JP2017076509A - Sealant film for exterior package material of power storage device, exterior package material for power storage device, power storage device, and method for manufacturing resin composition for sealant film of power storage device exterior package material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant film for an exterior package material of a power storage device, which can prevent the fracture of an exterior package material owing to the rise in internal pressure because it is arranged so that a break (delamination) is caused in the sealant layer for degasification when the internal pressure of a power storage device increases excessively, and which is hard to allow the break to proceed continuously from its initial break point with the break for fracture prevention caused, and which enables the adequate suppression of its whitening in molding.SOLUTION: A sealant film for an exterior package material of a power storage device comprises a laminate of 2 or more layers consisting of: a first resin layer 7 including 50 mass% or more of random copolymers including propylene as a copolymerization component, and another copolymerization component except propylene; and a second resin layer 8 formed by a composition including a first elastomer-modified olefin-based resin of which the melting point is 155°C or higher and the crystal melting energy is 50 J/g or more, a second elastomer-modified olefin-based resin of which the melting point is 135°C or higher and the crystal melting energy is 30 J/g or less, and a particular polymer component.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, an electricity storage device constituted using the exterior material, and a resin for the sealant film The present invention relates to a method for producing a composition.

  In the present specification and claims, the term “melting point” means a melting peak temperature measured by differential scanning calorimetry (DSC) according to JIS K7121-1987, and “crystal melting energy”. "Means the heat of fusion (crystal melting energy) measured by differential scanning calorimetry (DSC) according to JIS K7122-1987.

  In the present specification and claims, the term “crystal melting energy” means that there are two or more crystal melting peak curves and two crystal melting energies (ΔHm1, ΔHm2) or three. If present, the highest value of crystal melting energy is assumed.

  In the present specification and claims, the term “polymer component” does not include either “first elastomer-modified olefin resin” or “second elastomer-modified olefin resin”.

  In the present specification and claims, “olefin elastomer” and “styrene elastomer” are defined, but elastomers containing both olefin and styrene are classified into the above “styrene elastomer” ( Classification) (to belong).

  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.

  In order to solve the above problems, the present applicant has, as a copolymer component, a first resin layer containing 50% by mass or more of a random copolymer containing propylene and other copolymer components other than propylene, and a melting point thereof. A first elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less, and a first elastomer-modified olefin resin having a melting temperature of 155 ° C. or more and a crystal melting energy of 50 J / g or more. And a second resin layer formed of a mixed resin containing two or more layers, and the first elastomer-modified olefin resin is an elastomer-modified homopolypropylene or / and an elastomer-modified random copolymer. The second elastomer-modified olefin resin comprises an elastomer-modified homopolypropylene. Or / and consisting of an elastomer-modified random copolymer, wherein 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, Proposed a sealant film for an electricity storage device exterior material in which the total value 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 in the second resin layer (Japanese Patent Application No. 2015-190977). With such a configuration, the cost can be suppressed, sufficient sealing strength can be secured, and when the internal pressure of the electricity storage device is excessively increased, destruction (peeling) is generated inside the sealant layer, and the degassing is performed, thereby increasing the internal pressure. It has been found that the material can be prevented from rupture, and when the rupture portion for preventing the rupture occurs, the continuous rupture does not easily proceed from the rupture portion, and whitening during molding can be suppressed.

  As a result of further earnest research, the present applicant has made it possible to sufficiently cause cohesive failure inside the sealant layer by setting the composition of the second resin layer of the sealant film having the above-described structure to be a specific composition. When a breakage (peeling) portion of the material occurs, the effect that continuous breakage from the breakage point is more difficult to proceed is obtained, and whitening at the time of molding can be further sufficiently suppressed. The invention has been completed. In addition, by producing a resin composition for the second resin layer by a specific method, it has been found that cohesive failure occurs more sufficiently inside the sealant layer, and the production method of the present invention has been completed. Is.

  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, a continuous sealant film for an electricity storage device, an exterior material for an electricity storage device, an electricity storage device, and a resin for the sealant film of an electricity storage device exterior material can be prevented from progressing continuously and can be sufficiently suppressed from being whitened during molding. It aims at providing the manufacturing method of a composition.

  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;
Two or more layers including a second resin layer formed of a composition containing a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, and a polymer component. Made of
The first elastomer-modified olefin resin comprises 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 content of the first elastomer-modified olefin resin is 50% by mass or more,
The polymer component is at least one polymer component selected from the group consisting of a random copolymer containing a copolymer component other than propylene and propylene as a copolymer component, homopolypropylene, an olefin elastomer, and a styrene elastomer. A sealant film for an exterior material of an electricity storage device, characterized in that:

[2] 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 resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or more, and a second elastomer-modified olefin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less Comprising a laminate of two or more layers comprising a second resin layer formed of a composition comprising a system resin and a polymer component,
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, a total value 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,
The polymer component is at least one polymer component selected from the group consisting of a random copolymer containing a copolymer component other than propylene and propylene as a copolymer component, homopolypropylene, an olefin elastomer, and a styrene elastomer. A sealant film for an exterior material of an electricity storage device, characterized in that:

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

  [4] The sealant film for an exterior material for an electricity storage device according to the above item 2 or 3, wherein the second elastomer-modified olefin resin has two or more crystallization peaks in a DSC measurement graph.

  [5] The sealant film for an exterior material for an electricity storage device according to any one of the aforementioned Items 1 to 4, wherein the content of the polymer component in the second resin layer is 1% by mass or more and less than 50% by mass.

[6] The elastomer in the elastomer-modified homopolypropylene is ethylene propylene rubber,
6. The sealant film for an exterior material of an electricity storage device according to any one of 1 to 5 above, wherein the elastomer in the elastomer-modified random copolymer is ethylene propylene rubber.

  [7] The exterior of the electricity storage device according to any one of [1] to [6], wherein the first resin layer further contains an antiblocking agent and a slip agent, and the second resin layer further contains a slip agent. Sealant film for materials.

  [8] The sealant film for an exterior material for an electricity storage device according to any one of the aforementioned Items 1 to 7, comprising only the first resin layer and the second resin layer laminated on one side of the first resin layer.

  [9] 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. 8. The sealant film for an exterior material for an electricity storage device according to any one of 1 to 7 above, comprising a laminate in which at least three layers are laminated.

[10] 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 9, 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.

  [11] An electricity storage device exterior case comprising the molded body of the electricity storage device exterior material according to [10].

  [12] A method for producing an exterior case for an electricity storage device, comprising subjecting the exterior material for an electricity storage device according to item 10 to deep drawing or stretch molding.

[13] An electricity storage device body,
The exterior member for an electricity storage device according to item 10 and / or the exterior member comprising the exterior case for an electricity storage device according to item 11 above,
The electricity storage device, wherein the electricity storage device body is covered with the exterior member.

[14] A pre-melt kneading step of obtaining a first melt-kneaded product by melt-kneading one or more elastomer components and one or more plastomer components;
The first melt-kneaded product, a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or more, a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g A method for producing a resin composition for a sealant film of an electricity storage device exterior material, comprising: a step of mixing a second elastomer-modified olefin resin that is the following to obtain a resin composition.

  [15] The elastomer component used in the preliminary melt-kneading step is an olefin elastomer, a styrene elastomer, and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. 15. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to item 14, which is one or more elastomer components selected from the group consisting of:

  [16] The plastomer component used in the preliminary melt kneading step is made of random polypropylene, homopolypropylene, and a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. 16. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to item 14 or 15, which is one or more plastomer components selected from the group.

[17] The elastomer component used in the pre-melt kneading step is a second elastomer-modified olefin resin having a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g or less,
The plastomer component used in the preliminary melt kneading step contains a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, and further comprising random polypropylene and / or homopolypropylene. 15. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to item 14 above.

[18] A pre-melt kneading step in which one or two or more elastomer components and one or more plastomer components are melt-kneaded to obtain a first melt-kneaded product;
Mixing the first melt-kneaded product with a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, to obtain a resin composition. The manufacturing method of the resin composition for sealant films of the electrical storage device exterior material characterized by these.

  [19] The elastomer component used in the preliminary melt-kneading step is an olefin elastomer, a styrene elastomer, and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. 19. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to item 18, which is one or more elastomer components selected from the group consisting of:

  [20] The plastomer component used in the preliminary melt-kneading step is made of random polypropylene, homopolypropylene, and a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. 20. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to the above item 18 or 19, which is one or more plastomer components selected from the group.

  [21] The sealant for an electricity storage device exterior material according to any one of the above items 14 to 20, wherein in the preliminary melt-kneading step, an elastomer component / plastomer component mixing mass ratio is set to a range of 5/95 to 70/30. The manufacturing method of the resin composition for films.

  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). Further, since the second resin layer contains the first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, the compatibility between the elastomer phase and the olefin resin phase is high. It is good, and the dispersibility of the elastomer phase is also good. With this, when the seal part breaks due to excessive increase in internal pressure of a pair of exterior materials in which the mutual inner sealant layers are heat-sealed. In the second resin layer (inside the sealant layer), cohesive failure occurs, and it is difficult for fracture (peeling) to occur at the interface between the metal foil layer and the inner sealant layer. When this occurs, there is an advantage that continuous destruction is difficult to proceed starting from the destruction location.

  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. In addition, since the melting point of the first elastomer-modified olefin resin is 155 ° C. or higher, the second resin layer is hardly crushed during heat sealing, and sufficient insulation can be secured.

  Furthermore, since the second resin layer contains the specific polymer component together with the first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, the internal pressure excessively increases. When the seal portion is broken by this, cohesive failure occurs sufficiently in the second resin layer (inside the sealant layer), and when the break (peeling) portion for preventing explosion occurs In addition to the effect that continuous breakage is less likely to proceed from the breakage point, whitening during molding can be more sufficiently suppressed.

  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], 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 has a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or more, a first elastomer-modified olefin resin having a melting point of 135 ° C. or higher, and a crystal melting energy of 30 J / g. Since the composition is a combination of the following second elastomer-modified olefin resin, the compatibility between the elastomer phase and the olefin resin phase is good, and the dispersibility of the elastomer phase is also good. When the seal part breaks due to an excessive increase in internal pressure of a pair of exterior materials in which the inner sealant layers of each other are heat-sealed, cohesive failure occurs in the second resin layer (inside the sealant layer) Since the breakage (peeling) hardly occurs at the interface between the metal foil layer and the inner sealant layer, the breakage (peeling) point for preventing bursting occurred. There is an advantage that hardly proceeds destruction continuous as a starting point the breaking point to.

  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. In addition, since the melting point of the first elastomer-modified olefin resin is 155 ° C. or higher, the second resin layer is hardly crushed during heat sealing, and sufficient insulation can be secured.

  Further, since the second resin layer further contains the specific polymer component, when the seal portion breaks due to an excessive increase in internal pressure, the second resin layer (inside the sealant layer) causes cohesive failure. When the above-mentioned destruction (peeling) part for preventing bursting occurs, the effect that the continuous destruction is more difficult to proceed from the destruction part is obtained, and whitening at the time of molding Can be sufficiently suppressed.

  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 [3], 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 [4], the effects described above can be more sufficiently ensured.

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

  In the invention of [6], the above effects can be more sufficiently ensured.

  In the invention of [7], excellent slipperiness can be imparted to the surface of the exterior material, and when molding the exterior material, molding with a deeper molding depth can be performed well, and whitening at the time of molding is sufficient Can be suppressed.

  In the inventions [8] and [9], the above effects can be more sufficiently ensured.

  In the invention of [10], productivity is good, costs can be suppressed, sufficient sealing 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 [11], productivity is good, costs can be suppressed, sufficient sealing 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 [12], cost can be suppressed, 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 increases 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 [13], 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.

  In the invention of [14], in the preliminary melt-kneading step, the elastomer component and the plastomer component are melt-kneaded to obtain a first melt-kneaded product, and the elastomer component and the plastomer component are mutually in the first melt-kneaded product. Since it is mixed with high dispersibility, this first melt-kneaded product is mixed with a specific first elastomer-modified olefin resin (plastomer phase) and a specific second elastomer-modified olefin resin (elastomer phase). By doing so, the obtained resin composition is very excellent in the compatibility of the interface of an elastomer phase and a plastomer phase (non-elastomeric phase). Therefore, the exterior device for an electricity storage device configured using the sealant film including the second resin layer formed of the obtained resin composition is a pair of exterior materials in which the mutual inner sealant layers are heat-sealed. When the seal portion breaks due to excessive increase in internal pressure, cohesive failure occurs sufficiently in the second resin layer (inside the sealant layer), and breaks at the interface between the metal foil layer and the inner sealant layer ( (Exfoliation) is very unlikely to occur, so when a fracture (peeling) part for preventing bursting occurs, the effect that continuous destruction is extremely difficult to proceed from the fractured part is obtained, and whitening at the time of molding is also achieved It can be suppressed more sufficiently.

  In the invention of [15], it is possible to obtain a resin composition excellent in compatibility at the interface between the elastomer phase and the plastomer phase (non-elastomeric phase).

  In the invention of [16], it is possible to obtain a resin composition more excellent in the compatibility of the interface between the elastomer phase and the plastomer phase (non-elastomeric phase).

  In the invention of [17], it is possible to obtain a resin composition further excellent in compatibility at the interface between the elastomer phase and the plastomer phase (non-elastomeric phase).

  In the invention of [18], in the preliminary melt-kneading step, the elastomer component and the plastomer component are melt-kneaded to obtain a first melt-kneaded product, and the elastomer component and the plastomer component are mutually in the first melt-kneaded product. Since the mixture is mixed with high dispersibility, the resin composition obtained by mixing the first melt-kneaded product and the specific first elastomer-modified olefin resin (plastomer phase) becomes an elastomer phase and a plastomer. Excellent compatibility at the interface of the phase (non-elastomeric phase). Therefore, the exterior device for an electricity storage device configured using the sealant film including the second resin layer formed of the obtained resin composition is a pair of exterior materials in which the mutual inner sealant layers are heat-sealed. When the seal portion breaks due to excessive increase in internal pressure, cohesive failure occurs sufficiently in the second resin layer (inside the sealant layer), and breaks at the interface between the metal foil layer and the inner sealant layer ( (Exfoliation) is very unlikely to occur, so when a fracture (peeling) part for preventing bursting occurs, the effect that continuous destruction is extremely difficult to proceed from the fractured part is obtained, and whitening at the time of molding is also achieved It can be suppressed more sufficiently.

  In the invention of [19], a resin composition excellent in the compatibility of the interface between the elastomer phase and the plastomer phase (non-elastomeric phase) can be obtained.

  In the invention [20], it is possible to obtain a resin composition more excellent in the compatibility of the interface between the elastomer phase and the plastomer phase (non-elastomeric phase).

  In the invention [21], it is possible to obtain a resin composition further excellent in compatibility at the interface between the elastomer phase and the plastomer phase (non-elastomeric phase).

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 composed of a laminate of two or more layers including a first resin layer 7 and a second resin layer 8. The first resin layer 7 contains 50% by mass or more of a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component.

The second resin layer 8 is formed of any one of the following compositions a) and b).
a) A composition comprising a first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔHm) of 50 J / g or more, and a specific polymer component.
b) a first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔHm) of 50 J / g or higher, a melting point (Tmp) of 135 ° C. or higher and a crystal melting energy A composition comprising a second elastomer-modified olefin resin having (ΔHm) of 30 J / g or less and a specific polymer component.

As the specific polymer component,
-Random copolymer containing "propylene" and "other copolymerization components excluding propylene" as copolymerization components,
・ Homopolypropylene,
・ Olefin elastomers, and
Use at least one polymer component selected from the group consisting of styrene elastomers. The “other copolymerization component excluding propylene” in the random copolymer is not particularly limited. For example, ethylene, 1-butene, 1-hexene, 1-pentene, 4methyl-1- In addition to olefin components such as pentene, butadiene and the like can be mentioned. Examples of the olefin elastomer include ethylene propylene rubber (EPR), ethylene butene rubber (EBR), ethylene-propylene-diene rubber (EPDM), isoprene rubber (IR), butadiene rubber (BR), butyl rubber (IIR) and the like. Is mentioned. Examples of the styrene elastomer include styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene rubber (SBR), and the like.

  In the present invention, the second resin layer 8 includes any of the above-mentioned specific polymer components in any of the constitutions a) and b), and therefore does not contain the specific polymer component (Reference Example 1). When the seal portion is broken due to excessive increase in internal pressure of the pair of exterior materials in which the inner sealant layers are heat-sealed and bonded to each other, the second resin layer 8 (sealant layer) Cohesive failure occurs sufficiently (inside) (obviously from comparison between Reference Examples 1 to 3 and Examples 1 to 29), and whitening during molding can be more sufficiently suppressed (Reference Examples 1 to 1). 3 is clear from the comparison between Examples 1 to 29).

  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 preferably composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer is used as a copolymerization component. It is an elastomer modified body of a random copolymer containing "propylene" and "other copolymerization component excluding propylene", and the "other copolymerization component excluding propylene" is not particularly limited, For example, in addition to olefin components such as ethylene, 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 preferably composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer is used as a copolymerization component. It is an elastomer modified body of a random copolymer containing "propylene" and "other copolymerization component excluding propylene", and the "other copolymerization component excluding propylene" is not particularly limited, For example, in addition to olefin components such as ethylene, 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.

  When the second resin layer 8 is formed of any one of the compositions a) and b), when the melting point of the first elastomer-modified olefin resin is less than 155 ° C., whitening occurs to some extent during molding, The second resin layer 8 is liable to be crushed during heat sealing, and the insulating property tends to be insufficient (see Comparative Example 3). Further, when the crystal melting energy (ΔHm) of the first elastomer-modified olefin resin is less than 50 J / g, the cohesion degree at the peeling interface is moderate, and the cohesive failure at 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). 5).

  In the case where the second resin layer 8 is formed of the composition b), if the melting point of the second elastomer-modified olefin resin is less than 135 ° C., whitening occurs to some extent during molding (see Comparative Example 4). Further, when the crystal melting energy (ΔHm) of the second elastomer-modified olefin resin exceeds 30 J / g, whitening occurs to some extent during molding (see Comparative Example 6).

  Further, in the second resin layer 8, if the first elastomer-modified olefin resin having a melting point (Tmp) of 155 ° C. or higher and a crystal melting energy (ΔHm) of 50 J / g or more is not contained, Whitening occurs to some extent, and the degree of cohesion at the peeling interface is moderate, and cohesive failure of the peeling interface is difficult to occur.In other words, peeling is likely to occur at the interface between the metal foil layer and the inner sealant layer during peeling. As a starting point, continuous peeling is likely to proceed, and further, the second resin layer 8 is liable to be crushed and the insulating properties are likely to be insufficient (see Comparative Example 2).

  The melting point of the first elastomer-modified olefin resin is preferably 155 ° C. or higher and 185 ° C. or lower. The crystal melting energy of the first elastomer-modified olefin resin is preferably 50 J / g or more and 75 J / g or less, and more preferably 53 J / g or more and 70 J / g or less. The melting point of the second elastomer-modified olefin resin is preferably 135 ° C. or higher and 175 ° C. or lower. The crystal melting energy of the second elastomer-modified olefin resin is preferably from 5 J / g to 30 J / g, more preferably from 10 J / g to 25 J / g, and more preferably from 10 J / g to 20 J / g. 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, propylene and hydrogen 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, propylene and hydrogen are further 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, propylene and hydrogen are further added to polymerize ethylene-propylene rubber (EPR) in which ethylene and propylene are copolymerized, whereby the first elastomer-modified olefin resin or the second elastomer-modified olefin system is polymerized. Resin 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 first elastomer-modified olefin resin is preferably 99% by mass to 50% by mass, more preferably 95% by mass to 70% by mass, and 90% by mass. % To 75% by mass is particularly preferred.

  In the second resin layer 8, the content of the polymer component is preferably 1% by mass or more and less than 50% by mass, more preferably 5% by mass or more and 45% by mass or less, and more preferably 10% by mass or more and 30% by mass. It is particularly preferable that the content is not more than mass%.

  When the second elastomer-modified olefin resin is contained in the second resin layer 8, the content of the second elastomer-modified olefin resin in the second resin layer 8 is 1% by mass to 50% by mass. Of these, 5 mass% to 30 mass% is more preferable, and 10 mass% to 25 mass% is particularly preferable.

  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 (crystallization temperature) on the high temperature side is 90 ° C. or higher, and the crystallization peak (crystallization temperature) on the low temperature side is 80 ° C. or less. Is preferred. 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 first resin layer 7 is preferably configured not to have 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 contains a slip agent in addition to the first elastomer-modified olefin resin or in addition to the first elastomer-modified olefin resin and the second elastomer-modified olefin resin. Is preferred.

  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 higher than the melting point of the thermoplastic resin constituting the inner sealant layer 3, and having a melting point higher by 20 ° C. or higher than the melting point of the thermoplastic resin. It is particularly preferable to use a conductive resin.

  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, the suitable example of the manufacturing method of the resin composition for sealant films (resin composition for 2nd resin layers) of an electrical storage device exterior material is demonstrated below.

  In the first production method, one or more elastomer components and one or more plastomer components are melt-kneaded to obtain a first melt-kneaded product (preliminary melt-kneading step).

  Next, the first melt-kneaded product obtained in the preliminary melt-kneading step is mixed with the first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. A resin composition is obtained (which may be mixed by melt kneading or the like in addition to normal mixing). In the first production method, the first elastomer-modified olefin resin is preferably composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer is used as a copolymer component. It is an elastomer-modified body of a random copolymer containing propylene and other copolymer components excluding propylene (the detailed structure of the first elastomer-modified olefin resin is as described above).

  In the second production method, one or more elastomer components and one or more plastomer components are melt-kneaded to obtain a first melt-kneaded product (preliminary melt-kneading step).

  Next, the first melt-kneaded product obtained in the preliminary melt-kneading step, the first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, and a melting point of 135 ° C. The resin composition is obtained by mixing with the second elastomer-modified olefin resin having the crystal melting energy of 30 J / g or less (which may be mixed by melt kneading in addition to normal mixing). In the second production method, the first elastomer-modified olefin resin is preferably made of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the second elastomer-modified olefin resin is an elastomer-modified homopolymer. Preferably, the elastomer-modified random copolymer is made of polypropylene or / and an elastomer-modified random copolymer, and the elastomer-modified random copolymer contains propylene and other copolymer components other than propylene as copolymer components. (The detailed configuration of the first and second elastomer-modified olefin resins is as described above).

  In the first and second production methods, the elastomer component used in the preliminary melt-kneading step includes an olefin elastomer, a styrene elastomer, and a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g or less. It is preferable that it is 1 type, or 2 or more types of elastomer components chosen from the group which consists of a certain 2nd elastomer modified olefin resin. The second elastomer-modified olefin resin that can be used in the preliminary melt-kneading step is preferably composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer is It is an elastomer-modified body of a random copolymer containing propylene and other copolymerization components excluding propylene as a copolymerization component (the detailed structure of the second elastomer-modified olefin resin is as described above). Examples of the olefin elastomer include ethylene propylene rubber (EPR), ethylene butene rubber (EBR), ethylene-propylene-diene rubber (EPDM), isoprene rubber (IR), butadiene rubber (BR), butyl rubber (IIR) and the like. Is mentioned. Examples of the styrene elastomer include styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene rubber (SBR), and the like.

  In the first and second production methods, the plastomer component used in the preliminary melt kneading step is random polypropylene, homopolypropylene, and a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. It is preferably one or more plastomer components selected from the group consisting of one elastomer-modified olefin resin. The first elastomer-modified olefin resin that can be used in the preliminary melt-kneading step is preferably composed of an elastomer-modified homopolypropylene and / or an elastomer-modified random copolymer, and the elastomer-modified random copolymer is It is an elastomer-modified body of a random copolymer containing propylene and other copolymerization components other than propylene as a copolymerization component (the detailed structure of the first elastomer-modified olefin resin is as described above). The random polypropylene that can be used in the preliminary melt-kneading step is a random copolymer containing “propylene” and “another copolymer component excluding propylene” as a copolymer component, and the “excluding propylene” The “other copolymerization component” is not particularly limited, and examples thereof include olefin components such as ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1-pentene, but also butadiene and the like. Can be mentioned.

  In the preliminary melt-kneading step, the mixing mass ratio of the elastomer component / plastomer component is preferably set in the range of 5/95 to 70/30.

  In the first production method, it is preferable that the mixing mass ratio of the first melt-kneaded product / the first elastomer-modified olefin resin is set in a range of 5/95 to 40/60.

  Further, in the second production method, 95 parts by mass to 50 parts by mass of the first elastomer-modified olefin resin and 5 parts by mass of the second elastomer-modified olefin resin with respect to 100 parts by mass of the first melt-kneaded product. It is preferable to mix 50 parts by weight to 50 parts by weight.

  In the manufacturing method described above, the above-described “sealant film for an exterior material of an electricity storage device” (a laminate of two or more layers including the first resin layer 7 and the second resin layer 8) of the present invention described above is produced. A portion obtained by cutting a portion that is not commercialized, such as an ear portion or an off-gauge portion, and pulverized product obtained by pulverization can be used as a kneading material in the preliminary melting and kneading step. .

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

<Reference 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, a 22 μm-thick second resin layer 8 (the first melting point is 163 ° C., and the crystal melting energy is 58 J / g. A second resin layer 8) having a composition of 1% by mass of a second elastomer-modified olefin resin having an elastomer-modified olefin resin of 99% by mass, a melting point of 144 ° C., and a crystal melting energy of 19 J / g, ethylene-propylene random A 30 μm thick sealant film in which these three layers are laminated by co-extrusion using a T-die so that three layers of the first resin layer 7 having a thickness of 4 μm made of a copolymer are laminated in this order. After obtaining (first resin layer / second resin layer / first resin layer) 3, one surface of the first resin layer 7 of the sealant film 3 is coated with a two-component curable maleic acid-modified polypropylene. The film is laminated on the other surface of the aluminum foil 4 after the dry laminating via the adhesive 6 and sandwiched between a rubber nip roll and a laminating roll heated to 100 ° C. and then subjected to dry laminating. Then, by aging (heating) at 50 ° C. for 5 days, an exterior material for an electricity storage device having the configuration shown in FIG. 2 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.

<Reference Example 2>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (melting point is 163 ° C., first elastomer-modified olefin resin having a crystal melting energy of 58 J / g, 90 mass%, melting point is 136 ° C., A power storage device having the structure shown in FIG. 2 was used in the same manner as in Reference Example 1 except that a second resin layer having a composition of 10% by mass of a second elastomer-modified olefin resin having a crystal melting energy of 18 J / g was used. An exterior material was obtained.

<Reference Example 3>
As the second resin layer 8, a second resin layer having a thickness of 22 μm (the melting point is 163 ° C., the first elastomer-modified olefin resin having a crystal melting energy of 58 J / g, 80 mass%, the melting point is 144 ° C., A power storage device having the configuration shown in FIG. 2 was used in the same manner as in Reference Example 1 except that a second resin layer having a composition of 20% by mass of a second elastomer-modified olefin resin having a crystal melting energy of 19 J / g was used. An exterior material was obtained.

<Example 1>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, a second elastomer having a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 3.5 parts by mass, a melting point of 144 ° C., and a crystal melting energy of 19 J / g. A first melt-kneaded product was obtained by melt-kneading 3.5 parts by mass of a modified olefin resin and 1 part by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) at 210 ° C. Next, 8 parts by mass of the first melt-kneaded product, 85.5 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, and a melting point of 136 ° C. A resin composition was obtained by mixing 9.5 parts by mass of a second elastomer-modified olefin resin having a crystal melting energy of 18 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 2>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 7 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 1 part by mass of a resin and 2 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 10 parts by mass of the first melt-kneaded product, 72 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a melting point of 144 ° C., and crystals A resin composition was obtained by mixing 18 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 3>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 4>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 21 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g A first melt-kneaded product was obtained by melting and kneading 3 parts by mass of a resin and 6 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) at 210 ° C. Next, a resin composition is prepared by mixing 30 parts by mass of the first melt-kneaded product with 70 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 5>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 35 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 5 parts by mass of a resin and 10 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 50 parts by mass of the first melt-kneaded product with 50 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 6>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 21 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 3 parts by mass of a resin, 3 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 3 parts by mass of homopolypropylene were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. . Next, 30 parts by mass of the first melt-kneaded product, 56 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a melting point of 144 ° C., and crystals A resin composition was obtained by mixing 14 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 7>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 8 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a system resin was mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 10 parts by mass of the first melt-kneaded product, 72 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a melting point of 144 ° C., and crystals A resin composition was obtained by mixing 18 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 8>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of resin, 2 parts by mass of ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 2 parts by mass of ethylene propylene rubber were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product It was. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 9>
As the resin composition constituting the second resin layer 8, a resin composition obtained as follows is used, and as the resin composition constituting the first resin layer 7, an ethylene-propylene random copolymer (Tmp; Except for using 145 ° C.), an exterior material 1 for an electricity storage device having the configuration shown in FIG. 2 was obtained in the same manner as in Reference Example 1. First, 16 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 4 parts by mass of ethylene propylene rubber (EPR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. . Next, 20 parts by mass of the first melt-kneaded product, 56 parts by mass of a first elastomer-modified olefin resin having a melting point of 166 ° C. and a crystal melting energy of 65 J / g, a melting point of 144 ° C., and crystals A resin composition was obtained by mixing 24 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. The 2nd resin layer 8 was comprised using this resin composition.

<Example 10>
As the resin composition constituting the second resin layer 8, a resin composition obtained as follows is used, and as the resin composition constituting the first resin layer 7, an ethylene-propylene random copolymer (Tmp; Except for using 145 ° C.), an exterior material 1 for an electricity storage device having the configuration shown in FIG. 2 was obtained in the same manner as in Reference Example 1. First, 14 parts by mass of homopolypropylene and 4 parts by mass of ethylene butylene rubber (EBR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded product, 56 parts by mass of a first elastomer-modified olefin resin having a melting point of 166 ° C. and a crystal melting energy of 65 J / g, a melting point of 144 ° C., and crystals A resin composition was obtained by mixing 24 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. The 2nd resin layer 8 was comprised using this resin composition.

<Example 11>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 6 parts by mass of a system resin was mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 12>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g and 6 parts by mass of ethylene propylene rubber (EPR) are mixed and melt-kneaded at 210 ° C. 1 A melt-kneaded product was obtained. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 13>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 210 parts by mixing 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g and 6 parts by mass of a styrene-ethylene-butylene-styrene copolymer (SEBS). A first melt-kneaded product was obtained by melt-kneading at 0 ° C. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 14>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.), a melting point of 144 ° C., and 6 parts by mass of a second elastomer-modified olefin resin having a crystal melting energy of 19 J / g are mixed. The mixture was melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 15>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 6 parts by mass of ethylene butylene rubber (EBR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. . Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 16>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 6 parts by mass of a styrene-ethylene-butylene-styrene copolymer (SEBS) are mixed and melt-kneaded at 210 ° C. 1 A melt-kneaded product was obtained. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 17>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene, melting point of 136 ° C., and 6 parts by mass of second elastomer-modified olefin resin having a crystal melting energy of 18 J / g are mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Got. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 18>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene and 6 parts by mass of ethylene propylene rubber (EPR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 19>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene and 6 parts by mass of styrene-ethylene-butylene-styrene copolymer (SEBS) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 20>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 6 parts by mass of a system resin was mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 21>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g and 6 parts by mass of ethylene propylene rubber (EPR) are mixed and melt-kneaded at 210 ° C. 1 A melt-kneaded product was obtained. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 22>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 210 parts by mixing 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g and 6 parts by mass of a styrene-ethylene-butylene-styrene copolymer (SEBS). A first melt-kneaded product was obtained by melt-kneading at 0 ° C. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 23>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.), a melting point of 144 ° C., and 6 parts by mass of a second elastomer-modified olefin resin having a crystal melting energy of 19 J / g are mixed. The mixture was melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 24>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 6 parts by mass of ethylene butylene rubber (EBR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. . Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 25>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) and 6 parts by mass of a styrene-ethylene-butylene-styrene copolymer (SEBS) are mixed and melt-kneaded at 210 ° C. 1 A melt-kneaded product was obtained. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 26>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene, melting point of 136 ° C., and 6 parts by mass of second elastomer-modified olefin resin having a crystal melting energy of 18 J / g are mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Got. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 27>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene and 6 parts by mass of ethylene propylene rubber (EPR) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<Example 28>
Except for using the resin composition obtained as follows as the resin composition constituting the second resin layer 8, in the same manner as in Reference Example 1, the exterior material 1 for the electricity storage device having the configuration shown in FIG. Got. First, 14 parts by mass of homopolypropylene and 6 parts by mass of styrene-ethylene-butylene-styrene copolymer (SEBS) were mixed and melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product with 80 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g. Got. Except having constituted the 2nd resin layer 8 using this resin composition, it carried out similarly to the reference example 1, and obtained the exterior material 1 for electrical storage devices.

<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 melting point of 163 ° C. and a crystal melting energy of 58 J / g was used. In the same manner as in Example 3, an exterior material for an electricity storage device was obtained.

<Comparative example 2>
As the resin composition constituting the second resin layer 8, an electricity storage device exterior material having the structure shown in FIG. 2 was obtained in the same manner as in Example 3 except that the resin composition obtained as follows was used. Obtained. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, a resin composition is prepared by mixing 20 parts by mass of the first melt-kneaded product and 80 parts by mass of a second elastomer-modified olefin resin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g. Got. An exterior material for an electricity storage device was obtained in the same manner as in Example 3 except that the second resin layer 8 was formed using this resin composition.

<Comparative Example 3>
As the resin composition constituting the second resin layer 8, an electricity storage device exterior material having the structure shown in FIG. 2 was obtained in the same manner as in Example 3 except that the resin composition obtained as follows was used. Obtained. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded product, a melting point of 145 ° C., a crystal melting energy of 57 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., and a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. An exterior material for an electricity storage device was obtained in the same manner as in Example 3 except that the second resin layer 8 was formed using this resin composition.

<Comparative example 4>
As the resin composition constituting the second resin layer 8, an electricity storage device exterior material having the structure shown in FIG. 2 was obtained in the same manner as in Example 3 except that the resin composition obtained as follows was used. Obtained. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded product, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 130 ° C., and a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 14 J / g. An exterior material for an electricity storage device was obtained in the same manner as in Example 3 except that the second resin layer 8 was formed using this resin composition.

<Comparative Example 5>
As the resin composition constituting the second resin layer 8, an electricity storage device exterior material having the structure shown in FIG. 2 was obtained in the same manner as in Example 3 except that the resin composition obtained as follows was used. Obtained. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded product, a melting point of 155 ° C., a crystal melting energy of 49 J / g of a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 19 J / g. An exterior material for an electricity storage device was obtained in the same manner as in Example 3 except that the second resin layer 8 was formed using this resin composition.

<Comparative Example 6>
As the resin composition constituting the second resin layer 8, an electricity storage device exterior material having the structure shown in FIG. 2 was obtained in the same manner as in Example 3 except that the resin composition obtained as follows was used. Obtained. First, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer-modified olefin having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of a resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded product, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 158 ° C., a crystal A resin composition was obtained by mixing 16 parts by mass of a second elastomer-modified olefin resin having a melting energy of 44 J / g. An exterior material for an electricity storage device was obtained in the same manner as in Example 3 except that the second resin layer 8 was formed using this resin composition.

<Example 29>
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, 14 parts by mass of a first elastomer-modified olefin resin having a melting point of 163 ° C. and a crystal melting energy of 58 J / g, a second elastomer modification having a melting point of 144 ° C. and a crystal melting energy of 19 J / g 2 parts by mass of an olefin resin and 4 parts by mass of an ethylene-propylene random copolymer (Tmp; 144 ° C., 152 ° C.) were melt-kneaded at 210 ° C. to obtain a first melt-kneaded product. Next, 20 parts by mass of the first melt-kneaded material, a melting point of 163 ° C., a crystal melting energy of 58 J / g, a first elastomer-modified olefin resin of 64 parts by mass, a melting point of 144 ° C., a crystal A resin composition for the second resin layer was obtained by mixing 16 parts by mass of the second elastomer-modified olefin resin having a melting energy of 19 J / g.

  Next, the first resin layer 7 made of ethylene-propylene random copolymer and having a thickness of 8 μm and the second resin layer 8 having a thickness of 22 μm (the second resin layer 8 made of the resin composition for the second resin layer) are laminated. As described above, by co-extrusion using a T-die, a sealant film (first resin layer 7 / second resin layer 8) 3 having a thickness of 30 μm formed by laminating these two layers is obtained, and then the sealant One surface of the first resin layer 7 of the film 3 is overlaid on the other surface of the aluminum foil 4 after the dry lamination via a two-component curable maleic acid-modified polypropylene adhesive 6, and a rubber nip roll; It is sandwiched between a laminating roll heated to 100 ° C. and pressed to be dry laminated, and then aged at 50 ° C. for 5 days (heated) to obtain the structure shown in FIG. To obtain a sheathing material 1 for a power storage device.

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 29 and Comparative Examples 1 to 6, melt kneading was performed by performing melt kneading at 210 ° C. using a 40φ extruder (L / D = 24) equipped with a screw with a tip dull form and a strand forming die. The obtained strands were water-cooled and solidified in a water tank and cut with a cutter to obtain pellets of the first melt-kneaded product (major particles having a major axis of 4 mm to 5 mm).

  In Examples 1 to 29 and Comparative Examples 1 to 6, 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 to 4, the following abbreviations representing the first and second elastomer-modified olefin resins represent the following resins, respectively.
“B-PP1A”: a first elastomer-modified olefin resin “B-PP1B” having a melting point of 163 ° C. and a crystal melting energy (ΔHm) of 58 J / g, a melting point of 166 ° C., and a crystal melting energy ( The first elastomer-modified olefin resin “B-PP1D” having a ΔHm of 65 J / g, the melting point is 145 ° C., and the crystal melting energy (ΔHm) is 57 J / g. B-PP1E ”: a first elastomer-modified olefin resin“ B-PP2A ”having a melting point of 155 ° C. and a crystal melting energy (ΔHm) of 49 J / g, a melting point of 144 ° C., and a crystal melting energy (Δ The second elastomer-modified olefin resin “B-PP2B” whose Hm) is 19 J / g, the melting point is 136 ° C., and the crystal melting energy The second elastomer-modified olefin resin “B-PP2C” having (ΔHm) of 18 J / g. The second elastomer-modified olefin resin having a melting point of 130 ° C. and a crystal melting energy (ΔHm) of 14 J / g. “B-PP2D”: a second elastomer-modified olefin resin having a melting point of 158 ° C. and a crystal melting energy (ΔHm) of 44 J / g.

In the tables, the following abbreviations indicate the following resins, respectively.
"EPR" ... ethylene-propylene rubber "EBR" ... ethylene-butene rubber "SEBS" ... styrene-ethylene-butylene-styrene copolymer "homo PP" ... homopolypropylene "r-PPA" ... ethylene-propylene random copolymer ( Melting point: 144 ° C, 152 ° C)
“R-PPB”: ethylene-propylene random copolymer (melting point: 145 ° C.).

  The “melting point” of each resin is the melting peak temperature (Tmp) measured by differential scanning calorimetry (DSC) according to JIS K7121-1987, and the “crystal melting energy” of each resin is JIS It is the heat of fusion (crystal melting energy; ΔHm) measured by differential scanning calorimetry (DSC) in accordance with K7122-1987, all 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

  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 a 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 Z0238-1998. 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)
“X” indicates that whitening is not observed or is hardly whitened and has a low degree of aggregation, “White” indicates that whitening has occurred to a certain degree and has a moderate degree of aggregation, and whitening has occurred remarkably and the degree of aggregation A sample having a larger value of “◯” was assigned, and a sample having whitening more markedly and having a higher degree of aggregation was designated “◎”.

<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 material for power storage devices of Examples 1 to 29 of the present invention (the packaging material for power storage devices using the sealant film of the present invention) has sufficient seal strength, Since the degree of whitening at the peeling interface was sufficiently large, the degree of aggregation at the peeling interface was high, causing cohesive failure within the sealant layer at the time of peeling, and whitening at the time of molding was sufficiently suppressed. Thus, when the exterior | cover material for electrical storage devices of Examples 1-29 of this invention was used, since the cohesive failure has arisen inside the sealant layer, the metal foil layer 4 and the inner side sealant layer 3 are peeled (destructed). 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 6 that deviated from the scope defined by 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 (21)

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;
Two or more layers including a second resin layer formed of a composition containing a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, and a polymer component. Made of
The first elastomer-modified olefin resin comprises 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 content of the first elastomer-modified olefin resin is 50% by mass or more,
The polymer component is at least one polymer component selected from the group consisting of a random copolymer containing a copolymer component other than propylene and propylene as a copolymer component, homopolypropylene, an olefin elastomer, and a styrene elastomer. A sealant film for an exterior material of an electricity storage device, characterized in that: 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 resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or more, and a second elastomer-modified olefin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less Comprising a laminate of two or more layers comprising a second resin layer formed of a composition comprising a system resin and a polymer component,
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, a total value 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,
The polymer component is at least one polymer component selected from the group consisting of a random copolymer containing a copolymer component other than propylene and propylene as a copolymer component, homopolypropylene, an olefin elastomer, and a styrene elastomer. A sealant film for an exterior material of an electricity storage device, characterized in that:   The sealant film for an exterior material for an electricity storage device according to claim 2, wherein the content rate 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 2 or 3, wherein the second elastomer-modified olefin-based 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 4, wherein the content of the polymer component in the second resin layer is 1% by mass or more and less than 50% by mass. The elastomer in the elastomer-modified homopolypropylene is ethylene propylene rubber,
The sealant film for an exterior material for an electricity storage device according to any one of claims 1 to 5, wherein the elastomer in the elastomer-modified random copolymer is ethylene propylene rubber.   The said 1st resin layer contains an anti blocking agent and a slip agent further, and the said 2nd resin layer contains a slip agent further for the exterior materials of the electrical storage device of any one of Claims 1-6. Sealant film.   The sealant film for an exterior material of an electricity storage device according to any one of claims 1 to 7, comprising only the first resin layer and a 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 7, wherein the sealant film is made of a laminate in which is laminated. A base material layer as an outer layer, an inner sealant layer made of the sealant film according to any one of claims 1 to 9, 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.   An exterior case for an electricity storage device comprising a molded body of the exterior material for an electricity storage device according to claim 10.   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 10. An electricity storage device body,
The exterior member for an electricity storage device according to claim 10 and / or the exterior member comprising the exterior case for an electricity storage device according to claim 11,
The electricity storage device, wherein the electricity storage device body is covered with the exterior member. A preliminary melt-kneading step of melt-kneading one or two or more elastomer components and one or two or more plastomer components to obtain a first melt-kneaded product;
The first melt-kneaded product, a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or more, a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g A method for producing a resin composition for a sealant film of an electricity storage device exterior material, comprising: a step of mixing a second elastomer-modified olefin resin that is the following to obtain a resin composition.   The elastomer component used in the preliminary melt-kneading step is composed of an olefin elastomer, a styrene elastomer, and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to claim 14, wherein the elastomer component is one or more types of elastomer components selected from the above.   The plastomer component used in the preliminary melt kneading step is selected from the group consisting of random polypropylene, homopolypropylene, and a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. The method for producing a resin composition for a sealant film of a power storage device exterior material according to claim 14, wherein the plastomer component is one or more plastomer components. The elastomer component used in the preliminary melt-kneading step is a second elastomer-modified olefin resin having a melting point of 135 ° C. or higher and a crystal melting energy of 30 J / g or less,
The plastomer component used in the preliminary melt kneading step contains a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, and further comprising random polypropylene and / or homopolypropylene. The manufacturing method of the resin composition for sealant films of the electrical storage device exterior material of Claim 14 formed. A preliminary melt-kneading step of melt-kneading one or two or more elastomer components and one or two or more plastomer components to obtain a first melt-kneaded product;
Mixing the first melt-kneaded product with a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher, to obtain a resin composition. The manufacturing method of the resin composition for sealant films of the electrical storage device exterior material characterized by these.   The elastomer component used in the preliminary melt-kneading step is composed of an olefin elastomer, a styrene elastomer, and a second elastomer-modified olefin resin having a melting point of 135 ° C. or more and a crystal melting energy of 30 J / g or less. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to claim 18, wherein the elastomer component is one or more types of elastomer components selected from the above.   The plastomer component used in the preliminary melt kneading step is selected from the group consisting of random polypropylene, homopolypropylene, and a first elastomer-modified olefin resin having a melting point of 155 ° C. or higher and a crystal melting energy of 50 J / g or higher. The method for producing a resin composition for a sealant film of an electricity storage device exterior material according to claim 18, wherein the composition is one or more plastomer components.   21. The electricity storage device exterior material for a sealant film according to any one of claims 14 to 20, wherein a mixing mass ratio of elastomer component / plastomer component is set in a range of 5/95 to 70/30 in the preliminary melt kneading step. A method for producing a resin composition.

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