamide, copolymer 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 individually by 1 type, and may be used in combination of 2 or more type. The stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.

  The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1. Moreover, the base material layer 1 may be formed by coating the above-mentioned material on the barrier layer 3.

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

  The base material layer 1 can be laminated (multi-layer structure) of at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery packaging. is there. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, and a multilayer structure in which a plurality of polyester films are laminated. When the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films The body is preferred. For example, when the base material layer 1 is formed from two resin films, the polyester resin and the polyester resin are laminated, the polyamide resin and the polyamide resin are laminated, or the polyester resin and the polyamide resin are laminated. It is preferable to use a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated. In addition, since the biaxially stretched polyester is difficult to discolor when the electrolyte solution adheres to the surface, for example, the base material layer 1 has a multilayer structure of a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film. The base material layer 1 is preferably a laminate having biaxially stretched nylon and biaxially stretched polyester in this order from the barrier layer 2 side. When the base material layer 1 has a multilayer structure, the thickness of each layer is preferably about 3 to 25 μm.

  When making the base material layer 1 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot-melt state such as a co-extrusion lamination method, a sandwich lamination method, or a thermal lamination method can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive. Furthermore, the adhesive 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 hot pressure type, an electron beam curable type, an ultraviolet curable type, and the like. Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 2. Further, the thickness of the adhesive can be the same as that of the adhesive layer 2.

  In the present invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant adheres to the surface of the base material layer 1 side. Although it does not restrict | limit especially as a lubricant, Preferably an amide type lubricant is mentioned. Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like. Specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc. Specific examples of the fatty acid ester amide include stearoamidoethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like. One type of lubricant may be used alone, or two or more types may be used in combination.

When there is a lubricant on the surface of the base layer 1, the amount of the lubricant is not particularly limited, but is preferably about 3 mg / m ² or more, more preferably 4 in an environment of a temperature of 24 ° C. and a relative humidity of 60%. to 15 mg / m ² about, even more preferably include about 5~14mg / m ^2.

  The thickness of the base material layer 1 is preferably about 4 μm or more, more preferably about 10 to 75 μm, from the viewpoint of making the battery packaging material excellent in moldability while reducing the thickness of the battery packaging material. More preferably, about 10-50 micrometers is mentioned.

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

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

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

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

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function of preventing water vapor, oxygen, light and the like from entering the battery, in addition to improving the strength of the battery packaging material. The barrier layer 3 is preferably a metal layer, that is, a layer formed of metal. Specific examples of the metal constituting the barrier layer 3 include aluminum, stainless steel, and titanium, and preferably aluminum. The barrier layer 3 can be formed by, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil. From the viewpoint of preventing the generation of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: (1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like, more preferably formed of a soft aluminum alloy foil.

  The thickness of the barrier layer 3 is not particularly limited as long as it exhibits a barrier function such as water vapor, but is preferably about 100 μm or less, more preferably about 10 to 100 μm, from the viewpoint of reducing the thickness of the battery packaging material. More preferably, about 10-80 micrometers is mentioned.

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

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

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

  In addition, as a method for specifically providing an acid-resistant film, for example, as an example, at least the surface on the inner layer side of the aluminum alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method. , Degreased by a known treatment method such as an acid activation method, and then a phosphoric acid metal salt such as chromium phosphate salt, titanium phosphate salt, zirconium phosphate salt, zinc phosphate salt and the like Treatment liquid (aqueous solution) mainly composed of a mixture of metal salts, or treatment liquid (aqueous solution) principally composed of a non-metallic phosphate and a mixture of these non-metallic salts, or acrylic resin In addition, a treatment liquid (aqueous solution) composed of a mixture with a water-based synthetic resin such as a phenol resin or a urethane resin is applied by a known coating method such as a roll coating method, a gravure printing method, or a dipping method. Ri, it is possible to form the acid-resistant coating. For example, when treated with a chromium phosphate salt treatment solution, it becomes an acid-resistant film made of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and treated with a zinc phosphate salt treatment solution. In this case, an acid-resistant film made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride or the like is obtained.

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

  Other examples of acid-resistant films include phosphate-based and chromic acid-based films. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate. Examples of the chromic acid system include chromium chromate.

  In addition, as another example of the acid-resistant film, by forming an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound, between the aluminum and the base material layer at the time of embossing molding Prevention of delamination, hydrogen fluoride generated by the reaction between electrolyte and moisture prevents dissolution and corrosion of the aluminum surface, especially the dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface This improves the wettability and prevents delamination between the base material layer and aluminum at the time of heat fusion. In the embossed type, it shows the effect of preventing delamination between the base material layer and aluminum at the time of press molding. Among substances that form an acid-resistant film, an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.

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

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

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

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

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

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

The composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry. By analyzing the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry, for example, a peak derived from at least one of Ce ⁺ and Cr ⁺ is detected.

  It is preferable that the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium. In addition, it is confirmed using X-ray photoelectron spectroscopy that the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contains at least one element selected from the group consisting of phosphorus, chromium and cerium. can do. Specifically, first, in the battery packaging material, the heat-fusible resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is put in an electric furnace, and organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, it confirms that these elements are contained using the X-ray photoelectron spectroscopy of the surface of aluminum alloy foil.

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

  The thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesion strength with the barrier layer 3 and the heat-sealing resin layer. About 1 to 50 nm. The thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.

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

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

  In the battery packaging material of the present invention, when the heat-fusible resin layer 4 is a single layer, the melting peak temperature of the heat-fusible resin layer 4 is 130 ° C. or lower, When the adhesive resin layer 4 is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer 4 (that is, the innermost layer) is 130 ° C. It is characterized by the following. That is, in the battery packaging material of the present invention, when the heat-fusible resin layer 4 is constituted by a single layer, the heat of the single layer constituting the surface opposite to the barrier layer 3 is formed. The melting peak temperature of the fusible resin layer 4 is 130 ° C. or lower. Further, when the heat-fusible resin layer 4 is composed of a plurality of layers, the heat-fusible resin layer 4 of the layer constituting at least the surface opposite to the barrier layer 3 among the multilayers. The melting peak temperature of is 130 ° C. or lower.

  Even when a battery in which an inorganic material is blended with a resin forming a separator is exposed to a high temperature environment, the barrier of the heat-fusible resin layer 4 is suppressed from the viewpoint of suppressing the expansion of the battery and leading to a gentle opening. The layer constituting the surface opposite to the layer 3 (in the present invention, the “layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer” is the heat-fusible resin layer Is a single layer heat-fusible resin layer, and when the heat-fusible resin layer is a multilayer, the barrier layer of the heat-fusible resin layer is The upper limit of the melting peak temperature of the innermost layer constituting the surface on the opposite side is preferably about 125 ° C. or lower, more preferably about 120 ° C. or lower, and further preferably about 118 ° C. or lower. The lower limit is preferably about 90 ° C. or higher. Preferred ranges of the melting peak temperature of the layer constituting the surface opposite to the barrier layer 3 of the heat-fusible resin layer 4 are about 90 to 130 ° C, about 90 to 125 ° C, and about 90 to 120 ° C. 90 to 118 ° C. When the battery packaging material of the present invention is used for a battery opened at a set temperature of 90 ° C. or higher and 100 ° C. or lower, the surface opposite to the barrier layer 3 of the heat-fusible resin layer 4 is constituted. As a preferable range of the melting peak temperature of the layer which is carrying out, about 90-99 degreeC is mentioned. When the battery packaging material of the present invention is used for a battery that is opened at a set temperature of more than 100 ° C. and not more than 110 ° C., the surface of the heat-fusible resin layer 4 opposite to the barrier layer 3 is used. As a preferable range of the melting peak temperature of the layer constituting the film, about 100 to 109 ° C. can be mentioned. When the battery packaging material of the present invention is used for a battery that is opened at a set temperature of more than 110 ° C. and 120 ° C. or less, the surface of the heat-fusible resin layer 4 opposite to the barrier layer 3 is used. As a preferable range of the melting peak temperature of the layer constituting the film, about 110 to 120 ° C. can be mentioned.

  Moreover, when the heat-fusible resin layer 4 is composed of multiple layers, the upper limit of the melting peak temperature of the layer located on the barrier layer 3 side is preferably about 170 ° C. or less, more preferably about 165 ° C. or less. More preferably, it is about 163 ° C. or less, particularly preferably 160 ° C. or less, and the lower limit is preferably about 100 ° C. or more. Moreover, as a preferable range of the melting peak temperature of the layer located in the barrier layer 3 side, about 100-170 degreeC, about 100-165 degreeC, about 100-163 degreeC, and about 100-160 degreeC are mentioned.

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

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

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

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

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

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

  The heat-fusible resin layer 4 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds of resin components are combined. As described above, the heat-fusible resin layer 4 may be composed of only one layer, but may be composed of two or more layers by the same or different resin components.

  Even when a battery in which an inorganic material is blended with a resin forming a separator is exposed to a high temperature environment, the barrier of the heat-fusible resin layer 4 is suppressed from the viewpoint of suppressing the expansion of the battery and leading to a gentle opening. The layer constituting the surface opposite to the layer 3 is preferably made of polypropylene. Moreover, when the heat-fusible resin layer is comprised by the multilayer, it is preferable that the layer located in the barrier layer 3 side of the fusible resin layer 4 is comprised by the polypropylene. In particular, when the battery packaging material of the present invention includes the adhesive layer 5, the layer located on the barrier layer 3 side of the fusible resin layer 4 is preferably made of polypropylene.

  In the present invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant adheres to the surface of the heat-fusible resin layer. Although it does not restrict | limit especially as a lubricant, Preferably an amide type lubricant is mentioned. Specific examples of the amide-based lubricant include those described above.

When a lubricant is present on the surface of the heat-fusible resin layer, the amount of the lubricant is not particularly limited, but is preferably about 3 mg / m ² or more, more preferably in an environment of a temperature of 24 ° C. and a relative humidity of 60%. 4~15mg / m ² approximately, more preferably include about 5~14mg / m ^2.

  Further, the thickness of the layer constituting the surface of the heat-fusible resin layer 4 opposite to the barrier layer 3 (that is, when the heat-fusible resin layer is a single layer, the heat of the single layer) When the heat-fusible resin layer is a multilayer, the thickness of the innermost layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer. ) Is not particularly limited as long as it functions as a heat-fusible resin layer. However, even when a battery in which an inorganic material is blended with a resin forming a separator is exposed to a high temperature environment, the battery expands. From the viewpoint of suppressing and leading to gentle opening, the upper limit is preferably about 60 μm or less, more preferably about 55 μm or less, further preferably about 50 μm or less, and the lower limit is preferably about 10 μm or more, More preferably about 15 μm or more, still more preferably about 20 μm or more. Moreover, as a preferable range of the thickness of the layer which comprises the surface on the opposite side to the barrier layer 3 of the heat-fusible resin layer 4, about 10-60 micrometers, about 10-55 micrometers, about 10-50 micrometers, about 15- 15 About 60 micrometers, about 15-55 micrometers, about 15-50 micrometers, about 20-60 micrometers, about 20-55 micrometers, about 20-50 micrometers are mentioned.

  When the heat-fusible resin layer is composed of multiple layers, the thickness of the layer located on the barrier layer 3 side of the heat-fusible resin layer 4 functions as a heat-fusible resin layer. If the battery in which the inorganic material is blended with the resin forming the separator is exposed to a high temperature environment, the upper limit is set from the viewpoint of suppressing the expansion of the battery and leading to a gentle opening. Is preferably about 60 μm or less, more preferably about 55 μm or less, and even more preferably about 50 μm or less. The lower limit is preferably about 10 μm or more, more preferably about 15 μm or more, and further preferably about 20 μm or more. It is done. Moreover, as a preferable range of the thickness of the layer located in the barrier layer 3 side of the heat-fusible resin layer 4, about 10-60 micrometers, about 10-55 micrometers, about 10-50 micrometers, about 15-60 micrometers, about 15-55 micrometers. About 15-50 micrometers, About 20-60 micrometers, About 20-55 micrometers, About 20-50 micrometers is mentioned.

  When the heat-fusible resin layer 4 is composed of multiple layers, the total thickness of the heat-fusible resin layer 4 is preferably about 20 to 100 μm, more preferably about 20 to 85 μm, and still more preferably 40 to About 80 μm can be mentioned.

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

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

  Furthermore, from the viewpoint of making the battery packaging material excellent in shape stability after molding while reducing the thickness of the battery packaging material, the adhesive layer 5 is a cured resin composition containing an acid-modified polyolefin and a curing agent. It may be a thing. Preferred examples of the acid-modified polyolefin include the same carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4.

  Further, the curing agent is not particularly limited as long as it can cure the acid-modified polyolefin. Examples of the curing agent include an epoxy curing agent, a polyfunctional isocyanate curing agent, a carbodiimide curing agent, and an oxazoline curing agent.

  The epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group. Examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.

  The polyfunctional isocyanate curing agent 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 isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurate, Examples thereof include mixtures and copolymers with other polymers.

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

  The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd.

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

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

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

[Surface coating layer]
In the battery packaging material of the present invention, the outer side of the base material layer 1 (the barrier layer of the base material layer 1) is optionally used for the purpose of improving design properties, electrolytic solution resistance, scratch resistance, moldability, and the like. If necessary, a surface coating layer may be provided on the side opposite to (3).

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

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

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

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

3. Production method of battery packaging material The production method of the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained. That is, in the method for producing a battery packaging material of the present invention, a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material is contained in a package formed of the battery packaging material. A method for producing a battery packaging material for use in a battery, wherein the battery is opened at a predetermined set temperature of 120 ° C. or lower, and includes at least a base material layer, a barrier layer, and heat fusion When the heat-fusible resin layer is a single layer as the heat-fusible resin layer, the melting peak temperature of the heat-fusible resin layer is When the heat-fusible resin layer is a multilayer, the melting peak of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer A method using a material whose temperature is 130 ° C. or lower. .

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

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

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

  As described above, the surface coating layer / base material layer 1 provided as necessary / adhesive layer 2 provided as necessary / barrier layer 3 whose surface is subjected to chemical conversion treatment as needed / as needed A laminate composed of the adhesive layer 5 / the heat-fusible resin layer 4 to be provided is formed. In order to strengthen the adhesiveness of the adhesive layer 2 or the adhesive layer 5, further, a hot roll contact type, a hot air type You may use for near- or far-infrared type heat processing.

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

4). Use of battery packaging material The battery packaging material of the present invention is used as a packaging material for sealing and housing a battery element including at least a positive electrode, a negative electrode, an electrolyte, and a separator containing an inorganic material. The Moreover, as described above, the battery packaging material of the present invention is used for a battery containing a resin and an inorganic material in a separator. The battery packaging material of the present invention is particularly suitably used for small batteries used in mobile devices such as mobile phones and laptop computers.

  Specifically, a battery element including at least a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material is a battery packaging material of the present invention, and metal terminals connected to each of the positive electrode and the negative electrode. In a state of projecting outward, the periphery of the battery element is covered so that a flange portion (region where the heat-fusible resin layers are in contact with each other) can be formed, and the heat-fusible resin layers of the flange portion are heated. By sealing and sealing, a battery using the battery packaging material is provided. In addition, when accommodating a battery element using the battery packaging material of the present invention, the battery packaging material of the present invention is used such that the sealant portion is on the inner side (surface in contact with the battery element).

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

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

<Manufacture of battery packaging materials>
Example 1-5, Comparative Example 1-5
Battery packaging materials having the laminated structure shown in Table 1 were produced. As shown in Table 1, the laminated structure of the battery packaging material is formed by laminating a coating layer, a base material layer, an adhesive layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in order from the left side of Table 1. Yes. In addition, an item not provided with a layer shown in Table 1 is denoted by “−”. For example, in Table 1, in Example 1, the heat-fusible resin layer is a single layer made of polypropylene (thickness 40 μm), and the single layer is described in the column of the layer located on the barrier layer side. The surface side is indicated as “−”. For Example 4-7 and Comparative Examples 1, 4 and 5, the configuration of the heat-fusible resin layer was similarly shown in Table 1. In these Examples 1, 4-7 and Comparative Examples 1, 4 and 5, the heat-fusible resin layer described in the column of “Barrier layer side” in Table 1 is a single layer. Both the barrier layer side and the surface side.

  In Table 1, in the item of coating layer, the type of lubricant forming the coating layer is described. In Example 1 and Comparative Example 1, the PET layer (polyethylene terephthalate layer), the adhesive layer, and the ON layer (stretched nylon layer) are laminated in this order from the coating layer side. In the adhesive layer located between the barrier layer and the heat-fusible resin layer, “PPA” means maleic anhydride-modified polypropylene, and “LM” means a two-component curable adhesive. The numerical value described after the material means the thickness of the layer.

  In Table 1, the heat-fusible resin layers of Examples 2 and 3 and Comparative Examples 2 and 3 are composed of two layers, a layer located on the barrier layer side and a layer located on the surface side. “PP” means polypropylene, and “CPP” means unstretched polypropylene. “EC” means that it is formed by extrusion coating (resin melt extrusion laminating).

First, an aluminum foil subjected to chemical conversion treatment on both surfaces was laminated as a barrier layer on one surface of the base material layer by a dry laminating method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 μm) was formed on the barrier layer. Subsequently, after laminating the adhesive layer and the base material layer on the barrier layer, an aging treatment was performed to prepare a base material layer / adhesive layer / barrier layer laminate. In addition, the chemical conversion treatment of the aluminum foil used as the barrier layer was performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium was 10 mg / m ² (dry weight). It was performed by applying and baking on both sides of the aluminum foil by the method. Next, an adhesive layer and a heat-fusible resin layer were laminated on the barrier layer side of the laminate to obtain a battery packaging material having a laminated structure shown in Table 1. The melting peak temperatures (melting points) of the respective layers constituting the adhesive layer and the heat-fusible resin layer are as shown in Table 1, respectively.

<Opening test>
Each battery packaging material obtained above was cut to prepare samples each having a short side of 90 mm and a long side of 150 mm. Next, each sample was molded using a molding die (female) having a diameter of 32 mm on the short side and 55 mm on the long side and a molding die (male) corresponding to this with a pressing pressure of 0.13 MPa and 3 mm. Cold forming was performed at a depth, and a recess was formed in the central portion. At this time, the clearance between the female mold and the male mold was set to 0.3 mm. Moreover, it shape | molded so that the short side and long side of a sample and a shaping die might correspond. Next, the sample after molding is folded at the folding position P shown in FIG. 5 so that the heat-fusible resin layers face each other, and the three peripheral edge portions 10a (FIG. 4A) )) Was thermally fused (175 ° C., 3 seconds, pressure 1.4 MPa). At this time, a separator having a short side of 30 mm and a long side of 52 mm (thickness 3 mm) and 0.5 g of water as a virtual electrolyte were sealed to form a case having an internal space (pressure 1 atm). The separator is a commercially available product in which an inorganic material (aluminum silicate particles) is blended with a polyethylene porous film, and the melting peak temperature of the resin constituting the separator shown in Table 1 (that is, the melting peak temperature of polyethylene) is 145 ° C. The thing which has was used.

  Next, the peripheral edge portion 10a was cut so that the width of the portion where the heat-fusible resin layers were heat-sealed was 3 mm to obtain a battery 10 for an unsealing test. Next, as shown in FIG. 4A, the battery for unsealing test 10 is placed in the space between the two stainless steel plates 20, and the interval w between the two stainless steel plates 21 is 7.0 mm. Thus, the fixing spacer 21 was adjusted. Next, in this state, it was put in an oven (DNF401 type manufactured by Yamato Scientific Co., Ltd.) set at 25 ° C. and 1 atm, and heated up to 120 ° C. at a heating rate of 10 ° C./10 minutes. As the temperature in the oven rises, the internal pressure of the unsealing test battery 10 rises and swells, resulting in a state as shown in FIG. Table 1 shows the expansion, opening temperature, and opening state when the environmental temperature in the oven is kept at 120 ° C. for 2 hours. The temperature is a set value in the test oven. The reason for holding the battery using the stainless steel plate and the fixing spacer is that the battery is usually fixed by a case or the like. In addition, water was used as a virtual electrolyte, and water was sealed with a battery packaging material, and the unsealing test was performed in terms of ensuring the safety of the unsealing test and using water instead of the electrolyte, This is because the opening performance can be evaluated.

  As shown in Table 1, the opening test batteries using the battery packaging materials of Examples 1, 4 and 5 did not expand greatly until reaching 120 ° C., and opened gently when reaching 120 ° C. . In addition, the unsealing test batteries using the battery packaging materials of Examples 2 and 3 did not expand greatly until reaching 119 ° C, and were gently opened when reaching 119 ° C. In addition, the battery for opening test using the battery packaging material of Example 6 did not expand greatly until reaching 111 ° C., and was gently opened when it reached 111 ° C. Further, the battery for unsealing test using the battery packaging material of Example 7 did not expand greatly until it reached 108 ° C., and was gently opened when it reached 108 ° C.

  On the other hand, the opening test batteries using the battery packaging materials of Comparative Examples 1 to 5 expanded greatly until reaching 120 ° C., and did not open even after 2 hours.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-fusion resin layer 5 Adhesive layer 10 Battery 10a for opening test Edge 20 Stainless steel plate 21 Fixing spacer M Molding part P Folding position

Claims (11)

A battery packaging material for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator is housed in a packaging body formed of the battery packaging material,
The separator includes a resin and an inorganic material,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
The battery packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. or less. Battery packaging material.   The battery packaging material according to claim 1, wherein a melting peak temperature of a resin constituting the separator is 130 ° C or higher. When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is lower than the melting peak temperature of the resin constituting the separator,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is the resin constituting the separator. The battery packaging material according to claim 1 or 2, which is lower than a melting peak temperature of the battery.   The battery packaging material according to claim 1, further comprising an adhesive layer between the heat-fusible resin layer and the barrier layer.   The battery packaging material according to any one of claims 1 to 4, wherein the battery is a battery opened at a predetermined set temperature of 90 ° C or higher and 120 ° C or lower. At least a battery element including a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material is a battery accommodated in a package formed of a battery packaging material,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
The battery packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is 130 ° C. or less. battery.   The battery according to claim 6, wherein a melting peak temperature of a resin constituting the separator is 130 ° C. or higher. When the heat-fusible resin layer is a single layer, the melting peak temperature of the heat-fusible resin layer is lower than the melting peak temperature of the resin constituting the separator,
When the heat-fusible resin layer is a multilayer, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer is the resin constituting the separator. The battery according to claim 6 or 7, wherein the battery has a melting peak temperature lower than that of the battery.   The battery according to any one of claims 6 to 8, further comprising an adhesive layer between the heat-fusible resin layer and the barrier layer.   The battery according to any one of claims 6 to 9, wherein the battery is a battery opened at a predetermined set temperature of 90 ° C or higher and 120 ° C or lower. A battery packaging material manufacturing method for use in a battery in which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator including a resin and an inorganic material is housed in a packaging body formed of the battery packaging material. There,
The battery is a battery that opens at a predetermined set temperature of 120 ° C. or less,
At least a step of laminating a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
When the heat-fusible resin layer is a single layer as the heat-fusible resin layer, the melting peak temperature of the heat-fusible resin layer is 130 ° C. or less, and the heat-fusible resin layer Battery having a melting peak temperature of 130 ° C. or lower of the layer constituting the surface opposite to the barrier layer of the heat-fusible resin layer when the heat-resistant resin layer is a multilayer. Method of manufacturing packaging materials.