JP2015050111A - Packaging material for batteries - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate type packaging material for batteries which is arranged so that it can keep a hermetic condition while being partially delaminated until the arrival at a particular temperature, and it can be rapidly and calmly opened on the arrival at the temperature, and which enables the suppression of excessive expansion of a packaging material for batteries and the runaway of a battery reaction.SOLUTION: A packaging material for batteries comprises a laminate having at least, a base material layer 1, a metal layer 3 and a sealant layer 4 in this order. The sealant layer has a first sealant layer 4a including an acid-modified polyolefin, and a second sealant layer 4b in turn. The sealant layer is arranged so that the first sealant layer is located on the side of the metal layer, and the second sealant layer is located to make an innermost layer. The first sealant layer includes at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer and a terpene phenol resin.

Description

  The present invention relates to a battery packaging material that can ensure safety even when the pressure or temperature in the battery continuously increases. More specifically, when the battery is heated, the present invention does not open until the battery reaches a certain temperature, and can maintain the battery element in a sealed state. The present invention also relates to a battery packaging material that can be gently opened to suppress excessive expansion of the battery packaging material and runaway battery reaction.

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

  On the other hand, depending on the type of electrolyte, the battery may generate a combustible gas and the pressure may increase. For example, when the battery is exposed to a high temperature, the organic solvent used in the electrolytic solution may be decomposed to generate a combustible gas and cause an increase in pressure. In addition, the battery may continuously increase in temperature due to charging due to overvoltage or discharging due to excessive current, causing battery reaction to runaway.

  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.

  Conventionally, as a packaging material for a battery that can suppress the tearing of the heat seal part and the break before the heat seal part even when the pressure in the battery rises continuously, the sealant layer or adjacent thereto It has been reported that one of the adhesive resin layers has a cleavage inducing portion in which the stress at the time of cleavage is smaller than the stress at the time of cleavage of the fused surface between the sealant layers (see Patent Document 2). However, Patent Document 2 is not designed to be opened gently when the pressure or temperature in the battery has been continuously increased. In fact, in Patent Document 2, when a strong stress is applied, delamination in which cleavage proceeds between layers having adhesiveness, or cohesive failure in which cracks progress in an adhesive layer occurs. Designed to be If the battery is opened by delamination or cohesive failure when the pressure or temperature in the battery rises, there is a concern that the risk of ignition, explosion, or the like may increase due to a sudden ejection of combustible gas.

  For this reason, the battery packaging material does not rupture until it reaches a certain set temperature in order to ensure safety when the pressure or temperature rises continuously in the battery. By maintaining the closed state, the gas in the battery packaging material is gradually released by gently opening when the set temperature is reached, while suppressing ignition etc. due to the sudden ejection of combustible gas. It is required to design.

  In addition, because the temperature that should be induced to open from the maintenance of the battery packaging material varies depending on the type and use of the battery, the battery packaging material is designed to have a sealing property and an opening property depending on the battery to be applied. There is a need to. For example, if there is a battery that is required to be induced from the sealed state to the unsealed state when it reaches 100 ° C., there is a battery that is required to be induced from the sealed state to the unsealed state when it reaches 150 ° C. Therefore, in the prior art, it is currently necessary to design the packaging material for the battery individually according to the temperature that should be guided to the opening from the maintenance of the seal, maintaining the sealed state at a predetermined set temperature Regarding the battery packaging materials that are induced to open from the beginning, the common design guidelines that do not depend on the difference in the set temperature are not clarified.

JP 2001-202927 A JP 2012-203982 A

  An object of this invention is to provide the battery packaging material which can ensure safety | security even when the raise in the pressure in a battery and temperature progresses continuously. More specifically, the present invention can maintain the battery element in a sealed state without being cleaved until reaching a certain temperature, and can quickly and gently open the battery element when the temperature is reached. It aims at providing the packaging material for batteries which can suppress the excessive expansion | swelling of the packaging material for batteries, and the runaway of a battery reaction.

  The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors have at least a base material layer, a metal layer, and a laminate having a sealant layer in this order, and the sealant layer contains acid-modified polyolefin. 1 sealant layer and second sealant layer in order, and in the sealant layer, the first sealant layer is positioned on the metal layer side, and the second sealant layer is positioned on the innermost layer. The battery packaging material in which the sealant layer includes at least one selected from the group consisting of ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin is used when various batteries are used. At least a portion between the metal layer and the outer surface (innermost layer side surface) of the sealant layer until reaching a certain temperature determined according to the heat resistance required for The battery element can be kept sealed by the sealant layer, but when it reaches the temperature (opening temperature), it quickly (within at least 30 minutes), pinholes etc. in the sealant layer of the peeled part It was found that it can be opened gently by causing a fine cleavage of. Furthermore, it has also been found that such a battery packaging material has a high sealing strength when the sealant layers are heat-sealed, and also has a high laminate strength between the metal layer and the sealant layer. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the invention of the aspect hung up below.
Item 1. It consists of a laminate having at least a base material layer, a metal layer, and a sealant layer in this order,
The sealant layer has a first sealant layer containing an acid-modified polyolefin and a second sealant layer in order,
In the sealant layer, the first sealant layer is disposed on the metal layer side, and the second sealant layer is disposed on the innermost layer,
The battery packaging material, wherein the first sealant layer includes at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin.
Item 2. Item 1. The total content of at least one selected from the group consisting of the ethylene vinyl acetate copolymer, the acrylic resin, the styrene polymer, and the terpene phenol resin in the sealant layer is 5% by mass or more. The packaging material for a battery as described.
Item 3. The melting point T _m2 of the second sealant layer and the melting point T _m1 of the first sealant layer have the following relationship:
T _m2 ≧ T _m1
Item 3. The battery packaging material according to Item 1 or 2, wherein
Item 4. The melting point T _m1 of the first sealant layer is 100 to 160 ° C., the softening point T _s1 of the first sealant layer is 60 to 150 ° C., a battery packaging material according to any one of claim 1 to 3.
Item 5. The melting point T _m2 of the second sealant layer is 100 to 160 ° C., the softening point T _s2 of the second sealant layer is 60 to 150 ° C., a battery packaging material according to any one of claim 1 to 4.
Item 6. When the temperature of the battery is raised, peeling occurs at least in part between the metal layer and the outer surface of the sealant layer until the set temperature is reached, but the packaging material is not opened. Item 6. The battery packaging material according to any one of Items 1 to 5, which is a battery packaging material used for a battery that is set so that the packaging material is opened to prevent battery ignition and reaction runaway.
Item 7. Item 7. The battery packaging material according to any one of Items 1 to 6, wherein the acidic polyolefin contained in the first sealant layer contains at least propylene as a constituent monomer.
Item 8. Item 8. The battery packaging material according to any one of Items 1 to 7, wherein the second sealant layer contains polyolefin.
Item 9. Item 9. The battery packaging material according to Item 8, wherein the polyolefin contained in the second sealant layer contains at least propylene as a constituent monomer.
Item 10. Item 10. The battery packaging material according to any one of Items 1 to 9, wherein the first sealant layer has a thickness of 5 to 40 μm, and the second sealant layer has a thickness of 5 to 40 μm.
Item 11. Item 11. The battery packaging material according to any one of Items 1 to 10, wherein the metal layer is an aluminum foil.
Item 12. Item 12. The battery packaging material according to any one of Items 1 to 11, further comprising an adhesive layer between the base material layer and the metal layer.

  The battery packaging material of the present invention comprises a laminate having at least a base material layer, a metal layer, and a sealant layer in this order. The sealant layer includes a first sealant layer containing an acid-modified polyolefin, and a second sealant layer. In the sealant layer, the first sealant layer is positioned on the metal layer side, and the second sealant layer is positioned on the innermost layer. The first sealant layer is an ethylene vinyl acetate copolymer. And at least one selected from the group consisting of acrylic resins, styrene polymers, and terpene phenol resins. The battery packaging material of the present invention adopts such a specific configuration, and when the temperature is raised to a predetermined set temperature T ° C., until the temperature reaches T ° C., the outer side of the metal layer and the sealant layer. At least a portion between the surface (the innermost layer side surface) is peeled off, and the battery element can be kept sealed. In addition, the battery packaging material of the present invention is rapidly opened after reaching the set temperature T ° C., and a minute tear such as a pinhole is generated in the peeled portion of the sealant layer so as to be opened in a gentle condition. Can do. As described above, the battery packaging material of the present invention does not cleave until reaching a predetermined set temperature, can maintain the battery element in a sealed state, and quickly and gently when the set temperature is reached. Therefore, even if the pressure or temperature in the battery continues to rise, excessive expansion of the battery packaging material and runaway battery reaction can be suppressed, and safety is ensured. Furthermore, the battery packaging material of the present invention has a high sealing strength when the sealant layers are heat-sealed, and also has a high laminate strength between the metal layer and the sealant layer.

It is a schematic sectional drawing of the packaging material for batteries of this invention. It is a schematic sectional drawing of the packaging material for batteries of this invention. A state (A) in which a sealed space is formed by heat-sealing two battery packaging materials of the present invention (A), a state in which peeling is caused by raising the temperature (B), and an opening temperature is reached, resulting in opening. About state (C), it is schematic sectional drawing of the one side surface (The left end is heat-sealed and the right side part is abbreviate | omitted). A state (A) in which a sealed space is formed by heat-sealing two battery packaging materials of the present invention (A), a state in which peeling is caused by raising the temperature (B), and an opening temperature is reached, resulting in opening. About state (C), it is schematic sectional drawing of the one side surface (The left end is heat-sealed and the right side part is abbreviate | omitted). A state (A) in which a sealed space is formed by heat-sealing two battery packaging materials of the present invention (A), a state in which peeling is caused by raising the temperature (B), and an opening temperature is reached, resulting in opening. About state (C), it is schematic sectional drawing of the one side surface (The left end is heat-sealed and the right side part is abbreviate | omitted). A state (A) in which a sealed space is formed by heat-sealing two battery packaging materials of the present invention (A), a state in which peeling is caused by raising the temperature (B), and an opening temperature is reached, resulting in opening. About state (C), it is schematic sectional drawing of the one side surface (The left end is heat-sealed and the right side part is abbreviate | omitted). A schematic cross-sectional view of one side showing the cleavage state that occurs when two conventional battery packaging materials are heat sealed to form a sealed space and heated to a certain temperature (the left end is heat sealed) The right part is omitted).

A. Battery packaging material The battery packaging material of the present invention comprises a laminate having at least a base material layer, a metal layer, and a sealant layer in this order, and the sealant layer includes a first sealant layer containing an acid-modified polyolefin, Two sealant layers in order, and in the sealant layer, the first sealant layer is disposed on the metal layer side, and the second sealant layer is disposed on the innermost layer. It contains at least one selected from the group consisting of vinyl copolymers, acrylic resins, styrene polymers, and terpene phenol resins. Hereinafter, the battery packaging material of the present invention will be described in detail.

1. As shown in FIG. 1, the battery packaging material is composed of a laminate having at least a base material layer 1, a metal layer 3, and a sealant layer 4 in this order. The sealant layer 4 has a first sealant layer 4a and a second sealant layer 4b, and is arranged such that the first sealant layer 4a is located on the metal layer 3 side and the second sealant layer 4b is located on the innermost layer. It has a laminated structure. That is, the battery packaging material of the present invention comprises a laminate having the base layer 1, the metal layer 3, the first sealant layer 4a, and the second sealant layer 4b in this order, and the base layer 1 is the outermost layer. The second sealant layer 4b is the innermost layer. When assembling the battery, the second sealant layers 4b located on the periphery of the battery element are brought into contact with each other and thermally welded to seal the battery element, thereby sealing the battery element. As shown in FIG. 1, the battery packaging material of the present invention may have an adhesive layer 2 between a base material layer 1 and a metal layer 3. Moreover, the battery packaging material of the present invention may have an adhesive layer 5 between the metal layer 3 and the sealant layer 4 as shown in FIG. Further, although not shown, the sealant layer 4 includes layers such as a third sealant layer 4c and a fourth sealant layer 4d in order from the first sealant layer 4a side between the first sealant layer 4a and the second sealant layer 4b. Further, it may be composed of three or more layers.

2. Unpacking mechanism of battery packaging material The battery packaging material of the present invention has a certain temperature (for example, any temperature in the range of 100 to 160 ° C.) determined according to the heat resistance required for various batteries. It has a sealing property until reaching the temperature and a quick and gentle opening property after reaching the temperature. The example of the opening mechanism of the packaging material for batteries of this invention is demonstrated using FIGS. 3 and 4 illustrate the case where the battery packaging material of the present invention has the adhesive layer 2, and in FIGS. 5 and 6, the battery packaging material of the present invention is the metal layer 3. The case where the adhesive layer 5 is provided between the sealant layer 4 is described. FIGS. 3 to 6 show cross-sectional views of one side when a battery element is sealed in two battery packaging materials of the present invention. In A of FIGS. 3 to 6, the edges of the sealant layers 4 of the two battery packaging materials are heat-sealed to form a sealed space. Although the battery element is accommodated in the sealed space, the battery element is omitted in FIGS. The battery packaging material of the present invention has at least one of the unsealing mechanisms shown in FIGS. 3 to 6 to provide a hermetic seal until reaching the above certain temperature and a quick and gentle unsealing property after reaching the temperature. It has. In FIG. 3A, (A-1) shows a cross-sectional view when two battery packaging materials are molded together, and (A-2) shows one battery packaging material. Sectional drawing at the time of forming only is shown. Hereinafter, in FIG. 3 to FIG. 6, the opening mechanism of the battery packaging material of the present invention will be described using a cross-sectional view in which two battery packaging materials are molded. Even when it is molded, it is opened by the same mechanism.

  First, in the opening mechanism shown in FIG. 3, when the temperature is raised from the state of FIG. 3A, as shown in FIG. 3B, at least a part of the interface between the metal layer 3 and the sealant layer 4 is peeled off (interface). Peeling). At this time, the sealant layer 4 is preferably in a bag shape (inner bag) and the battery element is kept sealed. When the temperature reaches a certain temperature (opening temperature), the state quickly shifts to the state shown in FIG. 3C, and a fine region such as a pinhole is formed in the region (preferably the inner bag) of the sealant layer 4 peeled from the metal layer 3. Rupture (indicated by reference numeral 10 in FIG. 3) occurs, and the bag is opened under mild conditions.

  Further, in the unsealing mechanism shown in FIG. 4, when the temperature is raised from the state of A in FIG. 4, as shown in B of FIG. 4, cohesive peeling occurs at least in part inside the sealant layer 4. At this time, it is preferable that the coherent and peeled portion of the sealant layer 4 is formed in a bag shape (inner bag) to keep the battery element sealed. When the temperature reaches a certain temperature (opening temperature), the state rapidly shifts to the state shown in FIG. 4C, and a fine tear such as a pinhole (in the inner bag) of the sealant layer 4 (preferably the inner bag) ( (Indicated by reference numeral 10 in FIG. 4) occurs, and the unsealed state is obtained under mild conditions.

  In the unsealing mechanism shown in FIG. 5, when the temperature is raised from the state of FIG. 5A, as shown in FIG. 5B, at least a part of the interface between the adhesive layer 5 and the sealant layer 4 is peeled off (interface). Peeling). At this time, the sealant layer 4 is preferably in a bag shape (inner bag) and the battery element is kept sealed. Then, when a certain temperature (opening temperature) is reached, the state quickly shifts to the state shown in FIG. 5C, and fine cracks such as pinholes (preferably inner bags) of the sealant layer 4 (preferably inner bags) ( 5) (indicated by reference numeral 10 in FIG. 5) occurs, and the unsealed state is obtained under mild conditions.

  Further, in the unsealing mechanism shown in FIG. 6, when the temperature is raised from the state of A in FIG. 6, as shown in B of FIG. 6, cohesive peeling occurs in at least a part of the sealant layer 4. At this time, it is preferable that the region where the sealant layer 4 is agglomerated and peeled is formed in a bag shape (inner bag) to keep the battery element sealed. Then, when a certain temperature (opening temperature) is reached, the state quickly shifts to the state shown in FIG. 6C, and fine cracks such as pin holes (preferably inner bags) of the sealant layer 4 (preferably the inner bag) ( (Indicated by reference numeral 10 in FIG. 6) occurs, and the unsealed state is obtained under mild conditions.

  As described above, in the battery packaging material of the present invention, when the temperature of the battery is increased, the metal is used until reaching a certain temperature (opening temperature) determined according to the heat resistance required for various batteries. At least part (at least part of the interface of each layer or at least part of the inside of each layer) between the outer surface of the layer and the sealant layer (the innermost layer side surface) peels off, but the battery element is sealed by the sealant layer. In addition, after reaching the temperature, it can be opened gently by causing minute cleavage such as pinholes in the sealant layer that has been peeled off from the metal layer quickly. In the present invention, the temperature at which peeling occurs (peeling temperature) is not more than the above opening temperature. When the peeling temperature is lower than the opening temperature, after the peeling temperature is reached and peeling occurs, the temperature is further increased, and after the opening temperature is reached, the portion of the sealant that has peeled off is rapidly cracked and gently released. Open. In addition, when the peeling temperature and the opening temperature are the same, the peeling temperature is reached and peeling occurs, and at the peeling temperature, the portion of the sealant that has been peeled off is rapidly cleaved to cause gentle opening. Led to.

  On the other hand, in the conventional battery packaging material, the packaging material is not opened until a certain temperature is reached, and is not designed to be opened gently after reaching the opening temperature. Conventional battery packaging materials are not opened quickly even if the temperature is significantly higher than the temperature determined by the heat resistance required for the battery. In some cases, the sealing state suddenly shifts to the opening state, and the flammable gas or the electrolytic solution is suddenly ejected. Here, FIG. 7A shows an example of a state of interfacial delamination in which cleavage progresses rapidly at the heat seal interface between the sealant layers in the conventional battery packaging material. Moreover, in a conventional battery packaging material, an example of a state of cohesive peeling in which cleavage proceeds rapidly in the vicinity of the heat seal interface of the sealant layer is shown in FIG. 7B. FIG. 7C shows an example of a state of delamination in which cracking proceeds between layers (interlayers within the sealant layer) after the sealant layer is broken in a conventional battery packaging material. The “root break” means that the sealant layer is broken at the inner edge of the heat seal portion. In the battery packaging material of the present invention, since the conventional interfacial peeling, cohesive peeling, or delamination does not occur and a sudden opening state is not caused, the pressure in the battery is higher than that of the conventional battery packaging material. Excellent safety when temperature and temperature rise continuously.

3. Composition of each layer forming base material for battery [base material layer 1]
In the battery packaging material of the present invention, the base material layer 1 is a layer forming the outermost layer. The material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy, acrylic, fluororesin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and a mixture or copolymer thereof.

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

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

  The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1. Moreover, the base material layer 1 may be formed by coating the above-mentioned raw material on the metal 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 also be laminated with at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery package. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, and a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated. When making the base material layer 1 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as a co-extrusion method, a sand lamination method, or a thermal laminating 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. Further, the bonding 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 curing type such as UV and EB, and the like. As an adhesive component, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin Resins, polyimide resins, amino resins, rubbers, and silicon resins can be used.

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

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

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

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

[Adhesive layer 2]
In the battery packaging material of the present invention, the adhesive layer 2 is a layer provided as necessary for the purpose of improving the adhesion between the base material layer 1 and the metal layer 3. The base material layer 1 and the metal layer 3 may be directly laminated.

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

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

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

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

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

  About thickness of the metal layer 3, 10-200 micrometers is preferable, for example, Preferably it is 20-100 micrometers.

  In addition, the metal layer 3 is preferably subjected to chemical conversion treatment on at least one surface, preferably at least the surface on the sealant layer side, and more preferably both surfaces for stabilization of adhesion, prevention of dissolution and corrosion, and the like. Here, the chemical conversion treatment is a treatment for forming an acid-resistant film on the surface of the metal layer 3. Chemical conversion treatment is, for example, chromate chromate treatment using a chromic acid compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc. ; Phosphoric acid chromate treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; aminated phenol heavy consisting of repeating units represented by the following general formulas (1) to (4) Examples thereof include chromate treatment using a coalescence.

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 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, 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. be able to. In the general formulas (1) to (4), X is preferably any one of a hydrogen atom, a hydroxyl group, and a droxyalkyl group. The number average molecular weight of the aminated phenol polymer composed of the repeating units represented by the general formulas (1) to (4) is, for example, about 500 to about 1,000,000, preferably about 1000 to about 20,000.

  In addition, as a chemical conversion treatment method for imparting corrosion resistance to the metal layer 3, a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed in phosphoric acid is coated. A method of forming a corrosion-resistant layer on the surface of the metal layer by performing a baking treatment at 150 ° C. or higher can be mentioned. A resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be formed on the corrosion-resistant treatment layer. Here, as the cationic polymer, for example, polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin in which a primary amine is grafted on an acrylic main skeleton, polyallylamine, or Examples thereof include aminophenols and derivatives thereof. These cationic polymers may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of the crosslinking agent include compounds having at least one functional group selected from the group consisting of isocyanate groups, glycidyl groups, carboxyl groups, and oxazoline groups, silane coupling agents, and the like. These crosslinking agents may be used alone or in combination of two or more.

  These chemical conversion treatments may be performed alone or in combination of two or more chemical conversion treatments. 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 these, chromic acid chromate treatment is preferable, and chromate treatment in which a chromic acid compound, a phosphoric acid compound, and the aminated phenol polymer are combined is more preferable.

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

  In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal layer by a bar coating method, a roll coating method, a gravure coating method, an immersion method or the like, and then the temperature of the metal layer is 70. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the metal layer 3, the metal layer 3 may be 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 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 metal layer 3.

[Sealant layer 4]
In the battery packaging material of the present invention, the sealant layer 4 corresponds to the innermost layer, and is a layer that seals the battery element by heat-sealing the sealant layers when the battery is assembled. The sealant layer 4 has a first sealant layer 4a and a second sealant layer 4b, and is arranged such that the first sealant layer 4a is located on the metal layer 3 side and the second sealant layer 4b is located on the innermost layer. It has a layered structure.

(First sealant layer)
The first sealant layer 4a includes acid-modified polyolefin and is a layer located on the metal layer side. The acid-modified polyolefin used for forming the first sealant layer 4a is a polymer modified by graft polymerization of polyolefin with an unsaturated carboxylic acid. Specific examples of the acid-modified polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene) ), A random or amorphous polypropylene copolymer (for example, a random copolymer of propylene and ethylene), and a terpolymer of ethylene-butene-propylene. Among these polyolefins, from the viewpoint of heat resistance, polyolefins having at least propylene as a constituent monomer are preferable, and ethylene-butene-propylene terpolymers and propylene-ethylene random copolymers are more preferable. Examples of the unsaturated carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like. Among these unsaturated carboxylic acids, maleic acid and maleic anhydride are preferable. These acid-modified polyolefins may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition to the acid-modified polyolefin, the first sealant layer 4a includes at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin. This makes it possible to lower the softening point while keeping the melting point of the first sealant layer 4a within a certain range. When the battery is exposed to a high temperature until reaching the set temperature T ° C, the first sealant layer 4a As shown in FIGS. 3 to 5, at least a part of the interface between the metal layer 3 and the sealant layer 4 or the inside of the sealant layer 4 can be peeled off. Thereafter, the swelled sealant layer 4 causes fine cleavage (pinholes and the like), and the gas inside the battery can be gently released. In the case where the peeled portion of the sealant layer 4 expands due to internal pressure and swells while maintaining a sealed state until fine cleavage occurs in at least a part of the peeled sealant layer 4, the gas inside the battery is more It becomes possible to release gently. Although details of this reason are not necessarily clear, ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin all constitute acid-modified polyolefin and metal layer 3 that form sealant layer 4. It is considered that it is possible to lead to such gentle opening due to the adhesive resin having high adhesiveness to metal. Furthermore, when the first sealant layer 4a includes at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin, the sealant layers 4 are heat-sealed. The sealing strength is increased, and the laminate strength between the metal layer 3 and the sealant layer 4 is also increased. Although the reason for this is not necessarily clear, as described above, these resins are both adhesive resins having high adhesiveness with the acid-modified polyolefin forming the sealant layer 4 and the metal forming the metal layer 3. Therefore, it is considered that the seal strength and the laminate strength can be increased.

  The ethylene vinyl acetate copolymer may be an acid-modified ethylene vinyl acetate copolymer that has been acid-modified with carboxylic acid or the like. The acrylic resin is not particularly limited as long as it is a homopolymer or copolymer of acrylic ester, methacrylic ester, acrylic acid, methacrylic acid or the like. The styrene polymer may be a homopolymer of styrene or a copolymer with other monomers. The terpene phenol resin is not particularly limited as long as it is a copolymer of a terpene monomer and phenol. In the first sealant layer 4a, the ethylene vinyl acetate copolymer, the acrylic resin, the styrene polymer, and the terpene phenol resin may be used alone or in combination of two or more. Good. The total content of the ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin in the first sealant layer 4a is not particularly limited, but reaches the set temperature when the battery is heated. Until this is done, the peeled portion of the sealant layer 4 is formed into a bag shape (inner bag) and the battery element is preferably maintained in a sealed state, and after reaching the set temperature, leads to opening under milder conditions, as well as the above From the viewpoint of further increasing the sealing strength and the laminate strength, it is preferably 5% by mass or more, more preferably 10 to 90% by mass, and still more preferably 15 to 85% by mass.

  The first sealant layer 4a may be formed of at least one selected from the group consisting of an acid-modified polyolefin, an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin. Resin components other than these may be included as necessary. When the first sealant layer 4a contains an acid-modified polyolefin and a resin component other than at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin, The total of the content of at least one selected from the group consisting of the acid-modified polyolefin in one sealant layer 4a and the ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin is as follows. Although it does not restrict | limit especially unless an effect is prevented, For example, 10-95 mass%, Preferably it is 30-90 mass%, Furthermore, 50-80 mass% is mentioned.

  In the first sealant layer 4a, in addition to at least one selected from the group consisting of acid-modified polyolefin, ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin, a resin that can be contained as necessary Examples of the component include polyolefin.

  The polyolefin may have an acyclic structure or a cyclic structure. Specific examples of the acyclic polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene) And crystalline or amorphous polypropylene such as a random copolymer of polypropylene (for example, a random copolymer of propylene and ethylene); a terpolymer of ethylene-butene-propylene, and the like. The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer. Examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, And isoprene. 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. These polyolefins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these polyolefins, those having characteristics as an elastomer (that is, polyolefin-based elastomers), particularly propylene-based elastomers, are preferable from the viewpoints of improving adhesive strength after heat sealing, preventing delamination after heat sealing, and the like. . Examples of the propylene-based elastomer include polymers containing propylene and one or more α-olefins having 2 to 20 carbon atoms (excluding propylene) as constituent monomers, and the number of carbon atoms constituting the propylene-based elastomer is 2. Specific examples of the α-olefin of ˜20 (excluding propylene) include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. These polyolefin-based elastomers may be used alone or in combination of two or more.

  About the content of the resin component which can be contained in the 1st sealant layer 4a as needed, it sets suitably in the range which does not disturb the objective of this invention. For example, when the first sealant layer 4a contains a propylene elastomer, the content of the propylene elastomer in the first sealant layer 4a is usually 5 to 70% by mass, preferably 10 to 60% by mass, and more preferably. 20-50 mass% is mentioned.

Further, the melting point T _m1 of the first sealant layer 4a is not particularly limited, but when the battery is heated, the peeled portion of the sealant layer 4 has a bag shape (inner bag) until reaching a certain temperature. From the viewpoint of suitably maintaining the state where the battery element is sealed and reaching the temperature, and leading to opening under milder conditions, preferably 100 to 160 ° C, more preferably 105 to 150 ° C, Preferably it is 110-140 degreeC. In addition, the softening point T _s1 of the first sealant layer 4a is not particularly limited, but from the same viewpoint as the melting point, it is preferably 60 to 150 ° C, more preferably 65 to 140 ° C, and further preferably 75 to 120 ° C. Is mentioned.

Here, the melting point T _m1 of the first sealant layer 4a is a value measured by the DSC method in accordance with the melting point of the resin component constituting the first sealant layer 4a in accordance with JIS K6921-2 (ISO1873-2.2: 95). It is. The first sealant layer 4a is, if it is formed of a blend resin including a plurality of resin components, the melting point T _m1 is the blend resin JIS K6921-2 (ISO1873-2.2: 95) to According to the DSC method, the ratio of the peak area of the melting point corresponding to each resin component was calculated with the total peak area being 1, and the value obtained by multiplying the melting point corresponding to each resin component and the ratio of the peak area (melting point × area Ratio), and the value calculated for each melting point (melting point × area ratio) is added.

Further, the softening point T _s1 of the first sealant layer 4a is a value measured by the Vicat softening temperature test method JIS K7206. When the first sealant layer 4a is formed of a blend resin containing a plurality of resin components, the softening point T _s1 is obtained by the sum of the softening point of the constituent components of the blend resin × the blending fraction. It is done.

  Moreover, as thickness of the 1st sealant layer 4a, 5-40 micrometers, for example, Preferably it is 10-35 micrometers, More preferably, 15-30 micrometers is mentioned.

(Second sealant layer)
The second sealant layer 4b is a layer that is laminated on the first sealant layer 4a and is positioned as the innermost layer of the battery packaging material. That is, in the battery packaging material of the present invention, the second sealant layers 4b are heat-sealed to seal the battery element. From the viewpoint of improving the sealability of the sealant layer 4, the second sealant layer 4b preferably contains polyolefin. The polyolefin used for forming the second sealant layer 4b is not particularly limited. For example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer Examples thereof include crystalline or amorphous polypropylene such as a block copolymer of propylene and ethylene (for example, a random copolymer of polypropylene and a random copolymer of propylene and ethylene), a terpolymer of ethylene-butene-propylene, and the like. Among these polyolefins, from the viewpoint of heat resistance, a polyolefin having at least propylene as a constituent monomer is preferable, more preferably a random copolymer of propylene-ethylene, a terpolymer of propylene-ethylene-butene, and a homopolymer of propylene. Can be mentioned. These polyolefins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The 2nd sealant layer 4b may be formed only from polyolefin, and may contain resin components other than polyolefin. When the resin component other than the polyolefin is contained in the second sealant layer 4b, the content of the polyolefin in the second sealant layer 4b is not particularly limited as long as the effect of the present invention is not hindered, for example, 10 to 95% by mass, Preferably 30-90 mass%, Furthermore, 50-80 mass% is mentioned.

  Examples of the resin component other than the polyolefin that can be included in the second sealant layer 4b include acid-modified polyolefin. Specific examples of the acid-modified polyolefin are the same as those exemplified in the first sealant layer 4a. When the resin component other than the polyolefin is contained in the second sealant layer 4b, the content of the resin component is appropriately set within a range that does not hinder the object of the present invention. For example, when the acid-modified polyolefin is contained in the second sealant layer 4b, the content of the acid-modified polyolefin in the second sealant layer 4b is usually 5 to 60% by mass, preferably 10 to 50% by mass, and more preferably. 20-40 mass% is mentioned.

In the present invention, the melting point T _m2 of the second sealant layer 4b and the melting point T _m1 of the first sealant layer 4a preferably satisfy the following relationship.
T _m2 ≧ T _m1
That is, when the melting point T _m2 of the second sealant layer 4b is _{equal to} or higher than the melting point T _m1 of the first sealant layer 4a, for example, as shown in FIG. A state in which the battery element is hermetically sealed as an (inner bag) can be suitably maintained. Then, when the opening temperature is reached, for example, the state rapidly changes to the state shown in C of FIGS. 3 to 6, and a fine tear such as a pinhole is generated in the peeled region of the sealant layer 4, and the opening state is more gentle. It becomes possible to lead to. From such a viewpoint, it is more preferable that the melting point T _m2 of the second sealant layer 4b and the melting point T _m1 of the first sealant layer 4a satisfy the following relationship.
T _m2 ≧ T _m1 +5

The method for calculating the melting point T _m2 and the softening point T _s2 of the second sealant layer 4b is the same as that for the melting point T _m1 of the first sealant layer 4a.

Further, the melting point T _m2 of the second sealant layer 4b is not particularly limited, but when the battery is heated, the peeled portion of the sealant layer 4 has a bag shape (inner bag) until the opening temperature is reached. From the viewpoint of suitably maintaining the battery element in a sealed state and reaching the opening under a milder condition after reaching the opening temperature, it is preferably 100 to 160 ° C, more preferably 105 to 150 ° C, and still more preferably 110-140 degreeC is mentioned. In addition, the softening point T _s2 of the second sealant layer 4b is not particularly limited, but from the same viewpoint, it is preferably 60 to 150 ° C, more preferably 65 to 140 ° C, and further preferably 70 to 120 ° C. It is done.

  As described above, since the melting point of the resin component is determined by the molecular weight, the type and ratio of the constituent monomer, etc., in the resin component blended in the second sealant layer 4b, for example, the melting point and softening point of the second sealant layer 4b. By satisfying the above range, the molecular weight, the type and ratio of constituent monomers, and the like are appropriately set so that the battery packaging material is gently opened.

  Moreover, as thickness of the 2nd sealant layer 4b, 5-40 micrometers, for example, Preferably it is 10-35 micrometers, More preferably, 15-30 micrometers is mentioned.

(3rd sealant layer, etc.)
As described above, the sealant layer 4 of the battery packaging material of the present invention includes the first sealant layer 4c, the fourth sealant layer 4d, and the like between the first sealant layer 4a and the second sealant layer 4b. You may have further in order from 4a side. That is, the sealant layer 4 may be composed of three or more layers further including a third sealant layer 4c and the like between the first sealant layer 4a and the second sealant layer 4b. From the viewpoint of improving the sealability of the sealant layer 4, the layer provided between the first sealant layer 4a and the second sealant layer 4b such as the third sealant layer 4c includes at least one of polyolefin and acid-modified polyolefin. Is preferred. Examples of the polyolefin used for forming the third sealant layer 4c and the like are the same as those exemplified for the second sealant layer 4b. In addition, examples of the acid-modified polyolefin used for forming the third sealant layer 4c include the same ones as exemplified in the first sealant layer 4a.

  Further, the melting point of the layer provided between the first sealant layer 4a and the second sealant layer 4b such as the third sealant layer 4c is not particularly limited, but reaches the opening temperature when the battery is heated. From the point of view of leading to opening under a milder condition after reaching the opening temperature, the peeled part of the sealant layer 4 is preferably in a bag shape (inner bag) until the battery element is sealed. Preferably 100-160 degreeC is mentioned. In addition, the softening point of these layers is not particularly limited, but from the same viewpoint, preferably 60 to 150 ° C can be mentioned.

  Moreover, as thickness of the 3rd sealant layer 4c etc., 5-40 micrometers, Preferably it is 10-35 micrometers, More preferably, 15-30 micrometers is mentioned, for example.

(Total thickness of sealant layer 4)
The total thickness of the sealant layer 4 is determined based on the thickness of each of the first sealant layer 4a, the second sealant layer 4b, and the third sealant layer 4c provided as necessary, for example, 15 to 120 μm. Preferably, it is 60-80 micrometers, More preferably, 30-60 micrometers is mentioned.

[Adhesive layer 5]
In the battery packaging material of the present invention, an adhesive layer is provided between the metal layer 3 and the sealant layer 4 for the purpose of firmly bonding the metal layer 3 and the sealant layer 4 as shown in FIG. 5 may be further provided. The adhesive layer 5 may be formed of one layer or may be formed of a plurality of layers.

  The adhesive layer 5 is formed of a resin capable of bonding the metal layer 3 and the sealant layer 4. The resin forming the adhesive layer 5 is not particularly limited as long as it is a resin capable of adhering the metal layer 3 and the sealant layer 4. For example, the resin component of the adhesive exemplified in the adhesive layer 2, the sealant layer Examples include acid-modified polyolefins exemplified in 4. The resin forming the adhesive layer 5 may be used alone or in combination of two or more.

  When the resin component of the adhesive exemplified in the adhesive layer 2 is used as the resin for forming the adhesive layer 5, the adhesive layer 5 can be formed in the same manner as the adhesive layer 2. Moreover, when using acid-modified polyolefin as resin which forms the contact bonding layer 5, the contact bonding layer 5 may be formed only from acid-modified polyolefin, and contains resin components other than acid-modified polyolefin as needed. May be. When the resin component other than the acid-modified polyolefin is contained in the adhesive layer 5, the content of the acid-modified polyolefin in the sealant layer 4 is not particularly limited as long as the effect of the present invention is not hindered, for example, 10 to 95% by mass, Preferably 30-90 mass%, Furthermore, 50-80 mass% is mentioned.

  Moreover, when the contact bonding layer 5 contains acid-modified polyolefin, it is preferable that the contact bonding layer 5 further contains a hardening | curing agent. By including the acid-modified polyolefin and the curing agent in the adhesive layer 5, the mechanical strength of the adhesive layer 5 can be increased, and the insulation of the battery packaging material can be effectively increased. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more types.

  The curing agent is not particularly limited as long as it cures the acid-modified polyolefin. As a hardening | curing agent, a polyfunctional isocyanate compound, a carbodiimide compound, an epoxy compound, an oxazoline compound etc. are mentioned, for example.

  The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate compound include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurate, mixtures thereof, Examples include copolymers with other polymers.

  The carbodiimide compound is not particularly limited as long as it is a compound having at least one carbodiimide group (—N═C═N—). As the carbodiimide compound, a polycarbodiimide compound having at least two carbodiimide groups is preferable. Specific examples of particularly preferred carbodiimide compounds include the following general formula (5):

[In General formula (5), n is an integer greater than or equal to 2. ]
A polycarbodiimide compound having a repeating unit represented by:
The following general formula (6):

[In General formula (6), n is an integer greater than or equal to 2. ]
A polycarbodiimide compound having a repeating unit represented by:
And the following general formula (7):

[In General formula (7), n is an integer greater than or equal to 2. ]
The polycarbodiimide compound represented by these is mentioned. In general formula (4)-(7), n is an integer of 30 or less normally, Preferably it is an integer of 3-20.

  The epoxy compound is not particularly limited as long as it is a compound having at least one epoxy group. Examples of the epoxy compound 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 oxazoline compound is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline compound include Epocross series manufactured by Nippon Shokubai Co., Ltd.

  From the standpoint of increasing the mechanical strength of the adhesive layer 5, the curing agent may be composed of two or more types of compounds.

  In the adhesive layer 5, the content of the curing agent is preferably in the range of 0.1 to 50 parts by weight, and in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the acid-modified polyolefin. More preferably. In the adhesive layer 5, the content of the curing agent is preferably in the range of 1 equivalent to 30 equivalents as a reactive group in the curing agent with respect to 1 equivalent of the carboxyl group in the acid-modified polyolefin. More preferably, it is in the range of 20 equivalents. Thereby, the insulation and durability of the battery packaging material can be further improved.

  From the viewpoint that the battery packaging material of the present invention can be maintained in a sealed state without being cleaved until it reaches a predetermined set temperature, and quickly and gently opens when the set temperature is reached. The melting point of the adhesive layer 5 is preferably about 60 to 160 ° C, more preferably about 70 to 140 ° C. From the same viewpoint, the softening point of the adhesive layer 5 is preferably about 50 to 150 ° C, more preferably about 60 to 130 ° C.

  The calculation method of the melting point and the softening point of the adhesive layer 5 is the same as that for the sealant layer 4.

  Although it does not restrict | limit especially as thickness of the contact bonding layer 5, Preferably it is 0.01 micrometer or more, More preferably, about 0.1-20 micrometers is mentioned. If the thickness of the adhesive layer 5 is less than 0.01 μm, it may be difficult to stably bond the metal layer 3 and the sealant layer 4.

4). Method for Producing Battery Packaging Material The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers having a predetermined composition are laminated is obtained. For example, the following method is exemplified. .

  First, a laminated body (hereinafter, also referred to as “laminated body A”) in which a base material layer 1, an adhesive layer 2, and a metal layer 3 are sequentially laminated as necessary is formed. Specifically, the laminate A is formed by thermally laminating the base material 1 and the metal layer 3 whose surface is subjected to chemical conversion treatment as necessary, using an adhesive that forms the adhesive layer 2 as necessary. It is performed by laminating by a method, a sand laminating method, or a combination thereof.

  The laminate A is formed by the thermal laminating method. For example, a multilayer film in which the base material layer 1 and the adhesive layer 2 are laminated is prepared in advance, and the metal layer 3 is superimposed on the adhesive layer 2 and heated with a heating roll. It can be performed by thermocompression bonding with the adhesive layer 2 sandwiched between the layer 1 and the metal layer 3. The laminate A is formed by the thermal laminating method in which a multilayer film in which the metal layer 3 and the adhesive layer 2 are laminated is prepared in advance, and the base material layer 1 is superposed on the heated metal layer 3 and the adhesive layer 2. It may be performed by thermocompression bonding while sandwiching the adhesive layer 2 between the base material layer 1 and the metal layer 3.

  In addition, the multilayer film in which the base material layer 1 and the adhesive layer 2 prepared in advance in the thermal laminating method are laminated on the resin film constituting the base material layer 1 by melt extrusion or solution coating of the adhesive constituting the adhesive layer 2. After being laminated and dried by (liquid coating), the adhesive layer 2 is formed by baking at a temperature equal to or higher than the melting point of the adhesive. By performing baking, the adhesive strength between the metal layer 3 and the adhesive layer 2 is improved. Similarly, for a multilayer film in which the metal layer 3 and the adhesive layer 2 prepared in advance in the thermal laminating method are laminated, the adhesive constituting the adhesive layer 2 is melt-extruded or solution into the metal foil constituting the metal layer 3 in the same manner. After being laminated by coating and dried, it is formed by baking at a temperature equal to or higher than the melting point of the adhesive constituting the adhesive layer 2.

  The laminate A is formed by the sand lamination method, for example, by melting and extruding the adhesive constituting the adhesive layer 2 onto the upper surface of the metal layer 3 and bonding the resin film constituting the base material layer 1 to the metal layer. Can be performed. At this time, it is desirable that the resin film is bonded and temporarily bonded, and then heated again to perform the main bonding. In the sand lamination method, the adhesive layer 2 may be multilayered with different resin types. In this case, a multilayer film in which the base material layer 1 and the adhesive layer 2 are laminated is prepared in advance, the adhesive constituting the adhesive layer 2 is melt-extruded on the upper surface of the metal layer 3, and the multilayer resin film and the thermal lamination method are used. What is necessary is just to laminate. Thereby, the adhesive layer 2 which comprises a multilayer film, and the adhesive layer 2 laminated | stacked on the upper surface of the metal layer 3 adhere | attach, and the two-layer adhesive layer 2 is formed. When the adhesive layer 2 is multilayered with different resin types, a multilayer film in which the metal layer 3 and the adhesive layer 2 are laminated is prepared in advance, and the adhesive constituting the adhesive layer 2 is melted on the base material layer 1 It may be extruded and laminated with the adhesive layer 2 on the metal layer 3. Thereby, the adhesive layer 2 composed of two different adhesives is formed between the multilayer resin film and the base material layer 1.

  Next, the sealant layer 4 (the first sealant layer 4a and the second sealant layer 4b) is laminated on the metal layer 3 of the laminate A. The sealant layer 4 is laminated on the metal layer 3 of the laminate A, for example, on the metal layer 3 of the laminate A, the first sealant layer 4a, and if necessary, the third sealant layer 4c and the second sealant layer. 4b can be sequentially applied by a method such as gravure coating or roll coating. Further, the lamination of the sealant layer 4 onto the metal layer 3 of the laminate A can also be performed by a method in which the first sealant layer 4a and the second sealant layer 4b are coextruded on the metal layer 3 of the laminate A. . Further, when the third sealant layer 4c is provided, the third sealant layer 4c and the second sealant layer 4b are coextruded after the first sealant layer 4a is applied or thermocompression-bonded on the metal layer 3 of the laminate A. Alternatively, the first sealant layer 4a and the third sealant layer 4c may be coextruded on the metal layer 3 of the laminate A, and then the second sealant layer 4b may be applied or thermocompression bonded. Further, an adhesive layer 5 may be provided between the metal layer 3 and the sealant layer 4.

  As described above, base material layer 1 / adhesive layer 2 formed as necessary / metal layer 3 whose surface is subjected to chemical conversion treatment as needed / adhesive layer 5 formed as needed / sealant layer 4 A laminate composed of (first sealant layer 4a, second sealant layer 4b such as third sealant layer 4c if necessary) is formed. You may use for heat processing, such as roll contact, a hot air, near or far infrared irradiation, dielectric heating, and heat resistance heating. Examples of such heat treatment conditions include 150 to 250 ° C. and 1 to 10 hours.

  Moreover, 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, and ozone treatment may be performed.

5. Characteristics and Applications of Battery Packaging Material The battery packaging material of the present invention has the above-described specific sealant layer, so that the outer surface of the metal layer and the sealant layer until reaching a certain temperature (opening temperature). (The innermost layer side surface) peels at least partly, but the battery element can be kept sealed by the sealant layer, and when the temperature reaches the opening temperature, the peeled part is quickly separated into the sealant layer. It can be opened gently by causing a fine tear such as a pinhole. In the battery packaging material of the present invention, the opening temperature can be set in advance according to characteristics such as heat resistance required for various batteries. In general, when the temperature inside the battery exceeds 150 ° C., the separator of the battery element melts, causing a short circuit between the positive electrode and the negative electrode, and a short circuit between the electrode and the metal layer of the battery packaging material. Runaway or fire may occur, which may cause battery explosion or explosion. For this reason, the opening temperature is generally set to a temperature of 150 ° C. or lower. For example, the battery packaging material of the present invention has the property that the packaging material does not open until reaching the certain temperature described above under the heating conditions shown below, and is opened within at least 30 minutes after reaching the opening temperature. It becomes possible to prepare.
<Heating conditions>
(1) A recess having a depth of 3 mm, a length of 35 and a width of 50 mm is formed at the center of the battery packaging material cut into a shape having a length of 80 mm and a width of 150 mm, and is formed into a shape having an edge around the recess. Two battery packaging materials molded into such a shape are prepared.
(2) The edge portions are overlapped so that the two sealant layers of the battery packaging material formed as described above face each other, and the edge portions are heat sealed (175 ° C., 3 seconds, surface pressure 1.4 MPa), A case having a sealed internal space (pressure 1 atm) is formed.
(3) Put the battery packaging material in the above-mentioned case into an oven that can be decompressed, set the pressure in the oven to 0 atm, and heat at a rate of temperature increase of 3 ° C./min. The heating temperature is a temperature until the battery packaging material is opened. For example, when the battery packaging material is not opened when it reaches 150 ° C., the temperature is maintained at 150 ° C., and the time from reaching 150 ° C. until opening is measured. In this test, the upper limit of the heating temperature is not limited to 150 ° C., and after raising the temperature to an arbitrarily set opening temperature (for example, a temperature between 100 to 160 ° C.), the temperature is maintained, The characteristics may be evaluated by measuring the time from when the temperature is reached until it is opened.

  The battery packaging material of the present invention has the opening characteristics described above, and is gently opened by micro-cleavage at the time of opening. Therefore, when the battery is heated, the metal layer and the sealant layer until reaching a certain set temperature. Battery packaging that is set to prevent the battery from firing and reaction runaway quickly after the set temperature is reached. It is suitably used as a material for use. The set temperature T determined by the battery differs depending on the type of battery to be packaged, application, safety standards, and the like. For example, there is a battery in which the set temperature T is set to 100 ° C. and a battery in which the set temperature is set to 150 ° C. for safety standards. The battery packaging material of the present invention is provided as a packaging material having a sealing property and an unsealing property corresponding to the set temperature required by the battery to be applied. In addition, the time required for the battery to transition to the unsealed state after reaching T ° C. is determined within a range in which safety can be ensured, and varies depending on the type and use of the battery, the rate of temperature increase, etc. Is within 30 minutes, and the battery packaging material of the present invention can satisfy the time.

  In addition, the battery packaging material of the present invention has a high sealing strength when the sealant layers are heat-sealed, and also has a high laminate strength between the metal layer and the sealant layer. In the battery packaging material of the present invention, the seal strength of the heat-sealed portion with the sealant layers 4 facing each other is preferably 30 (N / 15 mm) or more, more preferably 50 (N / N) at 25 ° C. 15 mm) or more. If the seal strength at 25 ° C. is too low, the seal may be opened before reaching the set temperature. In the battery packaging material of the present invention, the laminate strength between the metal layer 3 and the sealant layer 4 at 25 ° C. is preferably 4 (N / 15 mm) or more, more preferably 6 (N / 15 mm) or more. It is done. If the laminate strength at 25 ° C. is too low, the laminate may be opened before reaching the set temperature.

  Specifically, the battery packaging material of the present invention can be used for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte, and is provided with a space for housing the battery element. . The space is formed by press-molding a laminated sheet cut into a short shape.

  More specifically, a battery element including at least a positive electrode, a negative electrode, and an electrolyte, with the battery packaging material of the present invention, in a state where the metal terminals connected to each of the positive electrode and the negative electrode protrude outward, A battery using a battery packaging material by covering the periphery of the battery element so that a flange portion (region where the sealant layers contact each other) can be formed, and heat-sealing and sealing the sealant layers of the flange portion. Is provided. In addition, when accommodating a battery element using the battery packaging material of the present invention, it is used so that the second sealant layer 4b of the battery packaging material of the present invention is on the inner side (surface in contact with the battery element).

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

B. The present invention further provides a method for screening a resin component used in a sealant layer formed in a battery packaging material having the above-described sealing and unsealing properties. .

Specifically, the screening method is a method of screening a resin component used in a sealant layer formed on a battery packaging material,
The battery packaging material is composed of a laminate having at least a base material layer, an adhesive layer, a metal layer, and a sealant layer in this order,
The sealant layer has a first sealant layer containing an acid-modified polyolefin and a second sealant layer in order,
In the sealant layer, the first sealant layer is disposed on the metal layer side, and the second sealant layer is disposed on the innermost layer,
Resin component forming the first sealant layer 4a so that the first sealant layer contains at least one selected from the group consisting of ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin. It is characterized by selecting.

  The meaning of each term in the screening method is as described in the column “A. Battery packaging material”.

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

Example 1-13 and Comparative Example 1-5
[Manufacture of battery packaging materials]
A metal layer 3 made of an aluminum foil (thickness 40 μm) subjected to chemical conversion treatment on both surfaces of a base material layer 1 made of a biaxially stretched nylon film (thickness 25 μm) was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of an aluminum foil to form an adhesive layer 2 (thickness 4 μm) on the metal layer 3. Next, after bonding the adhesive layer 2 and the base material layer 1 on the metal layer 3 under pressure and heating, an aging treatment is carried out at 40 ° C. for 24 hours, whereby base material layer 1 / adhesive layer 2 / metal layer 3 A laminate was prepared. In addition, the chemical conversion treatment of the aluminum foil used as the metal layer 3 is performed by rolling a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry weight). The coating was applied to both surfaces of the aluminum foil and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.

  Next, the first sealant layer is formed on the metal layer 3 by co-extruding the resin component forming the first sealant layer and the resin component forming the second sealant layer on the metal layer 3 side of the laminate in a molten state. A second sealant layer was laminated. In Examples 9 and 13, a multilayer CPP film (unstretched PP film) composed of a third sealant layer and a second sealant layer was further formed on the first sealant layer by a sand lamination method. In Comparative Example 3, a multilayer CPP (PP unstretched film) composed of a third sealant layer, a fourth sealant layer, and a second sealant layer was laminated on the first sealant layer by a sand lamination method. The resin components forming each sealant layer are as shown in Table 2. Moreover, about melting | fusing point of each sealant layer, it is the value measured by DSC method. Thus, a battery packaging material comprising a laminate in which the base material layer 1 / adhesive layer 2 / metal layer 3 / sealant layer 4 were sequentially laminated was obtained.

[Evaluation of sealing and unsealing properties of battery packaging materials]
After each battery packaging material obtained in Examples 1 to 13 and Comparative Examples 1 to 5 is cut into 80 mm × 150 mm, a molding die (female die) having a diameter of 35 mm × 50 mm and a molding die corresponding thereto (Male type) was cold-molded at a depth of 3.0 mm at 0.4 MPa, and a recess was formed at the center. Regarding the battery packaging material after cold forming, it was visually observed whether or not pinholes were generated on the surface of the base material layer 1, and no pinholes were observed in any of the battery packaging materials. It was. Also, the two battery packaging materials after molding are stacked so that the sealant layers face each other, and the edge where the sealant layers overlap is heat sealed (175 ° C., 3 seconds, surface pressure 1.4 MPa). A case with a sealed internal space (pressure 1 atm) was formed. Thus, the battery packaging material in the form of a case is put in an oven that can be decompressed, and the pressure in the oven is set to 0 atm, and the temperature is increased to 150 ° C. at a temperature increase rate of 3 ° C./min. did. When the package was not opened even when the temperature reached 150 ° C., the temperature of 150 ° C. was maintained as it was. The temperature (peeling temperature) at which peeling occurred between the metal layer and the sealant layer of the battery packaging material, the time until peeling after reaching the peeling temperature, the opening temperature at which the battery packaging material was opened, and the opening temperature The time from opening to opening until opening was visually confirmed.

  Based on the results observed in the test, the sealing and unsealing properties of each battery packaging material were evaluated according to the following criteria.

[Measurement of seal strength]
The battery packaging materials are stacked so that the sealant layers face each other, heat sealed under conditions of 190 ° C. and a surface pressure of 1.0 MPa for 3 seconds, and left at 25 ° C. for 2 minutes, and then a tensile tester (Shimadzu) The sealant layer of the heat seal part was peeled by 10 mm at a rate of 30 mm / min with AGS-50D (trade name) manufactured by Seisakusho, and the maximum strength at the time of peeling was defined as the seal strength (N / 15 mm). The results are shown in Table 2.

[Measurement of laminate strength]
At 25 ° C., each of the cut battery packaging materials was peeled 10 mm at a rate of 50 mm / min between the metal layer and the sealant layer with a tensile tester (manufactured by Shimadzu Corp., AGS-50D (trade name)). The maximum strength at the time of peeling was defined as the laminate strength (N / 15 mm). The results are shown in Table 2.

In Table 2, the abbreviations of the resin components are as follows.
PPa (A): maleic acid-modified random polypropylene, melting point 160 ° C., softening point 145 ° C.
PPa (B): maleic acid-modified random polypropylene, melting point 140 ° C., softening point 130 ° C.
PPa (C): maleic acid-modified random polypropylene, melting point 125 ° C., softening point 115 ° C.
PPa (D): maleic acid-modified homopolypropylene, melting point 160 ° C., softening point 156 ° C.
PP (A): random polypropylene, melting point 160 ° C., softening point 85 ° C.
PP (B): random polypropylene, melting point 140 ° C., softening point 85 ° C.
PP (C): random polypropylene, melting point 125 ° C., softening point 80 ° C.
PP (D): homopolypropylene, melting point 160 ° C., softening point 150 ° C.
PP (E): random polypropylene, melting point 155 ° C., softening point 145 ° C.
PP (F): homopolypropylene, melting point 160 ° C., softening point 156 ° C.
EPR140: Propylene elastomer, melting point 140 ° C, softening point 125 ° C
EVA (A): ethylene vinyl acetate copolymer, melting point 90 ° C., softening point 50 ° C.
Acid-modified EVA (A): carboxylic acid-modified ethylene vinyl acetate copolymer, melting point 90 ° C., softening point 50 ° C.
EVA (B): ethylene vinyl acetate copolymer, melting point 90 ° C., softening point 80 ° C.
Acid-modified EVA (B): carboxylic acid-modified ethylene vinyl acetate copolymer, melting point 90 ° C., softening point 80 ° C.
EVA (C): ethylene vinyl acetate copolymer, no melting point, softening point 60 ° C.
Acid-modified EVA (C): carboxylic acid-modified ethylene vinyl acetate copolymer, no melting point, softening point 60 ° C
Acrylic resin: Polymethacrylate, no melting point, softening point 80 ° C
TP: terpene phenol copolymer, no melting point, softening point 100 ° C.
Styrene polymer: atactic polystyrene, no melting point, softening point 100 ° C.
Amorphous PP: Amorphous polypropylene, no melting point, softening point 70 ° C
LDPE: Low density polyolefin, melting point 100 ° C, softening point 80 ° C
Acid-modified LDPE: Carboxylic acid-modified low density polyolefin, melting point 100 ° C., softening point 80 ° C.
LLDPE: Linear low density polyolefin, melting point 120 ° C, softening point 60 ° C
Acid-modified LLDPE: carboxylic acid-modified linear low density polyolefin, melting point 120 ° C., softening point 60 ° C.

  The obtained results are shown in Table 2. From this result, in addition to acid-modified polyolefin, ethylene vinyl acetate copolymer, acid-modified ethylene vinyl acetate copolymer, amorphous polypropylene, acrylic resin, and styrene polymer are used as the adhesive resin in the first sealant layer. In the battery packaging materials of Examples 1 to 13, until the opening temperature was reached, at least a part of the sealant layer was peeled off, but no tearing occurred, and the sealant layer became a bag shape and the internal sealing performance was maintained. It had been. Further, after reaching the opening temperature, a minute tear such as a pinhole occurred in the peeled portion of the sealant layer, and the state shifted to a gentle opening state. Furthermore, the battery packaging materials of Examples 1 to 13 exhibited high sealing strength and laminate strength. On the other hand, although the first sealant layer contains acid-modified polyolefin, the battery packaging materials of Comparative Examples 1 to 3 in which the adhesive resin as described above was not used had low seal strength and laminate strength. Moreover, in the battery packaging material of Comparative Example 4 using an acid-modified polyolefin having a high melting point and not using the above-described adhesive resin, peeling and opening occurred even after 5 hours had passed after reaching 150 ° C. However, when the temperature rises as it is, the separator of the battery element is melted, and the battery reaction is runaway or ignited due to a short circuit between the positive electrode and the negative electrode, which may cause the battery to burst or explode. Further, in Comparative Example 5 in which only the ethylene vinyl acetate copolymer was used for the first sealant layer, opening was abruptly caused at a low temperature of 90 ° C., causing cohesive failure at the heat seal portion and root seal breakage.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Metal layer 5 Adhesive layer 4 Sealant layer 4a 1st sealant layer 4b 2nd sealant layer 10 Fine cleavage

Claims (12)

It consists of a laminate having at least a base material layer, a metal layer, and a sealant layer in this order,
The sealant layer has a first sealant layer containing an acid-modified polyolefin and a second sealant layer in order,
In the sealant layer, the first sealant layer is disposed on the metal layer side, and the second sealant layer is disposed on the innermost layer,
The battery packaging material, wherein the first sealant layer includes at least one selected from the group consisting of an ethylene vinyl acetate copolymer, an acrylic resin, a styrene polymer, and a terpene phenol resin.   The total of at least one content selected from the group consisting of the ethylene vinyl acetate copolymer, acrylic resin, styrene polymer, and terpene phenol resin in the first sealant layer is 5% by mass or more. Item 4. A battery packaging material according to Item 1. The melting point T _m2 of the second sealant layer and the melting point T _m1 of the first sealant layer have the following relationship:
T _m2 ≧ T _m1
The battery packaging material according to claim 1 or 2, wherein The melting point T _m1 of the first sealant layer is 100 to 160 ° C., the softening point T _s1 of the first sealant layer is 60 to 150 ° C., packaging material for battery according to any one of claims 1 to 3 . The melting point T _m2 of the second sealant layer is 100 to 160 ° C., the softening point T _s2 of the second sealant layer is 60 to 150 ° C., packaging material for battery according to any one of claims 1 to 4 .   When the temperature of the battery is raised, peeling occurs at least in part between the metal layer and the outer surface of the sealant layer until the set temperature is reached, but the packaging material is not opened. The battery packaging material according to any one of claims 1 to 5, which is a battery packaging material used for a battery that is set so that the packaging material is opened to prevent ignition and reaction runaway of the battery.   The battery packaging material according to any one of claims 1 to 6, wherein the acidic polyolefin contained in the first sealant layer contains at least propylene as a constituent monomer.   The battery packaging material according to any one of claims 1 to 7, wherein the second sealant layer contains a polyolefin.   The battery packaging material according to claim 8, wherein the polyolefin contained in the second sealant layer contains at least propylene as a constituent monomer.   The battery packaging material according to any one of claims 1 to 9, wherein the first sealant layer has a thickness of 5 to 40 µm, and the second sealant layer has a thickness of 5 to 40 µm.   The battery packaging material according to any one of claims 1 to 10, wherein the metal layer is an aluminum foil.   The battery packaging material according to claim 1, further comprising an adhesive layer between the base material layer and the metal layer.