JP2017068959A - Sealant film for exterior package material of power storage device, exterior package material for power storage device, and power storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant film for an exterior package material of a power storage device, which can cause a break in a sealant layer (delamination) to vent gas thereby to prevent the increase in internal pressure from rupturing an exterior package material in the excessive rise in the internal pressure of a power storage device, which is hard for the break to continuously spread from a break point where the break for preventing the rupture is caused, and which enables the suppression of whitening in shaping.SOLUTION: A sealant film for an exterior package material of a power storage device comprises a laminate composed of two or more layers including: a first resin layer 7 including 50 mass% or more of a random copolymer including propylene as a copolymerization component and another copolymerization component other than propylene; and a second resin layer 8 formed from a mixed resin including a first elastomer-modified olefin based resin of 105°C or higher in crystallization temperature and 50 J/g or larger in crystallization energy, and a second elastomer-modified olefin based resin of 85°C or higher in crystallization temperature and 30 J/g or smaller in crystallization energy.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sealant film used for constituting an exterior material of an electricity storage device, an exterior material for an electricity storage device using the sealant film, and an electricity storage device constituted using the exterior material.

  In the present specification and claims, the term “crystallization temperature” means a crystallization peak temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121-1987, and “ The term “crystallization energy” means heat of crystallization (crystallization energy) measured by differential scanning calorimetry (DSC) according to JIS K7122-1987.

  In the present specification and claims, the term “crystallization temperature” means that there are two or more crystallization peaks and two crystallization temperatures (Tcp1, Tcp2) or three or more. In this case, the value of the highest crystallization temperature shall be indicated.

  In the present specification and claims, the term “crystallization energy” means that there are two or more crystallization peaks and two crystallization energies (ΔHc1, ΔHc2) or three or more. If present, it shall refer to the highest crystallization energy value.

  In the present specification and claims, the term “aluminum” is used to include aluminum and its alloys.

  Lithium ion secondary batteries are widely used as power sources for notebook computers, video cameras, mobile phones, electric vehicles, and the like. As this lithium ion secondary battery, one having a configuration in which the periphery of a battery main body (a main body including a positive electrode, a negative electrode, and an electrolyte) is surrounded by a case is used. As this case material (exterior material), for example, an outer layer made of a heat-resistant resin film, an aluminum foil layer, and an inner layer made of a thermoplastic resin film are known to be bonded and integrated in this order.

  The power storage device is configured to be sealed by sandwiching a power storage device main body between a pair of exterior materials and fusion-bonding (heat-sealing) the peripheral edges of the pair of exterior materials.

  By the way, in the case of a lithium ion secondary battery or the like, gas is likely to be generated in the battery body during overcharge or overheating, and for this reason, the gas gradually accumulates in the internal space covered with the exterior material. Internal internal pressure may increase. Since there is a concern that the exterior material may burst when the increase in internal pressure increases, a technique for preventing such explosion of the exterior material has been proposed.

  For example, Patent Document 1 includes an electrode laminate in which a positive electrode and a negative electrode formed in a sheet shape are laminated via a separator, and the electrode laminate is placed in a metal laminate film container together with an electrolytic solution. An electric storage device with an explosion-proof function, wherein the container is hermetically sealed by a heat sealing portion formed by heat-sealing the metal laminate film in a band shape along the outer peripheral edge of the container, A blade support that is attached and fixed in a state where the peripheral portion is sandwiched, and a blade member that is supported by the blade support and disposed at a position closer to the center than the heat sealing portion in the container. A drilling device, wherein the blade support moves in an outer peripheral direction of the container by being pushed out by the container that expands and deforms when gas is generated, and the blade member moves together with the blade support. In explosion-proof function electric storage device has been made as to cut through the container is described.

  Patent Document 2 discloses a storage element body impregnated with an electrolytic solution, an exterior body for sealing the electrical storage element body, a first gas release mechanism provided inside the exterior body, and the exterior body. And a gas from the internal space of the exterior body in which the power storage element body exists passes through each of the gas discharge mechanism portions in order from the internal space. A pressure adjusting device that allows the gas to be released into the external space and that prevents the gas from entering from the external space into the internal space at each of the gas releasing mechanisms, and between each of the gas releasing mechanisms, A power storage device is described in which buffer spaces individually partitioned by each of the gas release mechanisms are formed.

JP 2012-156404 A JP 2012-156489 A

  However, when providing a drilling device having a blade support and a blade member as in Patent Document 1, a new process for providing the drilling device is required, the manufacturing process becomes complicated, and productivity is also increased. There was a problem of lowering. Moreover, since it is necessary to provide a new component called a drilling device, the cost increases accordingly.

  In addition, when providing a safety valve mechanism (gas release mechanism, etc.) for escaping gas generated inside the exterior body outside the exterior body as in Patent Document 2, a new process for providing the safety valve mechanism is required. Thus, there are problems that the manufacturing process becomes complicated and the productivity decreases. Moreover, since it is necessary to provide a new component called a safety valve mechanism, the cost increases accordingly.

  The present invention has been made in view of such a technical background, has good productivity, can suppress costs, can secure sufficient seal strength, and excessively increases the internal pressure of the electricity storage device. Occasionally, destruction (peeling) occurs inside the sealant layer, and degassing is performed to prevent the exterior material from rupturing due to an increase in internal pressure. Thus, an object of the present invention is to provide a sealant film for an exterior material of an electricity storage device, an exterior material for an electricity storage device, and an electricity storage device that are less likely to cause continuous destruction and can be suppressed from whitening during molding.

  In order to achieve the above object, the present invention provides the following means.

[1] A first resin layer containing 50% by mass or more of a random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component;
A first elastomer-modified olefin-based resin having a crystallization temperature of 105 ° C. or more and a crystallization energy of 50 J / g or more, and a crystallization temperature of 85 ° C. or more and a crystallization energy of 30 J / g or less. A second resin layer formed of a mixed resin containing two elastomer-modified olefin resins, and a laminate of two or more layers,
The first elastomer-modified olefin resin comprises an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer,
The second elastomer-modified olefin resin is composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component,
In the second resin layer, the total amount of the content of the first elastomer-modified olefin resin and the content of the second elastomer-modified olefin resin is 50% by mass or more, Sealant film.

  [2] The sealant film for an exterior material of an electricity storage device according to the above item 1, wherein the content rate of the second elastomer-modified olefin resin in the second resin layer is 1% by mass to 50% by mass.

  [3] The sealant film for an exterior material for an electricity storage device according to item 1 or 2, wherein the elastomer is ethylene propylene rubber.

[4] The first resin layer contains an antiblocking agent and a slip agent together with the random copolymer,
The sealant for an exterior material of an electricity storage device according to any one of the preceding items 1 to 3, wherein the second resin layer contains a slip agent together with the first elastomer-modified olefin resin and the second elastomer-modified olefin resin. the film.

  [5] The sealant film for an exterior material for an electricity storage device according to any one of items 1 to 4, wherein the second elastomer-modified olefin-based resin has two or more crystallization peaks in a DSC measurement graph.

  [6] The sealant film for an exterior material for an electricity storage device according to any one of the aforementioned Items 1 to 5, comprising only the first resin layer and the second resin layer laminated on one side of the first resin layer.

  [7] including the second resin layer, a first resin layer laminated on one surface of the second resin layer, and a first resin layer laminated on the other surface of the second resin layer. 6. The sealant film for an exterior material for an electricity storage device according to any one of 1 to 5 above, comprising a laminate in which at least three layers are laminated.

[8] A base material layer as an outer layer, an inner sealant layer made of the sealant film according to any one of items 1 to 7, and a metal foil layer disposed between both the layers,
In the inner sealant layer, the first resin layer is disposed on the innermost layer side.

  [9] An exterior case for an electricity storage device comprising the molded body of the exterior material as described in 8 above.

  [10] A method for manufacturing an exterior case for an electricity storage device, comprising subjecting the exterior material for an electricity storage device according to item 8 to deep drawing or overmolding.

[11] An electricity storage device body,
The exterior member for an electricity storage device according to item 8 and / or the exterior member comprising the exterior case for an electricity storage device according to item 9 above,
The electricity storage device, wherein the electricity storage device body is covered with the exterior member.

  In the invention of [1], since the first resin layer containing 50% by mass or more of a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component is provided, By disposing the first resin layer on the innermost layer side of the inner sealant layer in the exterior material, the first resin layer can be sufficiently sealed even at a relatively low temperature (sufficient sealing strength can be ensured). The second resin layer includes a first elastomer-modified olefin resin having a crystallization temperature of 105 ° C. or more and a crystallization energy of 50 J / g or more, a crystallization temperature of 85 ° C. or more and a crystallization energy. Since the composition is a combination of a second elastomer-modified olefin resin having a viscosity of 30 J / g or less, the compatibility between the elastomer component and the olefin resin is good, and the dispersibility of the elastomer component is also good. Thus, when the seal portion breaks due to excessive increase in internal pressure of the pair of exterior materials in which the inner sealant layers are heat-sealed, the cohesive failure occurs in the second resin layer (inside the sealant layer). The above-mentioned destruction (peeling) for preventing bursting because it is difficult to break (peel) at the interface between the metal foil layer and the inner sealant layer. The time of the place occurs the advantage that hardly proceeds destruction continuous as a starting point the fracture site.

  Further, since the compatibility of the interface between the elastomer phase and the olefin resin phase is good, voids (cavities generated inside the molded product) are hardly generated, and whitening during molding is also suppressed. Further, since the crystallization temperature of the first elastomer-modified olefin resin is 105 ° C. or higher, the second resin layer is hardly crushed during heat sealing, and sufficient insulation can be ensured.

  Furthermore, since it is not necessary to provide a separate new component (a drilling device or a gas discharge mechanism as in the prior art) in order to allow gas to escape to the outside, the cost can be reduced by that amount, and more compactness can be achieved. And the productivity is good.

  In the invention of [2], the above effects can be sufficiently ensured. In particular, the second resin layer is more difficult to be crushed during heat sealing, and further sufficient insulation can be secured.

  In the invention of [3], the above effects can be more sufficiently ensured.

  In the invention of [4], excellent slipperiness can be imparted to the surface of the exterior material, and when the exterior material is molded, molding with a deeper molding depth can be performed well, and whitening at the time of molding is sufficient Can be suppressed.

  In the invention of [5], the effects described above can be more sufficiently ensured.

  In the inventions [6] and [7], the above effects can be more sufficiently ensured.

  In the invention of [8], productivity is good, costs can be suppressed, sufficient seal strength can be secured, and when the internal pressure of the electricity storage device rises excessively, the second resin layer (inside the sealant layer) Since cohesive failure occurs, it is possible to prevent rupture of the exterior material due to an increase in internal pressure, and at the same time, when the above-mentioned rupture location for preventing rupture occurs, continuous rupture starting from the rupture location Therefore, it is possible to provide an exterior material for an electricity storage device that is difficult to proceed and can suppress whitening during molding.

  In the invention of [9], productivity is good, costs can be suppressed, sufficient seal strength can be secured, and when the internal pressure of the electricity storage device rises excessively, the second resin layer (inside the sealant layer) Since cohesive failure occurs, it is possible to prevent rupture of the exterior material due to an increase in internal pressure, and at the same time, when the above-mentioned rupture location for preventing rupture occurs, continuous rupture starting from the rupture location Therefore, it is possible to provide an outer case for an electricity storage device that is difficult to progress and can suppress whitening during molding.

  In the invention of [10], cost can be suppressed and sufficient sealing strength can be secured, and cohesive failure occurs in the second resin layer (inside the sealant layer) when the internal pressure of the electricity storage device rises excessively. In addition, it is possible to prevent the exterior material from being ruptured due to an increase in internal pressure due to degassing, and when the rupture portion for preventing the rupture occurs, it is difficult to proceed with continuous breakage starting from the rupture portion. An exterior case for an electricity storage device that can also suppress whitening at the time can be produced with high production efficiency.

  In the invention of [11], sufficient sealing strength can be secured for the exterior material, and when the internal pressure of the electricity storage device is excessively increased, cohesive failure occurs in the second resin layer (inside the sealant layer), and gas is released. As a result, it is possible to prevent the exterior material from being ruptured due to an increase in internal pressure, and when the above-mentioned fractured portion for preventing the bursting occurs, it is difficult for continuous fracture to proceed from the fractured portion, and whitening during molding is also suppressed. It is possible to provide an electricity storage device that can be used.

It is sectional drawing which shows one Embodiment of the exterior material for electrical storage devices which concerns on this invention. It is sectional drawing which shows other embodiment of the exterior material for electrical storage devices which concerns on this invention. It is sectional drawing which shows one Embodiment of the electrical storage device which concerns on this invention. It is a perspective view shown in the separated state before heat-sealing the exterior material (planar thing) which comprises the electrical storage device of FIG. 3, the electrical storage device main-body part, and an exterior case (molded object shape | molded by the solid shape).

  One embodiment of an exterior material 1 for an electricity storage device according to the present invention is shown in FIG. The power storage device exterior material 1 is used, for example, as an exterior material for a lithium ion secondary battery. The electricity storage device exterior material 1 may be used as it is without being molded, or may be used as an exterior case 10 after being subjected to molding such as deep drawing molding or overhang molding. Good (see FIG. 4).

  In the power storage device exterior material 1, the base material layer (outer layer) 2 is laminated and integrated on one surface of the metal foil layer 4 via the first adhesive layer 5, and the other side of the metal foil layer 4. The inner sealant layer (inner layer) 3 is laminated and integrated on the surface with the second adhesive layer 6 interposed therebetween (see FIGS. 1 and 2).

  In the exterior material 1 of FIG. 1, the inner sealant layer (inner layer) 3 is composed of only a first resin layer 7 and a second resin layer 8 laminated on one side of the first resin layer. One resin layer 7 is arranged on the innermost layer side.

  2, the inner sealant layer (inner layer) 3 includes a second resin layer 8, a first resin layer 7 laminated on one surface of the second resin layer 8, and the The first resin layer 7 is laminated on the other surface of the second resin layer 8. The first resin layer 7 is disposed on the innermost layer side.

  The detailed configuration of the first resin layer 7 and the second resin layer 8 will be described later.

  In the present invention, the inner sealant layer (inner layer) 3 has excellent chemical resistance against highly corrosive electrolytes used in lithium ion secondary batteries and the like, and heat seals the exterior material. It plays a role of imparting sex.

  In the present invention, the inner sealant layer (inner layer) 3 is a first resin containing 50% by mass or more of a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component. Layer 7, a first elastomer-modified olefin resin having a crystallization temperature (Tcp) of 105 ° C. or more and a crystallization energy (ΔHc) of 50 J / g or more, and a crystallization temperature (Tcp) of 85 ° C. or more. And a second resin layer 8 formed of a mixed resin containing a second elastomer-modified olefin resin having a crystallization energy (ΔHc) of 30 J / g or less. Become. The innermost layer of the inner sealant layer (inner layer) 3 is preferably formed of the first resin layer 7 (see FIGS. 1 and 2).

  The first elastomer-modified olefin resin (first polypropylene block copolymer) is composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer includes “propylene” and It is an elastomer-modified body of a random copolymer containing “another copolymer component excluding propylene”, and the “another copolymer component excluding propylene” is not particularly limited. In addition to olefin components such as 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene, butadiene and the like can be given. The elastomer is not particularly limited, but EPR (ethylene propylene rubber) is preferably used.

  The second elastomer-modified olefin resin (second polypropylene block copolymer) is composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer includes “propylene” and It is an elastomer-modified body of a random copolymer containing “another copolymer component excluding propylene”, and the “another copolymer component excluding propylene” is not particularly limited. In addition to olefin components such as 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene, butadiene and the like can be given. The elastomer is not particularly limited, but EPR (ethylene propylene rubber) is preferably used.

  The first resin layer 7 includes 50% by mass or more of a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component. The “other copolymerization component excluding propylene” is not particularly limited, and examples thereof include olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene. Other examples include butadiene. Sufficient heat seal strength can be ensured when the content of the random copolymer is 50% by mass or more. Especially, it is preferable that the content rate of the said random copolymer in the said 1st resin layer 7 is set to 70 mass% or more. The random copolymer (a random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component) is preferably a random copolymer having a melting point of 2 or more. The heat-seal performance can be further improved by the low-melting-point random copolymer component (heat-seal strength can be further increased), and at the time of heat-sealing by the high-melting-point random copolymer component, The effect that one resin layer 7 is hard to be crushed and sufficient insulation can be secured is obtained.

  The second resin layer 8 includes a first elastomer-modified olefin resin having a crystallization temperature (Tcp) of 105 ° C. or more and a crystallization energy (ΔHc) of 50 J / g or more, and a crystallization temperature (Tcp). And a second elastomer-modified olefin resin having a crystallization energy (ΔHc) of 30 J / g or less. When the crystallization temperature of the first elastomer-modified olefin resin is less than 105 ° C., whitening is prominent during molding, and the second resin layer 8 is liable to be crushed during heat sealing, and the insulating property tends to be insufficient (Comparative Example 4). reference). In addition, when the crystallization temperature of the second elastomer-modified olefin resin is less than 85 ° C., whitening significantly occurs during molding (see Comparative Example 5). Further, when the crystallization energy (ΔHc) of the first elastomer-modified olefin resin is less than 50 J / g, the cohesion degree of the peeling interface is moderate, and the cohesive failure of the peeling interface hardly occurs, that is, the metal foil layer at the time of peeling. Peeling is likely to occur at the interface between the inner sealant layer and the inner sealant layer, and continuous peeling is likely to proceed starting from the peeled portion of the interface, and the second resin layer 8 is liable to be crushed and the insulating property is likely to be insufficient (Comparative Example). 6). When the crystallization energy (ΔHc) of the second elastomer-modified olefin resin exceeds 30 J / g, whitening occurs to some extent during molding, and the degree of cohesion at the peeling interface is moderate, and the cohesive failure at the peeling interface. In other words, peeling is likely to occur at the interface between the metal foil layer and the inner sealant layer at the time of peeling, and continuous peeling is likely to proceed starting from the peeling portion of this interface (see Comparative Example 7). Further, if the first elastomer-modified olefin resin having a crystallization temperature (Tcp) of 105 ° C. or higher and a crystallization energy (ΔHc) of 50 J / g or more is not contained, whitening occurs to some extent during molding. , The cohesion degree of the peeling interface is medium, and the cohesive failure of the peeling interface is difficult to occur, that is, the peeling is likely to occur at the interface between the metal foil layer and the inner sealant layer at the time of peeling. Peeling is likely to proceed, and the second resin layer 8 is liable to be crushed, resulting in insufficient insulation (see Comparative Example 2). Further, if the second elastomer-modified olefin resin having a crystallization temperature (Tcp) of 85 ° C. or higher and a crystallization energy (ΔHc) of 30 J / g or less is not contained, whitening is remarkably generated during molding. In addition, the cohesion degree of the peeling interface is medium, and the cohesive failure of the peeling interface is difficult to occur, i.e., peeling is likely to occur at the interface between the metal foil layer and the inner sealant layer at the time of peeling. There is a problem that the peeling is likely to proceed (see Comparative Example 3).

  Therefore, in the present invention, the second resin layer 8 includes a first elastomer-modified olefin resin having a crystallization temperature (Tcp) of 105 ° C. or more and a crystallization energy (ΔHc) of 50 J / g or more, And a second elastomer-modified olefin resin having a crystallization temperature (Tcp) of 85 ° C. or more and a crystallization energy (ΔHc) of 30 J / g or less.

  The crystallization temperature of the first elastomer-modified olefin resin is preferably 105 ° C. or higher and 135 ° C. or lower. The crystallization energy of the first elastomer-modified olefin resin is preferably 50 J / g or more and 75 J / g or less. The melting point of the second elastomer-modified olefin resin is preferably 85 ° C. or higher and 125 ° C. or lower. The crystallization energy of the second elastomer-modified olefin resin is preferably 5 J / g or more and 30 J / g or less, more preferably 10 J / g or more and 25 J / g or less, and more preferably 10 J / g or more and 20 J / g or less. It is particularly preferred that it is g or less.

  Regarding the first elastomer-modified olefin resin and the second elastomer-modified olefin resin, the mode of “elastomer modification” may be graft polymerization or other modified modes.

  The first elastomer-modified olefin resin and the second elastomer-modified olefin resin can be produced, for example, by the following reactor-made method. This is merely an example, and is not particularly limited to those manufactured by such a manufacturing method.

  First, homopolypropylene is polymerized by supplying Ziegler-Natta catalyst, promoter and propylene to the first reactor. The obtained homopolypropylene is transferred to the second reactor in a state containing unreacted propylene and a Ziegler-Natta catalyst. In the second reactor, further propylene is added to polymerize the homopolypropylene. The obtained homopolypropylene is moved to the third reactor in a state containing unreacted propylene and a Ziegler-Natta catalyst. In the third reactor, ethylene and propylene are further added to polymerize ethylene-propylene rubber (EPR) obtained by copolymerizing ethylene and propylene, whereby the first elastomer-modified olefin resin or the second elastomer-modified olefin resin is obtained. Can be manufactured. For example, the first elastomer-modified olefin resin can be produced by adding a solvent and producing it in the liquid phase, and the second elastomer-modified olefin resin can be produced by reacting in the gas phase without using a solvent. Can be manufactured.

  In the second resin layer 8, the content of the second elastomer-modified olefin resin is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, and more preferably 10% by mass. It is particularly preferred to be ˜25% by weight.

  The content of the first elastomer-modified olefin resin in the second resin layer 8 is preferably 99% by mass to 50% by mass, more preferably 95% by mass to 70% by mass, and 90% by mass. It is particularly preferable that the content be ˜75% by mass.

  The second resin layer 8 preferably has a sea-island structure. Due to such a sea-island structure, when the seal portion breaks due to excessive increase in internal pressure, breakage occurs at the interface between the olefinic resin phase and the elastomer phase in the second resin layer 8. As a result, cohesive failure occurs inside the second resin layer 8, and therefore, failure (peeling) hardly occurs at the interface between the metal foil layer and the inner sealant layer. In this case, it is possible to obtain an effect that it is difficult for continuous destruction to proceed from the destruction portion. It is preferable that the elastomer (component) forms an island in the sea-island structure.

  The second elastomer-modified olefin resin preferably has two or more crystallization peaks in a DSC (differential scanning calorimeter) measurement graph. In the case of having two crystallization peaks, the crystallization peak on the high temperature side (crystallization temperature Tcp2) is 90 ° C. or more, and the crystallization peak on the low temperature side (crystallization temperature Tcp1) is 80 ° C. or less. Preferably there is. In the case of having three or more crystallization peaks, the crystallization peak on the highest temperature side (crystallization temperature) is 90 ° C. or higher, and the crystallization peak on the lowest temperature side (crystallization temperature) is 80 ° C. It is preferable that:

  The integrated value (area) of the crystallization peak curve is the crystallization energy (ΔHc). When the DSC measurement graph has two crystallization peaks, the integrated value of the lower temperature crystallization peak (Tcp1) curve is the crystallization energy “ΔHc1”, and the higher temperature crystal. The integrated value of the crystallization peak (Tcp2) curve is the crystallization energy “ΔHc2” (see Tables 1 and 2).

  The first resin layer 7 is preferably not in the form of a sea-island structure. In such a case, the electricity storage device body 31 is accommodated in the exterior material 1 and / or the exterior case 10, and the peripheral portions (including the flange portion 29) are heat sealed to enclose the electricity storage device body 31. Later, when the peripheral portion (including the flange portion 29) is bent, the formation of voids (spaces) at the interface between the olefin resin phase and the elastomer phase in the first resin layer 7 can be sufficiently suppressed. There is an advantage that sufficient insulation can be secured. In particular, when the first resin layer 7 is arranged at a position adjacent to the metal foil layer 7 (see FIG. 2), the above effect becomes remarkable.

  The first resin layer 7 preferably contains an antiblocking agent and a slip agent together with the random copolymer. The second resin layer 8 preferably contains a slip agent together with the first elastomer-modified olefin resin and the second elastomer-modified olefin resin.

  The anti-blocking agent is not particularly limited, and examples thereof include silica and aluminum silicate. The slip agent is not particularly limited, and examples thereof include fatty acid amides such as erucic acid amide, stearic acid amide, and oleic acid amide, and waxes such as crystallin wax and polyethylene wax.

  The sealant film constituting the inner sealant layer (inner layer) 3 is preferably produced by a molding method such as multilayer extrusion molding, inflation molding, T-die cast film molding or the like.

  The thickness of the inner sealant layer (inner layer) 3 is preferably set to 20 μm to 80 μm. When the thickness is 20 μm or more, the occurrence of pinholes can be sufficiently prevented, and when the thickness is set to 80 μm or less, the amount of resin used can be reduced and the cost can be reduced. Especially, it is especially preferable that the thickness of the inner sealant layer (inner layer) 3 is set to 30 μm to 50 μm.

  The inner sealant layer (inner layer) 3 is formed on the second resin layer 8, the first resin layer 7 laminated on one surface of the second resin layer 8, and the other surface of the second resin layer 8. In the case of a three-layer laminated structure composed of the laminated first resin layers 7 (see FIG. 2), the thickness ratio of the first resin layer 7 / second resin layer 8 / first resin layer 7 is The range is preferably 0.5 / 9 / 0.5 to 3/4/3.

  The method for laminating the sealant film constituting the inner sealant layer (inner layer) 3 on the metal foil layer 4 is not particularly limited, but includes a dry laminate method, a sandwich laminate method (an adhesive film such as acid-modified polypropylene). And then laminating this between the metal foil and the sealant film, followed by heat laminating with a hot roll).

  In the present invention, the base material layer (outer layer) 2 is preferably formed of a heat resistant resin layer. As the heat-resistant resin constituting the heat-resistant resin layer 2, a heat-resistant resin that does not melt at the heat sealing temperature when heat-sealing the exterior material is used. As the heat resistant resin, it is preferable to use a heat resistant resin having a melting point higher by 10 ° C. or more than the melting point of the thermoplastic resin constituting the inner sealant layer 3, and 20 higher than the melting point of the thermoplastic resin constituting the inner sealant layer 3. It is particularly preferable to use a heat resistant resin having a melting point higher by at least ° C.

  The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include polyamide films such as nylon films, polyester films, and the like, and these stretched films are preferably used. Among them, the heat-resistant resin layer 2 includes a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film or a biaxially stretched polyethylene film. It is particularly preferable to use a phthalate (PEN) film. The nylon film is not particularly limited, and examples thereof include 6 nylon film, 6,6 nylon film, MXD nylon film, and the like. The heat-resistant resin layer 2 may be formed as a single layer, or may be formed as a multilayer composed of a polyester film / polyamide film (such as a multilayer composed of PET film / nylon film). Also good.

  The thickness of the base material layer (outer layer) 2 is preferably 2 μm to 50 μm. When using a polyester film, the thickness is preferably 2 μm to 50 μm, and when using a nylon film, the thickness is preferably 7 μm to 50 μm. By setting it above the above preferred lower limit value, it is possible to ensure sufficient strength as an exterior material, and by setting it below the above preferred upper limit value, it is possible to reduce the stress at the time of molding such as stretch forming, draw forming, etc. and improve moldability Can be made.

  In the present invention, the metal foil layer 4 plays a role of providing the exterior material 1 with a gas barrier property that prevents oxygen and moisture from entering. Although it does not specifically limit as said metal foil layer 4, For example, aluminum foil, SUS foil (stainless steel foil), copper foil etc. are mentioned, Among these, aluminum foil and SUS foil (stainless steel foil) are used. Is preferred. The thickness of the metal foil layer 4 is preferably 20 μm to 100 μm. When it is 20 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing metal foil, and when it is 100 μm or less, it is possible to reduce the stress at the time of forming such as stretch forming and draw forming, thereby improving formability. be able to.

The metal foil layer 4 is preferably subjected to chemical conversion treatment on at least the inner surface (surface on the second adhesive layer 6 side). By performing such a chemical conversion treatment, corrosion of the metal foil surface by the contents (battery electrolyte or the like) can be sufficiently prevented. For example, the metal foil is subjected to chemical conversion treatment by the following treatment. That is, for example, on the surface of the metal foil that has been degreased,
1) phosphoric acid;
Chromic acid,
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a metal salt of fluoride and a nonmetal salt of fluoride; 2) phosphoric acid;
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of chromic acid and a chromium (III) salt, 3) phosphoric acid,
At least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins;
At least one compound selected from the group consisting of chromic acid and a chromium (III) salt;
An aqueous solution of a mixture comprising at least one compound selected from the group consisting of a fluoride metal salt and a fluoride non-metal salt. After applying an aqueous solution of any one of the above 1) to 3), drying is performed. Then, chemical conversion treatment is performed.

The conversion coating, chromium coating weight preferably is 0.1mg / m ² ~50mg / m ² as a (per one surface), in particular 2mg / m ² ~20mg / m 2 preferred.

  The first adhesive layer 5 is not particularly limited, and examples thereof include a polyurethane adhesive layer, a polyester polyurethane adhesive layer, and a polyether polyurethane adhesive layer. The thickness of the first adhesive layer 5 is preferably set to 1 μm to 5 μm. Especially, it is especially preferable that the thickness of the said 1st adhesive bond layer 5 is set to 1 micrometer-3 micrometers from a viewpoint of thickness reduction of the exterior material 1 and weight reduction.

  Although it does not specifically limit as said 2nd adhesive bond layer 6, For example, what was illustrated as said 1st adhesive bond layer 5 can be used, However, The polyolefin-type adhesive agent with few swelling by electrolyte solution is used. Is preferred. The thickness of the second adhesive layer 6 is preferably set to 1 μm to 5 μm. Especially, it is especially preferable that the thickness of the said 2nd adhesive bond layer 6 is set to 1 micrometer-3 micrometers from a viewpoint of thickness reduction of the exterior material 1 and weight reduction.

  An exterior case (battery case or the like) 10 can be obtained by molding the outer packaging material 1 of the present invention (deep drawing molding, stretch molding, etc.) (FIG. 4). In addition, the exterior material 1 of this invention can also be used as it is, without using for shaping | molding (FIG. 4).

  One Embodiment of the electrical storage device 30 comprised using the exterior | packing material 1 of this invention is shown in FIG. The electricity storage device 30 is a lithium ion secondary battery. In this embodiment, as shown in FIGS. 3 and 4, an exterior member 15 is configured by an exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1. Accordingly, a power storage device main body 31 (electrochemical element or the like) 31 having a substantially rectangular parallelepiped shape is stored in the storage recess of the external case 10 obtained by molding the exterior material 1 of the present invention. On the inner sealant layer 3 side of the inner sealant layer 3 of the present invention without being molded, and the peripheral portion of the inner sealant layer 3 of the planar exterior material 1; The power storage device 30 of the present invention is configured by sealing and sealing the inner sealant layer 3 of the flange portion (sealing peripheral portion) 29 of the outer case 10 by heat sealing (FIG. 3). 4). The inner surface of the housing recess of the outer case 10 is an inner sealant layer 3, and the outer surface of the housing recess is a base material layer (outer layer) 2 (see FIG. 4).

  In FIG. 3, reference numeral 39 denotes a heat seal portion in which the peripheral portion of the exterior material 1 and the flange portion (sealing peripheral portion) 29 of the external case 10 are joined (welded). In the electricity storage device 30, the tip end portion of the tab lead connected to the electricity storage device main body 31 is led out of the exterior member 15, but is not shown.

  The power storage device main body 31 is not particularly limited, and examples thereof include a battery main body, a capacitor main body, and a capacitor main body.

  The width of the heat seal part 39 is preferably set to 0.5 mm or more. Sealing can be reliably performed by setting it as 0.5 mm or more. Especially, it is preferable to set the width | variety of the said heat seal part 39 to 3 mm-15 mm.

  In the above embodiment, the exterior member 15 has a configuration including the exterior case 10 obtained by molding the exterior material 1 and the planar exterior material 1 (see FIGS. 3 and 4). It is not particularly limited to such a combination. For example, the exterior member 15 may be composed of a pair of planar exterior materials 1 or may be composed of a pair of exterior cases 10. May be.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Example 1>
After applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol on both surfaces of the aluminum foil 4 having a thickness of 35 μm, drying is performed at 180 ° C. Then, a chemical conversion film was formed. The amount of chromium deposited on this chemical film was 10 mg / m ² per side.

  Next, a biaxially stretched 6 nylon film 2 having a thickness of 15 μm was dry-laminated (laminated) on one surface of the chemical conversion-treated aluminum foil 4 via a two-component curable urethane adhesive 5.

  Next, a 4 μm-thick first resin layer 7 made of an ethylene-propylene random copolymer and a 22 μm-thick second resin layer 8 (crystallization temperature is 114 ° C., crystallization energy is 54.2 J / g) The second resin layer 8 having a composition of 99% by mass of the first elastomer-modified olefin resin and 1% by mass of the second elastomer-modified olefin resin having a crystallization temperature of 96 ° C. and a crystallization energy of 15 J / g. ), And by co-extrusion using a T-die so that the first resin layer 7 made of an ethylene-propylene random copolymer and having a thickness of 4 μm is laminated in this order, these three layers are laminated. After obtaining a sealant film (first resin layer / second resin layer / first resin layer) 3 having a thickness of 30 μm, one surface of the first resin layer 7 of the sealant film 3 is coated with a two-component curable maleic acid. Degeneration Dry laminate is carried out by being superimposed on the other surface of the aluminum foil 4 after the dry lamination, and sandwiched between a rubber nip roll and a laminate roll heated to 100 ° C. via a polypropylene adhesive 6. Then, after that, it was aged (heated) at 50 ° C. for 5 days, thereby obtaining the electricity storage device exterior material 1 having the configuration shown in FIG.

As the two-component curable maleic acid-modified polypropylene adhesive, 100 parts by mass of maleic acid-modified polypropylene (melting point: 80 ° C., acid value: 10 mgKOH / g) as a main agent, isocyanurate of hexamethylene diisocyanate as a curing agent (NCO content: 20% by mass) 8 parts by mass, and using an adhesive solution in which a solvent is further mixed, the aluminum foil 4 has a solid content applied amount of 2 g / m ² . After applying to the other surface and drying by heating, it was superimposed on one surface of the first resin layer 7 of the sealant film 3.

<Example 2>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1 except that a second elastomer layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was used. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Comparative Example 1>
As the resin constituting the first resin layer 7, instead of the ethylene-propylene random copolymer, a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g is used. Except having used, it carried out similarly to Example 2, and obtained the exterior | packing material for electrical storage devices.

<Comparative example 2>
As the second resin layer 8, a 22 μm thick second resin layer (second resin layer made of a second elastomer-modified olefin resin having a crystallization temperature of 96 ° C. and a crystallization energy of 15 J / g) is used. Except that, an exterior material for an electricity storage device was obtained in the same manner as in Example 1.

<Comparative Example 3>
Second resin layer 8 having a thickness of 22 μm (second resin layer made of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g) Except that was used, an exterior material for an electricity storage device was obtained in the same manner as in Example 1.

<Example 3>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 106 ° C. and a crystallization energy of 54.0 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1 except that a second elastomer layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was used. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Comparative example 4>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 96 ° C. and a crystallization energy of 53.0 J / g, a crystallization temperature) In the same manner as in Example 1, except that a second resin layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g is 96 ° C. An exterior material was obtained.

<Example 4>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) 2 is the same as in Example 1 except that a second resin layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 14 J / g is used. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Comparative Example 5>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) In the same manner as in Example 1, except that a second elastomer layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 10 J / g is used. An exterior material was obtained.

<Comparative Example 6>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 106 ° C. and a crystallization energy of 45.5 J / g, a crystallization temperature) In the same manner as in Example 1, except that a second resin layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g is 96 ° C. An exterior material was obtained.

<Example 5>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (80% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1, except that a second elastomer layer having a composition of 20% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was 96 ° C. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Example 6>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (70% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1 except that a second resin layer having a composition of 30% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was 96 ° C. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Example 7>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (80% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 117 ° C. and a crystallization energy of 61.2 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1, except that a second elastomer layer having a composition of 20% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was 96 ° C. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Example 8>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (70% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 117 ° C. and a crystallization energy of 61.2 J / g, a crystallization temperature) 2 was used in the same manner as in Example 1 except that a second resin layer having a composition of 30% by mass of a second elastomer-modified olefin resin having a crystallization energy of 15 J / g was 96 ° C. The exterior | packing material 1 for electrical storage devices of the structure shown in this was obtained.

<Comparative Example 7>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) In the same manner as in Example 1, except that a second resin layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystallization energy of 40 J / g is used. An exterior material was obtained.

<Comparative Example 8>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (99% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) Was obtained in the same manner as in Example 1 except that a second resin layer having a composition of 1 mass% of EPR with a crystallization energy of 11 J / g was used.

<Comparative Example 9>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (90% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) Was obtained in the same manner as in Example 1 except that a second resin layer having a composition of EPR 10% by mass with a crystallization energy of 11 J / g was used.

<Comparative Example 10>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (80% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) Was obtained in the same manner as in Example 1 except that the second resin layer having a composition of 20 mass% EPR with a crystallization energy of 11 J / g was used.

<Comparative Example 11>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (70% by mass of a first elastomer-modified olefin resin having a crystallization temperature of 114 ° C. and a crystallization energy of 54.2 J / g, a crystallization temperature) Was obtained in the same manner as in Example 1 except that a second resin layer having a composition of 30 mass% EPR with a crystallization energy of 11 J / g was used.

<Example 9>
After applying a chemical conversion treatment solution composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and alcohol on both surfaces of the aluminum foil 4 having a thickness of 35 μm, drying is performed at 180 ° C. Then, a chemical conversion film was formed. The amount of chromium deposited on this chemical film was 10 mg / m ² per side.

  Next, a biaxially stretched 6 nylon film 2 having a thickness of 15 μm was dry-laminated (laminated) on one surface of the chemical conversion-treated aluminum foil 4 via a two-component curable urethane adhesive 5.

  Next, an 8 μm-thick first resin layer 7 made of an ethylene-propylene random copolymer, and a 22 μm-thick second resin layer 8 (crystallization temperature is 114 ° C., crystallization energy is 54.2 J / g) The second elastomer layer 8 having a composition of 90% by mass of the first elastomer-modified olefin resin, crystallization temperature of 96 ° C., and 10% by mass of the second elastomer-modified olefin resin having a crystallization energy of 15 J / g. After obtaining a sealant film (first resin layer 7 / second resin layer 8) 3 having a thickness of 30 μm by co-extrusion using a T-die so that the two layers are laminated. Then, one surface of the first resin layer 7 of the sealant film 3 is overlapped on the other surface of the aluminum foil 4 after the dry lamination via a two-component curable maleic acid-modified polypropylene adhesive 6. Then, it is sandwiched between a rubber nip roll and a laminating roll heated to 100 ° C. and subjected to pressure laminating to dry laminate, and then aged (heated) at 50 ° C. for 5 days, as shown in FIG. An exterior material 1 for an electricity storage device having a configuration was obtained.

As the two-component curable maleic acid-modified polypropylene adhesive, 100 parts by mass of maleic acid-modified polypropylene (melting point: 80 ° C., acid value: 10 mgKOH / g) as a main agent, isocyanurate of hexamethylene diisocyanate as a curing agent (NCO content: 20% by mass) 8 parts by mass, and using an adhesive solution in which a solvent is further mixed, the aluminum foil 4 has a solid content applied amount of 2 g / m ² . After applying to the other surface and drying by heating, it was superimposed on one surface of the first resin layer 7 of the sealant film 3.

  In Examples 1 to 9 and Comparative Examples 1 to 11, the first elastomer-modified olefin resin is composed of an EPR-modified homopolypropylene and an EPR modified body of an ethylene-propylene random copolymer, and the second elastomer-modified olefin resin. Consists of an EPR-modified homopolypropylene and an EPR-modified product of an ethylene-propylene random copolymer. The EPR means ethylene-propylene rubber.

In Tables 1 and 2, the following abbreviations representing the first and second elastomer-modified olefin resins represent the following resins, respectively.
“B-PP1X”: a first elastomer-modified olefin resin “B-PP1Y” having a crystallization temperature (Tcp) of 114 ° C. and a crystallization energy (ΔHc) of 54.2 J / g, a crystallization temperature ( The first elastomer-modified olefin resin “B-PP1Z” having a Tcp) of 117 ° C. and a crystallization energy (ΔHc) of 61.2 J / g, the crystallization temperature (Tcp) of 106 ° C., and crystallization The first elastomer-modified olefin resin “B-PP1V” having an energy (ΔHc) of 54.0 J / g. The crystallization temperature (Tcp) is 96 ° C., and the crystallization energy (ΔHc) is 53.0 J / g. The first elastomer-modified olefin resin “B-PP1W” which is g. The first crystallization temperature (Tcp) is 106 ° C. and the crystallization energy (ΔHc) is 45.5 J / g. Lastomer-modified olefin resin “B-PP2X”: second elastomer-modified olefin resin “B-PP2Y”: crystal having a crystallization temperature (Tcp2) of 96 ° C. and a crystallization energy (ΔHc2) of 15 J / g The second elastomer-modified olefin resin “B-PP2Z” having a crystallization temperature (Tcp) of 88 ° C. and a crystallization energy (ΔHc) of 14 J / g, a crystallization temperature (Tcp) of 83 ° C. The second elastomer-modified olefin resin “B-PP2V” having a crystallization energy (ΔHc) of 10 J / g. The crystallization temperature (Tcp) is 108 ° C., and the crystallization energy (ΔHc) is 40 J / g. Second elastomer-modified olefin resin.

In the tables, the following abbreviations indicate the following resins, respectively.
“EPR”: ethylene-propylene rubber “r-PPA”: ethylene-propylene random copolymer “r-PPB”: ethylene-propylene random copolymer.

  The “crystallization temperature” of each resin is the crystallization peak temperature (Tcp) measured by differential scanning calorimetry (DSC) according to JIS K7121-1987, and the “crystallization energy” of each resin. "Is the crystallization energy (ΔHc) measured by differential scanning calorimetry (DSC) in accordance with JIS K7122-1987, both measured under the following measurement conditions.

Temperature rising / lowering speed: Temperature rising / lowering speed from 23 ° C to 210 ° C at 10 ° C / min Sample fee: 5mg metering Container: Using aluminum pan Equipment: "DSC-60A" manufactured by Shimadzu Corporation
Regarding “crystallization energy”, when there is only one crystallization peak, “crystallization energy” is expressed as “ΔHc”, and when there are two crystallization peaks, the temperature is low. The “crystallization energy” of the higher crystallization peak is expressed as “ΔHc1”, and the “crystallization energy” of the higher temperature crystallization peak is expressed as “ΔHc2”.

  Regarding “crystallization temperature”, when only one crystallization peak exists, “crystallization temperature” is expressed as “Tcp”, and when two crystallization peaks exist, the lower one The crystallization peak (crystallization temperature) is represented by “Tcp1”, and the crystallization peak (crystallization temperature) of the higher temperature is represented by “Tcp2”.

  For each of the electricity storage device exterior materials obtained as described above, the seal strength is measured based on the following measurement method and evaluation method, and the degree of aggregation of the peeling interface when peeling is evaluated, and whitening at the time of molding The presence or absence of was evaluated.

<Seal strength measurement method>
After cutting out two test bodies having a width of 15 mm and a length of 150 mm from the obtained exterior material, Tester Sangyo Co., Ltd. in a state in which these two test bodies were overlapped so that the inner sealant layers were in contact with each other. Using a heat seal device (TP-701-A) manufactured by the manufacturer, heat seal is performed by single-sided heating under the conditions of heat seal temperature: 200 ° C., seal pressure: 0.2 MPa (gauge display pressure), and seal time: 2 seconds. went.

  Next, with respect to the pair of exterior materials in which the inner sealant layers are heat-sealed as described above, the exterior materials are manufactured using Shimadzu Access Corp. strograph (AGS-5kNX) in accordance with JIS Z0238-1988. The peel strength when the (test body) was peeled 90 degrees between the sealant inner sealant layers at a tensile rate of 100 mm / min was measured, and this was taken as the seal strength (N / 15 mm width).

  The seal strength of 30 N / 15 mm width or more is regarded as acceptable. The seal strength is desirably 40 N / 15 mm width or more.

<Evaluation method of cohesion degree of peeling interface>
After measuring the above sealing strength (peel strength), both sides of the peeled portion (destructed portion) of the inner sealant layer of the exterior material are visually observed, and the presence or absence or degree of whitening of the peeled portion (destructed portion) on both sides It can be judged that the stronger the strength, the greater the degree of aggregation).
(Criteria)
“○” indicates that whitening is remarkable and the degree of aggregation is large, “△” indicates that whitening occurs to some extent and the degree of aggregation is moderate, and “white” is not observed or there is almost no whitening and the degree of aggregation is The lower one was marked “x”.

<Evaluation method for whitening during molding>
After deep-drawing into a rectangular parallelepiped shape with a depth of 5 mm on the exterior material using the deep-drawing molding tool manufactured by Amada Co., Ltd. under the following molding conditions, the inner surface of the housing recess (inner sealant layer) of the resulting molded body 3 surface) was observed visually, and the presence or absence or degree of whitening was evaluated based on the following criteria.
(Criteria)
The molded body after molding was visually observed, and “◎” indicates that whitening was not recognized or hardly whitened, “○” indicates that whitening was small, and whitening occurred to some extent. Was marked with “Δ”, and marked whitening was marked with “x”.
(Molding condition)
Mold: Punch: 33.3 mm x 53.9 mm, Die: 80 mm x 120 mm, Corner R: 2 mm, Punch R: 1.3 mm, Die R: 1 mm
Wrinkle holding pressure: Gauge pressure: 0.475 MPa, actual pressure (calculated value): 0.7 MPa
Material: SC (carbon steel) material, punch R only is chrome plated.

<Comprehensive evaluation>
The above three evaluation results are comprehensively evaluated and evaluated in four stages. “◎” indicates that the overall evaluation is particularly excellent, “○” indicates that the overall evaluation is excellent, and the overall evaluation is slightly inferior. “△” was given for the existing product, and “X” was given for the poor overall evaluation.

  As is apparent from the table, the packaging materials for power storage devices of Examples 1 to 9 of the present invention (the packaging materials for power storage devices using the sealant film of the present invention) have sufficient seal strength, Since the degree of whitening at the peeling interface was large, the degree of aggregation at the peeling interface was high, and at the time of peeling, cohesive failure occurred inside the sealant layer, and whitening at the time of molding was also suppressed. Thus, when the exterior | cover material for electrical storage devices of Examples 1-9 of this invention was used, since the cohesive failure has arisen inside a sealant layer, the metal foil layer 4 and the inner side sealant layer 3 are peeled at the time of peeling (fracture). Peeling (destruction) is unlikely to occur at the interface, and therefore, when a delamination location (destruction location) for preventing rupture occurs, there is an advantage that continuous destruction is difficult to proceed starting from the delamination location (destruction location). .

  On the other hand, in Comparative Examples 1 to 11 that deviated from the scope of the claims of the present invention, the overall evaluation was “x”.

  The sealant film for an exterior material of an electricity storage device according to the present invention is used as a sealant film for an exterior material of an electricity storage device such as a mobile storage battery, an in-vehicle storage battery, a regenerative energy recovery storage battery, a capacitor (capacitor), or an all-solid battery.

  The exterior material for an electricity storage device according to the present invention is used as an exterior material for an electricity storage device such as a mobile storage battery, an in-vehicle storage battery, a regenerative energy recovery storage battery, a capacitor (capacitor), or an all solid state battery.

  The power storage device according to the present invention is used as a mobile storage battery, an in-vehicle storage battery, a regenerative energy recovery storage battery, a capacitor (capacitor), an all-solid battery, or the like.

DESCRIPTION OF SYMBOLS 1 ... Exterior material for electrical storage devices 2 ... Base material layer (outer layer)
3 ... Inner sealant layer (sealant film)
4 ... Metal foil layer 7 ... First resin layer 8 ... Second resin layer 10 ... Exterior case for electrical storage device (molded article)
15 ... Exterior member 30 ... Power storage device 31 ... Power storage device main body

Claims (11)

A first resin layer containing 50% by mass or more of a random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component;
A first elastomer-modified olefin-based resin having a crystallization temperature of 105 ° C. or more and a crystallization energy of 50 J / g or more, and a crystallization temperature of 85 ° C. or more and a crystallization energy of 30 J / g or less. A second resin layer formed of a mixed resin containing two elastomer-modified olefin resins, and a laminate of two or more layers,
The first elastomer-modified olefin resin comprises an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer,
The second elastomer-modified olefin resin is composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer,
The elastomer-modified random copolymer is an elastomer-modified body of a random copolymer containing propylene and other copolymer components excluding propylene as a copolymer component,
In the second resin layer, the total amount of the content of the first elastomer-modified olefin resin and the content of the second elastomer-modified olefin resin is 50% by mass or more, Sealant film.   2. The sealant film for an exterior material for an electricity storage device according to claim 1, wherein the content ratio of the second elastomer-modified olefin resin in the second resin layer is 1% by mass to 50% by mass.   The sealant film for an exterior material for an electricity storage device according to claim 1, wherein the elastomer is ethylene propylene rubber. The first resin layer contains an antiblocking agent and a slip agent together with the random copolymer,
The said 2nd resin layer contains the slip agent with the said 1st elastomer modified olefin resin and the said 2nd elastomer modified olefin resin, The exterior material of the electrical storage device of any one of Claims 1-3 Sealant film.   The sealant film for an exterior material for an electricity storage device according to any one of claims 1 to 4, wherein the second elastomer-modified olefin resin has two or more crystallization peaks in a DSC measurement graph.   The sealant film for an exterior material for an electricity storage device according to any one of claims 1 to 5, comprising only the first resin layer and the second resin layer laminated on one side of the first resin layer.   At least three layers including the second resin layer, a first resin layer laminated on one surface of the second resin layer, and a first resin layer laminated on the other surface of the second resin layer. The sealant film for an exterior material for an electricity storage device according to any one of claims 1 to 5, wherein the sealant film is made of a laminated body. A base material layer as an outer layer, an inner sealant layer comprising the sealant film according to any one of claims 1 to 7, and a metal foil layer disposed between these two layers,
In the inner sealant layer, the first resin layer is disposed on the innermost layer side.   The exterior case for electrical storage devices which consists of a molded object of the exterior material of Claim 8.   The manufacturing method of the exterior case for electrical storage devices characterized by carrying out the deep drawing shaping | molding or the extending | stretching shaping | molding of the electrical storage device exterior material of Claim 8. An electricity storage device body,
An exterior member comprising the exterior material for an electricity storage device according to claim 8 and / or the exterior case for an electricity storage device according to claim 9;
The electricity storage device, wherein the electricity storage device body is covered with the exterior member.

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