JP7019991B2 - Battery packaging materials, their manufacturing methods, and batteries - Google Patents

Description

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

Conventionally, various types of batteries have been developed, but in all batteries, a packaging material is an indispensable member for encapsulating a battery element such as an electrode or an electrolyte. Conventionally, metal packaging materials have been widely used for 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 thinner and lighter weight. However, the metal packaging material for batteries, which has been widely used in the past, has a drawback that it is difficult to keep up with the diversification of shapes and there is a limit to weight reduction.

Therefore, in recent years, as a battery packaging material that can be easily processed into various shapes and can be made thinner and lighter, a film in which a base material layer / adhesive layer / barrier layer / heat-sealing resin layer is sequentially laminated. A shaped laminate has been proposed. Such a film-shaped packaging material for a battery is formed so that the battery element can be sealed by heat-sealing the peripheral portions of the heat-sealing resin layers so as to face each other.

In recent years, batteries have been required to have a higher energy density, but ensuring safety has become 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 membrane is generally used as the separator. The battery shutdown function is a function in which the pores of the separator are blocked to cut off the current when the battery temperature rises, and this function suppresses thermal runaway of the battery.

With the increase in energy density of batteries in recent years, the separator is 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 with the resin forming the separator is known (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-60061

The heat resistance of the separator can be improved by blending an inorganic material with 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 be decomposed to generate a flammable gas, which may cause an increase in pressure. In addition, the battery may continuously raise the temperature inside the battery due to charging due to overvoltage, discharging due to excessive current, or the like, causing a runaway of the battery reaction. Further, when the battery is exposed to a high temperature environment higher than the melting peak temperature of the resin constituting the separator, the separator may melt down, a short circuit may occur inside the battery, and the battery temperature may rise further. ..

In a battery using a film-shaped battery packaging material, such an increase in pressure or temperature inside the battery may cause the battery packaging material to be cleaved and cause ignition due to the ejection of flammable gas. Further, if the pressure and temperature in the battery continue to rise and the battery reaction goes out of control in a state where the packaging material for the battery is excessively expanded, the battery may explode. For this reason, a battery element provided with a separator having improved heat resistance by blending an inorganic material with a resin, a positive electrode, a negative electrode, and an electrolyte is used for a battery housed in a package made of a packaging material. Depending on the application, it is required to suppress the expansion of the battery when exposed to a high temperature environment and gently open the package material at a predetermined temperature.

For example, small batteries used in mobile devices such as mobile phones and laptops are always in the hands of the user, and if the battery expands significantly and then explosively opens, the danger is extremely high. For this reason, small batteries for mobile use are set to be gently opened by suppressing the expansion of the battery at a predetermined temperature (preferably 120 ° C. or lower) when exposed to a high temperature environment. You are required to be there.

An object of the present invention is to provide a battery packaging material capable of suppressing expansion of a battery and gently opening 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 made diligent studies to solve the above problems. As a result, the battery element having the positive electrode, the negative electrode, the electrolyte, and the separator is used for the battery contained in the package formed of the battery packaging material, and the separator is a battery packaging material. The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower, and the packaging material for the battery is at least a base material layer, a barrier layer, and a heat-sealing property. It is composed of a laminated body including resin layers in this order, and when the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower, and the above-mentioned When the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130 ° C. or lower for a battery. It has been found that the packaging material can suppress the expansion of the battery and gently open the battery even when the battery is exposed to a high temperature environment (for example, about 90 to 120 ° C.). The present invention has been completed by further studies based on such findings.

That is, the present invention provides a battery packaging material and a battery according to the following aspects.
Item 1. A battery packaging material for using a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator in a battery housed in a package formed of the battery packaging material.
The separator contains a resin and an inorganic material, and the separator contains a resin and an inorganic material.
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
The battery packaging material is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower.
When the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130 ° C. or lower. Packaging material for batteries.
Item 2. Item 2. The packaging material for a battery 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-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is lower than the melting peak temperature of the resin constituting the separator.
When the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is the resin constituting the separator. Item 3. The packaging material for a battery according to Item 1 or 2, which is lower than the melting peak temperature of.
Item 4. Item 2. The packaging material for a battery according to any one of Items 1 to 3, wherein an adhesive layer is provided between the heat-sealing resin layer and the barrier layer.
Item 5. Item 2. The battery packaging material according to any one of Items 1 to 4, wherein the battery is a battery that is opened at a predetermined set temperature of 90 ° C. or higher and 120 ° C. or lower.
Item 6. A battery in which 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 housed in a package formed of a battery packaging material.
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
The battery packaging material is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower.
When the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130 ° C. or lower. battery.
Item 7. Item 6. The battery according to Item 6, wherein the melting peak temperature of the resin constituting the separator is 130 ° C. or higher.
Item 8. When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is lower than the melting peak temperature of the resin constituting the separator.
When the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is the resin constituting the separator. Item 6. The battery according to Item 6 or 7, which is lower than the melting peak temperature of.
Item 9. Item 6. The battery according to any one of Items 6 to 8, wherein an adhesive layer is provided between the heat-sealing resin layer and the barrier layer.
Item 10. Item 2. The battery according to any one of Items 6 to 9, wherein the battery is a battery that is opened at a predetermined set temperature of 90 ° C. or higher and 120 ° C. or lower.
Item 11. A method for manufacturing a battery packaging material for using a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material for a battery housed in a package formed of the battery packaging material. There,
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
At least, it includes a step of laminating a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
When the heat-sealing resin layer is a single layer as the heat-sealing resin layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower, and the heat-sealing is also carried out. When the sex resin layer is a plurality of layers, a battery having a melting peak temperature of 130 ° C. or lower, which constitutes a surface opposite to the barrier layer of the heat-sealing resin layer, is used. Manufacturing method of packaging materials for.

According to the present invention, it is possible to provide a battery packaging material capable of suppressing expansion of a battery and gently opening the battery when the battery including a separator containing a resin and an inorganic material is exposed to a high temperature environment. ..

It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a schematic diagram for demonstrating the method of the opening test of the packaging material for a battery in an Example. F. It is a schematic diagram which shows the position where the sample after molding is folded back in the opening test.

The packaging material for a battery of the present invention is a packaging material for a battery for which a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator is housed in a package formed of the packaging material for the battery. The separator contains a resin and an inorganic material, the battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower, and the packaging material for the battery is at least a base material layer and a barrier layer. , And a laminated body including the heat-sealing resin layer in this order, and when the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130. When the temperature is below ° C. and the heat-sealing resin layer is a plurality of layers, the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130. It is characterized by being below ° C. Hereinafter, the battery packaging material of the present invention will be described in detail.

In this specification, the numerical range indicated by "-" means "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.

1. 1. Laminated Structure and Characteristics of Battery Packaging Material As shown in FIG. 1, the battery packaging material is composed of a laminate having at least a base material layer 1, a barrier layer 3, and a heat-sealing resin layer 4 in this order. In the packaging material for batteries of the present invention, the base material layer 1 is on the outermost layer side, and the heat-sealing resin layer 4 is on the innermost layer side. That is, at the time of assembling the battery, the heat-weldable resin layers 4 located on the peripheral edge of the battery element are heat-welded to each other to seal the battery element, whereby the battery element is sealed.

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 thereof, if necessary. It may be provided. Further, as shown in FIG. 3, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-bondable resin layer 4 for the purpose of enhancing their adhesiveness, if necessary. Further, for the purpose of improving designability, electrolytic solution resistance, scratch resistance, moldability, etc., if necessary, on the outside of 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 packaging material for a battery 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, the heat resistance of the separator is enhanced, so that the battery is designed to operate even in a high temperature environment. However, as described above, even in a battery having improved heat resistance of the separator, there is a possibility that the packaging material for the battery may be cleaved due to an increase in pressure or temperature inside the battery. Therefore, the battery packaging material, which has improved heat resistance by blending an inorganic material with the resin forming the separator, should be gently opened by suppressing the expansion of the battery even when exposed to a high temperature environment. Is required. In particular, for example, a small battery used in a mobile device such as a mobile phone or a notebook computer is always in the hands of the user, and if the battery expands significantly and then is opened explosively, the danger is extremely high. For this reason, small batteries for mobile use are set to be gently opened by suppressing the expansion of the battery when exposed to a predetermined high temperature environment (preferably 120 ° C. or lower). Is required.

In the present invention, gentle opening means, for example, flammability before the battery expands significantly, rather than explosively opening after the battery expands significantly after the battery reaches a set temperature. It means that the gas will be released quietly and the package will be opened.

The packaging material for a battery of the present invention is a battery that is opened at a predetermined set temperature of 120 ° C. or lower. More specifically, when the temperature of the battery is raised to a specified set temperature of 120 ° C. or lower, 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 released. It is used for batteries that are set to open. Further, when the heat-sealing resin layer 4 is a single layer, the melting peak temperature of the heat-sealing resin layer 4 is 130 ° C. or lower, and the heat-sealing resin layer 4 is a plurality of layers. The melting peak temperature of the layer constituting the surface of the heat-sealing resin layer 4 opposite to the barrier layer 3 is 130 ° C. or lower (that is, the barrier of the heat-sealing resin layer 4). Since the melting peak temperature of the innermost layer constituting the surface opposite to the layer 3 is set to 130 ° C. or lower), the battery in which the inorganic material is mixed with the resin forming the separator is in a predetermined high temperature environment ( When exposed to (preferably 120 ° C. or lower), 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 packaging material for a battery 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, further 140 ° C. or higher, more preferably 130 to 150 ° C. It can be suitably used for a battery having excellent heat resistance set at 140 to 150 ° C. Further, from the viewpoint of suppressing the expansion of the battery and gently opening the package, when the heat-sealing resin layer 4 is a single layer, the melting peak temperature of the heat-sealing resin layer constitutes the separator. When the temperature is lower than the melting peak temperature of the resin and the heat-sealing resin layer 4 is a plurality of layers, the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer. It is preferable that the melting peak temperature is lower than the melting peak temperature of the resin constituting the separator.

Further, in the present invention, the set temperature at which the battery is opened is not particularly limited as long as it is 120 ° C. or lower, and is set to an appropriate temperature according to the application of the battery. The upper limit of the set temperature is about 120 ° C. or lower, 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. The preferred range of the set temperature leading to opening is, for example, about 90 to 120 ° C, about 90 to 110 ° C, about 90 to 100 ° C, about 95 to 120 ° C, about 95 to 110 ° C, and about 95 to 100 ° C. Can be mentioned.

The separator included in the battery in which the packaging material for a battery of the present invention is used is not particularly limited as long as it contains an inorganic material, but as described above, the melting peak temperature of the resin forming the separator is 130 ° C. or higher. It is desirable that it has excellent heat resistance. Specific examples of the separator include a polyolefin porous membrane in which an inorganic material is blended. Such separators are known, and examples thereof include those disclosed in the above-mentioned Patent Document 1.

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

Further, as the inorganic material, either a synthetic product or a natural product can be used without particular limitation. Natural products are not particularly limited, but are, for example, kaolinite, dikite, nacrite, halloysite, pyrophyllite, audinite, montmorillonite, byderite, nontronite, volcon scoreite, saponite, saconite, sinholdite, vermiculite, etc. Vermiculite, Amesite, Keliaite, Freiponite, Brindriite, Black Mica, Phlogopite, Annite, East Knight, Siderophyllite Tetraferi Annite, Scale Mica, Polylysionite, Muscovite, Celadon Stone, Iron Celadon Stone, Annite, Annite, Aluminoceradon stone, Tobelite, Soda mica, Clintnite, Kinoshita, Vite mica, Ananda stone, Pearl mica, Clinocloa, Chamosite, Penantite, Nimite, Baileicroa, Donbacite, Cookaite, Sudoite, etc. Can be mentioned. One type of inorganic material may be used alone, or two or more types may be used in combination.

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

The thickness of the laminate constituting the packaging material for the battery of the present invention is not particularly limited, but when the battery in which the inorganic material is mixed with the resin forming the separator while reducing the thickness is exposed to a high temperature environment. 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, still more preferably about 180 μm or less, and the lower limit is preferably about 180 μm or less. Approximately 60 μm or more can be mentioned. The thickness range of the laminated body is preferably about 60 to 250 μm, about 60 to 200 μm, and about 60 to 180 μm.

2. 2. Each layer forming the packaging material for batteries [base material layer 1]
In the packaging material for batteries of the present invention, the base material layer 1 is a layer located on the outermost layer side. The material forming the base material layer 1 is not particularly limited as long as it has an insulating property. Examples of the material forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, polycarbonate, and mixtures and copolymers thereof. Can be mentioned. Among these, the base material layer 1 preferably has at least one of a layer formed of polyester and a layer formed of polyamide.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and ethylene terephthalate as the main constituents of the copolymerized polyester and butylene terephthalate as the main constituent of the repeating unit. Examples thereof include the copolymerized polyester. Further, as the copolymerized polyester having ethylene terephthalate as the main body of the repeating unit, specifically, a copolymer polyester having ethylene terephthalate as the main body of the repeating unit and polymerizing with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate)). (Abbreviated after), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) , Polyethylene (terephthalate / decandicarboxylate) and the like. Further, as the copolymerized polyester having butylene terephthalate as the main body of the repeating unit, specifically, a copolymer polyester polymerizing with butylene isophthalate using butylene terephthalate as the main body of the repeating unit (hereinafter, polybutylene (terephthalate / isophthalate)). (Abbreviated after), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decantycarboxylate), polybutylene naphthalate and the like. These polyesters may be used alone or in combination of two or more. Polyester has an advantage that it has excellent electrolytic solution resistance and is less likely to cause whitening or the like due to adhesion of the electrolytic solution, and is preferably used as a material for forming the base material layer 1.

Specific examples of the polyamide include an aliphatic polyamide 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 stands for isophthalic acid, T stands for terephthalic acid) and other hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamides, polymethoxylylenazi Aroma-containing polyamide such as pamide (MXD6); alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM6); further, a lactam component and an isocyanate component such as 4,4'-diphenylmethane-diisocyanate are copolymerized. Examples thereof include polyesteramide copolymers and polyetheresteramide copolymers, which are copolymers of the polyamides and copolymerized polyamides with polyesters and polyalkylene ether glycols; and copolymers thereof. These polyamides may be used alone or in combination of two or more. The stretched polyamide film has excellent 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, particularly a biaxially stretched resin film, has improved heat resistance due to orientation crystallization, and is therefore preferably used as the base material layer 1. Further, the base material layer 1 may be formed by coating the above material on the barrier layer 3.

Among these, examples of the resin film forming the base material layer 1 include nylon and polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, and particularly preferably biaxially stretched nylon.

The base material layer 1 can be laminated (multilayer structure) with at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery package. be. Specific examples thereof 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 in which a plurality of biaxially stretched nylon films are laminated, and a laminate in which a plurality of biaxially stretched polyester films are laminated. The body is preferred. For example, when the base material layer 1 is formed from two layers of resin films, the structure is such that 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. Is preferable, and a configuration in which polyethylene terephthalate and polyethylene terephthalate are laminated, a configuration in which nylon and nylon are laminated, or a configuration in which polyethylene terephthalate and nylon are laminated are more preferable. Further, since the biaxially stretched polyester is difficult to discolor when the electrolytic solution adheres to the surface, for example, the base material layer 1 has a multilayer structure 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 the base material layer 1 has a multilayer structure, each resin film may be adhered via an adhesive, or may be directly laminated without an adhesive. In the case of adhering without using an adhesive, for example, a method of adhering in a heat-melted state such as a coextrusion laminating method, a sandwich laminating method, and a thermal laminating method can be mentioned. When adhering via an adhesive, the adhesive used may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a thermal pressure type, an electron beam curing type, an ultraviolet curing type and the like. Specific examples of the adhesive include the same adhesives as those 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 the lubricant is attached to the surface on the base material layer 1 side. The lubricant is not particularly limited, but an amide-based lubricant is preferable. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides. 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 unsaturated fatty acid amides include oleic acid amides and erucic acid amides. Specific examples of the substituted amide include N-oleyl palmitate amide, N-stearyl stearyl amide, N-stearyl oleate amide, N-oleyl stealic acid amide, N-stearyl erucate amide and the like. Further, specific examples of trimethylolamide include trimethylolstearic acid amide. Specific examples of the saturated fatty acid bisamide include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstea. Examples thereof include acid amides, hexamethylene bisbechenic acid amides, hexamethylene hydroxystearic acid amides, N, N'-disteallyl adipic acid amides, and N, N'-distearyl sebasic acid amides. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amides, ethylene biserukaic acid amides, hexamethylene bisoleic acid amides, N, N'-diorail adipic acid amides, and N, N'-diorail sevacinic acid amides. And so on. Specific examples of the fatty acid ester amide include stearoamide ethyl stearate and the like. Specific examples of the aromatic bisamide include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, and N, N'-distearylisophthalic acid amide. The lubricant may be used alone or in combination of two or more.

When the lubricant is present on the surface of the base material layer 1, the abundance thereof 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%. It is about 15 mg / m ² , more preferably about 5 to 14 mg / 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, it is about 10 to 50 μm.

[Adhesive layer 2]
In the packaging material for batteries 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 by an adhesive capable of adhering the base material layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive mechanism used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a thermal 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, and copolymerized polyester; polyether. Adhesives; Polyurethane adhesives; Epoxy resins; Phenolic resin resins; Polyamide resins such as nylon 6, nylon 66, nylon 12, and copolymerized polyamides; polyolefins such as polyolefins, carboxylic acid-modified polyolefins, and metal-modified polyolefins. Resin, polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; polycarbonate; urea resin, amino resin such as melamine resin; rubber such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber; Examples include silicone-based resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane-based adhesive is preferable.

The thickness of the adhesive layer 2 is not particularly limited as long as it functions as an adhesive layer, and examples thereof include about 1 to 10 μm, preferably about 2 to 5 μm.

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function of improving the strength of the battery packaging material and preventing water vapor, oxygen, light and the like from entering the inside of the battery. The barrier layer 3 is preferably a metal layer, that is, a layer made of metal. Specific examples of the metal constituting the barrier layer 3 include aluminum, stainless steel, titanium, and the like, preferably aluminum. The barrier layer 3 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like, and is formed of a metal foil. Is preferable, and it is more preferable to form it with an aluminum alloy foil. From the viewpoint of preventing the formation of wrinkles and pinholes in the barrier layer 3 during the manufacture of battery packaging materials, the barrier layer may be, for example, annealed aluminum (JIS H4160: 1994 A8021HO, JIS H4160: It is more preferably formed from a soft aluminum alloy foil such as 1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O).

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

Further, it is preferable that at least one surface, preferably both sides, of the barrier layer 3 is subjected to chemical conversion treatment in order to stabilize adhesion, prevent 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. The chemical conversion treatment includes, for example, chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium bicarbonate, acetylacetate chromate, chromium chloride, potassium sulfate chromium; phosphorus. Phosphoric acid treatment with a phosphoric acid compound such as sodium acid, potassium phosphate, ammonium phosphate, polyphosphoric acid; for an aminoated phenol polymer having repeating units represented by the following general formulas (1) to (4). Examples include the chromate treatment that was used. In the amination phenol polymer, the repeating unit represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. May be 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. Further, R ¹ and R ² are the same or different, respectively, and 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. Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group. Examples of the hydroxyalkyl groups represented by X, R ¹ and R ² include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group and 3-. A linear or branched chain having 1 to 4 carbon atoms in which one hydroxy group such as a hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, or a 4-hydroxybutyl group is substituted. Alkyl groups can be 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 the same 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 aminoated phenol polymer having the repeating unit represented by the general formulas (1) to (4) is preferably, for example, about 5 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 material in which metal oxides such as aluminum oxide, titanium oxide, cerium oxide and tin oxide and fine particles of 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 by performing a baking treatment at 150 ° C. or higher can be mentioned. Further, a resin layer obtained by cross-linking a cationic polymer with a cross-linking agent may be further formed on the acid-resistant film. Here, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of polyethyleneimine and a polymer having a carboxylic acid, a primary amine graft acrylic resin obtained by graft-polymerizing a primary amine on an acrylic main skeleton, and polyallylamine. Alternatively, a derivative thereof, aminophenol and the like can be mentioned. As these cationic polymers, only one kind may be used, or two or more kinds may be used in combination. Examples of the cross-linking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent, and the like. As these cross-linking agents, only one kind may be used, or two or more kinds may be used in combination.

As a method for specifically providing the acid-resistant film, for example, as an example, at least the inner layer side surface of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, or an electrolytic acid cleaning method. , The degreasing treatment is performed by a well-known treatment method such as an acid activation method, and then the degreased surface is subjected to a phosphoric acid metal salt such as a chromium phosphate salt, a titanium phosphate salt, a zirconium phosphate salt or a zinc phosphate salt, and these. A treatment solution (aqueous solution) containing a mixture of metal salts as a main component, or a treatment solution (aqueous solution) containing a mixture of a non-metal phosphate and these non-metal salts as a main component, or an acrylic resin with these. By applying a treatment liquid (aqueous solution) consisting of a mixture with a water-based synthetic resin such as a phenol-based resin or a urethane-based resin by a well-known coating method such as a roll coating method, a gravure printing method, or a dipping method, an acid-resistant film is formed. Can be formed. For example, when treated with a chromium phosphate-based treatment liquid, an acid-resistant film composed of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc. is formed and treated with a zinc phosphate-based treatment liquid. If so, the acid-resistant film is made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride and the like.

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

Further, as another example of the acid resistant film, a phosphate-based film or a chromic acid-based film can be mentioned. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, chromium phosphate and the like, and examples of the chromium acid system include chromium chromate and the like.

Further, as another example of the acid-resistant film, by forming an acid-resistant film such as a phosphate, a chromate, a fluoride, and a triazinethiol compound, the aluminum and the base material layer at the time of embossing are formed. Prevention of delamination, hydrogen fluoride generated by the reaction between the electrolyte and water prevents the aluminum surface from melting and corroding, especially the aluminum oxide present on the aluminum surface from melting and corroding, and adhering to the aluminum surface. It improves the property (wetting property) and shows the effect of preventing the delamination of the base material layer and aluminum during heat fusion, and in the embossed type, the effect of preventing the delamination of the base material layer and aluminum during press molding. Among the substances forming 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 drying and baking treatment is good.

Further, the acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a cross-linking agent for cross-linking the anionic polymer, and the phosphoric acid or phosphate is the above-mentioned. About 1 to 100 parts by mass may be blended with respect to 100 parts by mass of cerium oxide. It is preferable that the acid-resistant film has a multilayer structure further including a cationic polymer and a layer having a cross-linking agent for cross-linking the cationic polymer.

Further, it is preferable that the anionic polymer is a poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component. Further, it is preferable that the cross-linking agent is at least one selected from the group consisting of a compound having a functional group of any of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group and a silane coupling agent.

Further, it is preferable that the phosphoric acid or phosphate is 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. Further, these chemical conversion treatments may be carried out by using one kind of compound alone or by using two or more kinds of compounds in combination. Among the chemical conversion treatments, chromate treatment and chemical conversion treatment in which a chromium compound, a phosphoric acid compound, and an amination phenol polymer are combined are preferable. Among the chromium compounds, a chromic acid compound is preferable.

Specific examples of the acid-resistant film include those containing at least one of phosphate, chromate, fluoride, and triazinethiol. Further, 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-based film, a chromate-based film, a fluoride-based film, and a triazinethiol compound film. The acid-resistant film may be one of these or a combination of a plurality of types. Further, the acid-resistant film is a treatment liquid consisting of a mixture of a metal phosphate and an aqueous synthetic resin after degreasing the chemical conversion-treated surface of the aluminum alloy foil, or a mixture of a non-metal phosphate and an aqueous synthetic resin. It may be formed of a treatment liquid made of.

The composition of the acid-resistant film can be analyzed by using, for example, a time-of-flight secondary ion mass spectrometry method. Analysis of the composition of the acid resistant film using time-of-flight secondary ion mass spectrometry detects, for example, peaks derived from at least one of Ce ⁺ and Cr ⁺ .

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. It was confirmed by X-ray photoelectron spectroscopy that the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contained 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-sealing resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is placed in an electric furnace, and the organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, X-ray photoelectron spectroscopy on the surface of the aluminum alloy foil is used to confirm that these elements are contained.

The amount of the acid-resistant film 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 chromate treatment, the chromium compound is chromium per 1 m ² of the surface of the barrier layer 3. Conversion is about 0.5 to 50 mg, preferably about 1.0 to 40 mg, phosphorus compound is about 0.5 to 50 mg, preferably about 1.0 to 40 mg, and aminated phenol polymer is 1.0. 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 force of the film and the adhesion to the barrier layer 3 and the heat-sealed resin layer. The degree, more preferably 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-dispersed 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, or the like, and then the temperature of the barrier layer is 70. It is carried out by heating to about 200 ° C. Further, before the chemical conversion treatment is applied to the barrier layer, the barrier layer may be subjected to a degreasing treatment by an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like in advance. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the barrier layer.

[Heat-fused resin layer 4]
In the battery packaging material of the present invention, the heat-sealing resin layer 4 corresponds to the innermost layer side, and is a layer in which the heat-sealing resin layers are heat-sealed to seal the battery element when the battery is assembled. ..

In the packaging material for batteries of the present invention, when the heat-sealing resin layer 4 is a single layer, the melting peak temperature of the heat-sealing resin layer 4 is 130 ° C. or lower, and the heat-sealing is performed. When the sex resin layer 4 is a plurality of layers, the melting peak temperature of the layer (that is, the innermost layer) constituting the surface opposite to the barrier layer of the heat-sealing resin layer 4 is 130 ° C. It is characterized by the following. That is, in the battery packaging material of the present invention, when the heat-sealing resin layer 4 is composed of a single layer, the heat of the single layer constituting the surface opposite to the barrier layer 3 The melting peak temperature of the fused resin layer 4 is 130 ° C. or lower. When the heat-sealing resin layer 4 is composed of a plurality of layers, the heat-bonding resin layer 4 of the plurality of layers constituting at least the surface opposite to the barrier layer 3 is formed. The melting peak temperature of the resin is 130 ° C. or lower.

The barrier of the heat-sealing resin layer 4 from the viewpoint of suppressing the expansion of the battery and leading to gentle opening even when the battery in which the resin forming the separator is mixed with an inorganic material is exposed to a high temperature environment. 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-sealing resin layer" is the heat-sealing resin layer. When is a single layer, it means a heat-sealing resin layer which is a single layer, and when the heat-sealing resin layer is a multi-layer, what is the barrier layer of the heat-sealing resin layer? The melting peak temperature of the innermost layer constituting the opposite surface is preferably about 125 ° C. or lower, more preferably about 120 ° C. or lower, still more preferably about 118 ° C. or lower. The lower limit is preferably about 90 ° C. or higher. The preferred range of the melting peak temperature of the layer constituting the surface of the heat-sealing resin layer 4 opposite to the barrier layer 3 is about 90 to 130 ° C, about 90 to 125 ° C, and about 90 to 120 ° C. , 90 to 118 ° C. When the packaging material for a battery of the present invention is used for a battery that is opened at a set temperature of 90 ° C. or higher and 100 ° C. or lower, the surface of the heat-sealing resin layer 4 opposite to the barrier layer 3 is formed. A preferable range of the melting peak temperature of the layer is about 90 to 99 ° C. Further, 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 110 ° C. or lower, the surface of the heat-sealing resin layer 4 on the opposite side of the barrier layer 3 A preferable range of the melting peak temperature of the layer constituting the above is about 100 to 109 ° C. Further, 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 lower, the surface of the heat-sealing resin layer 4 on the opposite side of the barrier layer 3 A preferable range of the melting peak temperature of the layer constituting the above is about 110 to 120 ° C.

When the heat-sealing resin layer 4 is composed of a plurality of 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 lower, more preferably about 165 ° C. or lower. Further, the temperature is more preferably about 163 ° C. or lower, particularly preferably 160 ° C. or lower, and the lower limit is preferably about 100 ° C. or higher. The preferred range of the melting peak temperature of the layer located on the barrier layer 3 side is about 100 to 170 ° C, about 100 to 165 ° C, about 100 to 163 ° C, and about 100 to 160 ° C.

The resin component used in the heat-bondable resin layer 4 can be heat-fused and is not particularly limited as long as the melting peak temperature is satisfied. For example, polyolefins, cyclic polyolefins, acid-modified polyolefins, etc. Examples thereof include acid-modified cyclic polyolefins. That is, the resin constituting the heat-sealing resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The fact that the resin constituting the heat-sealing resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited. For example, when maleic anhydride-modified polyolefin is measured by infrared spectroscopy, peaks derived from maleic anhydride are detected in the vicinity of wave number 1760 cm ^-1 and wave number 1780 cm ^-1 . However, if the degree of acid denaturation is low, the peak may become 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, a block copolymer of polypropylene (for example, a block copolymer of propylene and ethylene), and polypropylene. Polypropylene such as random copolymers of polyethylene (eg, random copolymers of propylene and ethylene); polyethylene-butene-propylene tarpolymers 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 which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like. Can be mentioned. Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene and the like. Among these polyolefins, cyclic alkene is preferable, and norbornene is more preferable.

The acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing the polyolefin with an acid component such as a carboxylic acid. Examples of the acid component used for the 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 means that a part of the monomer constituting the cyclic polyolefin is copolymerized in place of α, β-unsaturated carboxylic acid or its anhydride, or α, β-with respect to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The same applies to the cyclic polyolefin that is modified with carboxylic acid. The acid component used for the modification is the same as that used for the modification of the polyolefin.

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

The heat-bondable resin layer 4 may be formed of one type of resin component alone, or may be formed of a blended polymer in which two or more types of resin components are combined. As described above, the heat-sealing resin layer 4 may be composed of only one layer, but may be composed of two or more layers with the same or different resin components.

The barrier of the heat-sealing resin layer 4 from the viewpoint of suppressing the expansion of the battery and leading to gentle opening even when the battery in which the inorganic material is mixed with the resin forming the separator is exposed to a high temperature environment. The layer constituting the surface opposite to the layer 3 is preferably made of polypropylene. When the heat-sealing resin layer is composed of a plurality of layers, the layer located on the barrier layer 3 side of the fusion-bonding resin layer 4 is preferably made of 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 fused 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 the lubricant is attached to the surface of the heat-sealing resin layer. The lubricant is not particularly limited, but an amide-based lubricant is preferable. Specific examples of the amide-based lubricant include the above-mentioned ones.

When the lubricant is present on the surface of the heat-sealing resin layer, the abundance thereof 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%. About 4 to 15 mg / m ² and more preferably about 5 to 14 mg / m ² are mentioned.

Further, the thickness of the layer constituting the surface of the heat-sealing resin layer 4 opposite to the barrier layer 3 (that is, when the heat-sealing resin layer is a single layer, the heat is a single layer). It is the thickness of the heat-sealing resin layer, and when the heat-sealing resin layer is a multi-layer, the thickness of the innermost layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer. ) Is not particularly limited as long as it functions as a heat-sealing resin layer, but even when a battery in which an inorganic material is mixed with the resin forming the 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, still more preferably about 50 μm or less, and the lower limit is preferably about 10 μm or more. More preferably, it is about 15 μm or more, and even more preferably about 20 μm or more. The preferred range of the thickness of the layer constituting the surface of the heat-sealing resin layer 4 opposite to the barrier layer 3 is about 10 to 60 μm, about 10 to 55 μm, about 10 to 50 μm, and 15 to. Examples thereof include about 60 μm, about 15 to 55 μm, about 15 to 50 μm, about 20 to 60 μm, about 20 to 55 μm, and about 20 to 50 μm.

Further, when the heat-sealing resin layer is composed of a plurality of layers, the thickness of the layer located on the barrier layer 3 side of the heat-sealing resin layer 4 exhibits the function as the heat-sealing resin layer. However, there is no particular limitation, but as an upper limit from the viewpoint of suppressing the expansion of the battery and leading to gentle opening even when the battery in which the inorganic material is mixed with the resin forming the separator is exposed to a high temperature environment. Is preferably about 60 μm or less, more preferably about 55 μm or less, still more 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. Be done. The preferred range of the thickness of the layer located on the barrier layer 3 side of the heat-sealing resin layer 4 is about 10 to 60 μm, about 10 to 55 μm, about 10 to 50 μm, about 15 to 60 μm, and about 15 to 55 μm. , About 15 to 50 μm, about 20 to 60 μm, about 20 to 55 μm, and about 20 to 50 μm.

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

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

The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the heat-sealing resin layer 4. As the resin used for forming the adhesive layer 5, the same adhesive as the adhesive exemplified in the adhesive layer 2 can be used in terms of the adhesive mechanism, the type of adhesive component, and the like. Further, as the resin used for forming the adhesive layer 5, polyolefin-based resins such as the polyolefins exemplified in the above-mentioned heat-sealing resin layer 4, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins can also be used. .. From the viewpoint of excellent adhesion between the barrier layer 3 and the heat-bondable 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 contain a polyolefin skeleton, and preferably contains 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, or the like, and the analysis method is not particularly limited. For example, when maleic anhydride-modified polyolefin is measured by infrared spectroscopy, peaks derived from maleic anhydride are detected in the vicinity of wave number 1760 cm ^-1 and wave number 1780 cm ^-1 . However, if the degree of acid denaturation is low, the peak may become small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

Further, from the viewpoint of making the packaging material for batteries excellent in shape stability after molding while reducing the thickness of the packaging material for batteries, the adhesive layer 5 is a curing of a resin composition containing an acid-modified polyolefin and a curing agent. It may be a thing. As the acid-modified polyolefin, preferably, the same examples as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat-sealing resin layer 4 can be exemplified.

The curing agent is not particularly limited as long as it cures the acid-modified polyolefin. Examples of the curing agent include an epoxy-based curing agent, a polyfunctional isocyanate-based curing agent, a carbodiimide-based curing agent, an oxazoline-based curing agent, and the like.

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

The polyfunctional isocyanate-based 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), and those obtained by polymerizing or nurate these. Examples thereof include a mixture and a copolymer with another polymer.

The carbodiimide-based 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-based curing agent, a polycarbodiimide compound having at least two or more 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 the Epocross series manufactured by Nippon Shokubai Co., Ltd.

The curing agent may be composed of two or more kinds of compounds from the viewpoint of enhancing the adhesion between the barrier layer 3 by the adhesive layer 5 and the heat-sealing resin layer 4.

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. It is more preferably 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 functions as an adhesive layer, but when the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 1 to 10 μm, more preferably 1 to 1. About 5 μm can be mentioned. Further, when the resin exemplified in the heat-sealing resin layer 4 is used, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. Further, in the case of a cured product of the acid-modified polyolefin and the curing agent, it is preferably 30 μm or less, more preferably about 0.1 to 20 μm, 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 packaging material for a battery of the present invention, the outer side of the base material layer 1 (barrier layer of the base material layer 1) is required for the purpose of improving designability, electrolytic solution resistance, scratch resistance, moldability, and the like. A surface coating layer may be provided on the side opposite to 3), if necessary.

The surface coating layer can be formed of, for example, polyvinylidene chloride, a polyester resin, a urethane resin, an acrylic resin, an 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 forming the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, an additive may be added to the 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. The shape of the additive is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape. As additives, specifically, talc, silica, graphite, kaolin, montmoriloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodium 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 Examples thereof include melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel. These additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. Further, the additive may be subjected to various surface treatments such as an insulation treatment and a high dispersibility treatment on the surface.

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

The thickness of the surface coating layer is not particularly limited as long as it exhibits the above-mentioned function as the surface coating layer, and examples thereof include about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. 3. Method for Manufacturing Battery Packaging Material The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate in which each layer having a predetermined composition is laminated can be obtained. That is, in the method for producing a packaging material for a battery 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 housed in a package formed of the packaging material for the battery. A method for manufacturing a packaging material for a battery for use in a battery, wherein the battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower, and is at least a base material layer, a barrier layer, and heat fusion. A step of laminating the sex resin layers in this order is provided, and when the heat-sealing resin layer is a single layer as the heat-sealing resin layer, the melting peak temperature of the heat-sealing resin layer is set. , 130 ° C. or lower, and when the heat-sealing resin layer is a multi-layer, the melting peak of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer. A method using a material having a temperature of 130 ° C. or lower can be mentioned.

An example of the method for manufacturing the packaging material for a battery 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, may be referred to as “laminate A”) is formed. Specifically, the laminated body A is formed by applying an adhesive used for forming the adhesive layer 2 on the base material layer 1 or, if necessary, on the barrier layer 3 whose surface has been chemically converted, by a gravure coating method. It can be carried out by a dry laminating method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a roll coating method.

Next, the adhesive layer 5 and the heat-sealing resin layer 4 are laminated on the barrier layer 3 of the laminated body A in this order. For example, (1) a method of laminating the adhesive layer 5 and the heat-sealing resin layer 4 on the barrier layer 3 of the laminated body A by co-extruding (co-extruded laminating method), (2) separately, the adhesive layer 5 A method of forming a laminated body in which the heat-sealing resin layer 4 is laminated and laminating this on the barrier layer 3 of the laminated body A by a thermal laminating method. (3) Adhesive on the barrier layer 3 of the laminated body A. An adhesive for forming the layer 5 is laminated by an extrusion method, solution coating, drying at a high temperature, baking, or the like, and a heat-sealing resin layer 4 is previously formed into a sheet on the adhesive layer 5. A method of laminating by a thermal laminating method, (4) Adhesion while pouring a melted adhesive layer 5 between the barrier layer 3 of the laminated body A and the heat-bondable resin layer 4 formed in the form of a sheet in advance. Examples thereof include a method of laminating the laminate A and the heat-sealing resin layer 4 via the layer 5 (sandwich laminating method).

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 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 material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 is not particularly limited. For example, after forming the surface coating layer 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 provided as needed / the base material layer 1 / the adhesive layer provided as needed 2 / the barrier layer 3 whose surface is chemically treated as needed / as needed. A laminated body composed of the provided adhesive layer 5 / heat-sealing resin layer 4 is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 or the adhesive layer 5, a hot roll contact type or a hot air type is further formed. , Near or far infrared type, etc. may be subjected to heat treatment.

In the packaging material for batteries of the present invention, each layer constituting the laminated body improves or stabilizes film forming property, laminating process, suitability for secondary processing (pouching, embossing) of the final product, etc., as necessary. Therefore, surface activation treatments such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

4. Uses of Battery Packaging Material The battery packaging material of the present invention is used as a packaging material for sealing and accommodating a battery element including at least a positive electrode, a negative electrode, an electrolyte, and a separator containing an inorganic material. To. Further, as described above, the packaging material for a battery of the present invention is characterized in that it is used for a battery containing a resin and an inorganic material in the separator. The battery packaging material of the present invention is particularly preferably used for small batteries used in mobile devices such as mobile phones and laptop computers.

Specifically, a battery element provided with at least a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material is provided with a metal terminal connected to each of the positive electrode and the negative electrode in the battery packaging material of the present invention. With the battery element protruding outward, the peripheral edge of the battery element is covered so that a flange portion (a region where the heat-sealing resin layers come into contact with each other) can be formed, and the heat-sealing resin layers of the flange portion are heated. By sealing and sealing, a battery using a battery packaging material is provided. When the battery element is housed using the battery packaging material of the present invention, the sealant portion of the battery packaging material of the present invention is used so as to be inside (the 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 the secondary battery to which the packaging material for a battery of the present invention is applied is not particularly limited, and 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 thereof include iron storage batteries, nickel / zinc storage batteries, silver oxide / zinc storage batteries, metal air batteries, polyvalent cation batteries, capacitors, and capacitors. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of 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.

<Manufacturing of packaging materials for batteries>
Example 1-5, Comparative Example 1-5
Battery packaging materials having the laminated structure shown in Table 1 were prepared. As shown in Table 1, in the laminated structure of the battery packaging material, a coating layer, a base material layer, an adhesive layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer are laminated in this order from the left side of Table 1. There is. In addition, items without a layer shown in Table 1 are indicated by "-". For example, in Table 1, in Example 1, the heat-sealing 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 written as "-". Similarly, in Examples 4-7 and Comparative Examples 1, 4 and 5, the configurations of the heat-sealing resin layer are shown in Table 1. In Examples 1, 4-7 and Comparative Examples 1, 4 and 5, the heat-sealing resin layer described in the column of "barrier layer side" in Table 1 is a single layer, so that the single layer is used. It is 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. Further, in Examples 1 and 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. Further, in the adhesive layer located between the barrier layer and the heat-sealing resin layer, "PPA" means maleic anhydride-modified polypropylene and "LM" means a two-component curable adhesive. The number after the material means the thickness of the layer.

Further, in Table 1, the heat-sealing 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. Further, "EC" means that it is formed by an extraction coating (resin melt extrusion laminating process).

First, an aluminum foil having been subjected to chemical conversion treatment on both sides was laminated on the surface of one side of the base material layer as a barrier layer by a dry laminating method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil to form an adhesive layer (thickness 3 μm) on the barrier layer. Next, after laminating the adhesive layer and the base material layer on the barrier layer, an aging treatment was carried out to prepare a laminated body of the base material layer / adhesive layer / barrier layer. In the chemical conversion treatment of the aluminum foil used as the barrier layer, a treatment liquid consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid was roll-coated so that the coating amount of chromium was 10 mg / m ² (dry weight). This was done by applying and baking on both sides of the aluminum foil by the method. Next, the adhesive layer and the heat-sealing resin layer were laminated on the barrier layer side of the laminated body to obtain a battery packaging material having the laminated structure shown in Table 1. The melting peak temperature (melting point) of each layer constituting the adhesive layer and the heat-sealing resin layer is as shown in Table 1, respectively.

<Opening test>
The packaging materials for batteries obtained above were cut to prepare samples having a short side of 90 mm and a long side of 150 mm, respectively. Next, each sample is molded to 3 mm at a pressing pressure of 0.13 MPa using a molding die (female mold) having a diameter of 32 mm on the short side and 55 mm on the long side and a molding die (male mold) corresponding to the molding die. Cold forming was performed at a depth to form a recess in the central portion. At this time, the clearance between the female type and the male type was set to 0.3 mm. Further, the sample was molded so that the short side and the long side of the molding die coincide with each other. Next, the molded sample is folded back with the heat-sealing resin layers facing each other at the folding position P shown in FIG. 5, and the three peripheral edges 10a (FIG. 4 (a)) in which the heat-sealing resin layers overlap each other. ) Was heat-sealed (175 ° C., 3 seconds, pressure 1.4 MPa). At this time, a separator (thickness 3 mm) having a short side of 30 mm and a long side of 52 mm and 0.5 g of water as a virtual electrolytic solution 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 in 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. Was used.

Next, the peripheral edge portion 10a was cut so that the width of the portion where the heat-sealing resin layers were heat-sealed to each other was 3 mm, and the opening test battery 10 was obtained. Next, as shown in FIG. 4A, the opening test battery 10 is placed in the space between the two stainless steel plates 20, and the distance w between the two stainless steel plates 21 is 7.0 mm. It was adjusted with the fixing spacer 21 as described above. Next, in this state, the mixture was placed in an oven (DNF401 type manufactured by Yamato Scientific Co., Ltd.) at a temperature of 25 ° C. and 1 atm, and the temperature was raised to 120 ° C. at a heating rate of 10 ° C./10 minutes. As the temperature inside the oven rises, the internal pressure of the opening test battery 10 rises and swells, resulting in the state shown in FIG. 4 (b). Table 1 shows the expansion, the temperature at the time of opening, and the state of opening when the environmental temperature in the oven was kept at 120 ° C. for 2 hours. The temperature is a set value in the test oven. The reason why the battery is held by using the stainless steel plate and the fixing spacer is that the battery is usually fixed by a case or the like. In addition, the reason why the opening test was conducted by using water as a virtual electrolytic solution and sealing the water with a battery packaging material is that the safety of the opening test is ensured and even if water is used instead of the electrolytic solution, the opening test is performed. This is because the opening performance can be evaluated.

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

On the other hand, the opening test batteries using the battery packaging materials of Comparative Examples 1 to 5 expanded significantly by the time they reached 120 ° C. and did not open even after 2 hours.

1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-sealing resin layer 5 Adhesive layer 10 Opening test battery 10a Edge 20 Stainless steel plate 21 Fixing spacer M Molded part P Folded position

Claims (11)

A battery packaging material for using a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator in a battery housed in a package formed of the battery packaging material.
The separator contains a resin and an inorganic material, and the separator contains a resin and an inorganic material.
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
The battery packaging material is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
The heat-sealing resin layer is composed of a single layer or two layers.
When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower.
When the heat-sealing resin layer has two layers , the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130 ° C. or lower. Packaging material for batteries. The packaging material for a battery according to claim 1, wherein the melting peak temperature of the resin constituting the separator is 130 ° C. or higher. When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is lower than the melting peak temperature of the resin constituting the separator.
When the heat-sealing resin layer is two layers , the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is the resin constituting the separator. The packaging material for a battery according to claim 1 or 2, which is lower than the melting peak temperature of the above. The packaging material for a battery according to any one of claims 1 to 3, wherein an adhesive layer is provided between the heat-sealing 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 that is opened at a predetermined set temperature of 90 ° C. or higher and 120 ° C. or lower. A battery in which 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 housed in a package formed of a battery packaging material.
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
The battery packaging material is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
The heat-sealing resin layer is composed of a single layer or two layers.
When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower.
When the heat-sealing resin layer has two layers , the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is 130 ° C. or lower. battery. The battery according to claim 6, wherein the melting peak temperature of the resin constituting the separator is 130 ° C. or higher. When the heat-sealing resin layer is a single layer, the melting peak temperature of the heat-sealing resin layer is lower than the melting peak temperature of the resin constituting the separator.
When the heat-sealing resin layer is two layers , the melting peak temperature of the layer constituting the surface opposite to the barrier layer of the heat-sealing resin layer is the resin constituting the separator. The battery according to claim 6 or 7, which is lower than the melting peak temperature of the above. The battery according to any one of claims 6 to 8, wherein an adhesive layer is provided between the heat-sealing resin layer and the barrier layer. The battery according to any one of claims 6 to 9, wherein the battery is a battery that is opened at a predetermined set temperature of 90 ° C. or higher and 120 ° C. or lower. A method for manufacturing a battery packaging material for using a battery element having a positive electrode, a negative electrode, an electrolyte, and a separator containing a resin and an inorganic material for a battery housed in a package formed of the battery packaging material. There,
The battery is a battery that is opened at a predetermined set temperature of 120 ° C. or lower.
At least, it includes a step of laminating a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
The heat-sealing resin layer is composed of a single layer or two layers.
When the heat-sealing resin layer is a single layer as the heat-sealing resin layer, the melting peak temperature of the heat-sealing resin layer is 130 ° C. or lower, and the heat-sealing is also carried out. When there are two sex resin layers, a battery having a melting peak temperature of 130 ° C. or lower, which constitutes a surface opposite to the barrier layer of the heat-sealing resin layer, is used. Manufacturing method of packaging materials for.

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