TW201841411A - Sealing film for use in exterior material of power storage device, exterior material for use in power storage device and manufacturing method thereof can obtain adequate lamination strength and adequate sealing strength - Google Patents

Abstract

The present invention provides a sealing film for use in exterior material of power storage device composed of more than two layers of laminated bodies. The two layers of laminated bodies comprises the first non-oriented film layer 7 allocated closest to the metal foil side, and a second non-oriented film layer 8 laminated on a surface on the side of the first non-oriented film layer. The first non-oriented film layer 7 contains a random polymer. The random polymer contains propylene taken as copolymerized component and other copolymerized components except propylene, and has a composition that does not contain lubricant or contains lubricant exceeding 0ppm and below 250ppm. The second non-oriented film layer 8 contains propylene copolymer and lubricant. The contained concentration of lubricant in the second non-oriented film layer 8 is 500ppm to 5000ppm. With this composition, the sealing film for use in exterior material of power storage device has an excellent formation, adequate lamination strength, and adequate sealing strength, in which it is difficult for the surface to produce white powder.

Description

 Sealing film for electrical storage device, external storage material for power storage device, and manufacturing method thereof  

The present invention relates to a battery or a capacitor used in a portable device such as a smart phone or a touch panel, a battery or a capacitor used in a hybrid vehicle, an electric vehicle, a wind power generation, a solar power generation, and a nighttime power storage. A sealing film for a material other than the power storage device, and a method for producing an exterior material for a power storage device using the sealing film.

In recent years, in addition to the power storage devices such as lithium ion batteries, lithium polymer batteries, lithium ion capacitors, and electric double layer capacitors, such as lithium-ion batteries, lithium polymer batteries, and electric double layer capacitors, such as smart phones and touch panel terminals. In place of the conventional metal can, a laminate of a heat resistant resin layer/adhesive layer/metal foil layer/adhesive layer/thermoplastic resin layer (inner sealing layer) is used. In addition, power supplies for electric vehicles and the like, large power supplies for storage purposes, capacitors, and the like are also increased by the laminate (outer material) having the above-described configuration. The laminate is formed into a three-dimensional shape such as a substantially rectangular parallelepiped shape by bulging or deep drawing. By forming such a three-dimensional shape, it is possible to secure a housing space for accommodating the main body portion of the power storage device.

In order to form such a three-dimensional shape into a good state without pinholes or cracks, it is required to improve the surface smoothness of the inner seal layer. In order to improve the surface smoothness of the inner sealing layer and to ensure good moldability, a laminated material for a battery container is provided which sequentially laminates an outer resin film, a first adhesive layer, a chemical conversion aluminum foil, and a second adhesive layer. The sealing film is composed of a random copolymer of propylene and an α-olefin having an α-olefin content of 2 to 10% by weight, and contains 1000 to 5000 ppm of a lubricant (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-288865

However, in the above-mentioned conventional technique, it is difficult to control the amount of lubricant deposition of the innermost layer surface of the outer casing (the inner surface of the inner seal layer) during the heating retention time of the production step of the exterior material (laminated material) or during storage. Although the smoothness at the time of molding is good, the lubricant is excessively deposited on the surface, and the lubricant adheres to the molding surface of the molding die during the molding of the exterior material to generate white powder (white powder produced by the lubricant). When such a white powder adheres and deposits on the molding surface, it is difficult to perform good molding. Therefore, it is necessary to clean the white powder adhering and depositing to remove the white powder, and the white powder is cleaned and removed to have the productivity of the exterior material. Reduced problems.

In addition, since a large amount of lubricant flows out from the side of the metal foil side in the inner sealing layer, the lamination strength (the lamination strength of the metal foil and the inner sealing layer) is lowered, and peeling is likely to occur between the metal foil and the inner sealing layer. The problem.

Of course, when the amount of the lubricant added (the lubricant content) is lowered, the adhesion of the white powder and the reduction of the lamination strength can be suppressed, but in this case, there is a problem that the amount of the surface lubricant is insufficient and the formability is deteriorated. Such a conventional technique makes it difficult to achieve both "excellent formability" and "suppressing the appearance of white powder on the surface of the exterior material and ensuring sufficient lamination strength".

The present invention has been made in view of the related art, and an object of the present invention is to provide a sealing film for a power storage device and an exterior material for a power storage device, and a method for producing the same, which are excellent in formability and white powder on a surface, and can be used. A sufficient lamination strength and sufficient sealing strength are obtained.

In order to achieve the foregoing objects, the present invention provides the following technical means.

[1] A sealing film for a power storage device, which is a sealing film formed by a laminate of two or more layers, wherein the two or more laminates include a first non-extended film layer and the first non-stretch film layer a second non-stretched film layer laminated on one side of the surface is characterized in that the first non-stretched film layer is disposed on a layer closest to the metal foil side of the sealing film; and the first non-stretched film layer is The random copolymerization system contains propylene and propylene as a copolymerization component, and the first non-stretched film layer contains no lubricant or contains more than 0 ppm of lubricant. And a composition of 250 ppm or less; the second non-stretched film layer contains a propylene-based copolymer and a lubricant; and the concentration of the lubricant in the second non-stretched film layer is 500 ppm to 5000 ppm.

[2] The sealing film for a power storage device according to the first aspect of the invention, further comprising a third non-stretch film layer, wherein the third non-stretch film layer is laminated in the second non-stretch film layer The side of the first unstretched film layer is laminated on the opposite side, and the third non-stretched film layer contains a random copolymer and a lubricant, and the random copolymerization system contains propylene and propylene as a copolymerization component. The other copolymerization component; the concentration of the lubricant in the third non-stretched film layer is 200 ppm to 3000 ppm.

[3] The sealing film for a power storage device according to the second aspect of the invention, wherein the concentration of the lubricant in the second non-stretched film layer is 1.0 times the concentration of the lubricant in the third non-stretched film layer. ~5.0 times.

[4] An exterior material for a power storage device, comprising: an inner sealing layer formed by the sealing film according to the above item 1 and a metal foil layer laminated on one side of the inner sealing layer; The amount of the lubricant on the surface of the non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

[5] An exterior material for a power storage device, comprising: an inner sealing layer formed by the sealing film according to the above item 2 or 3; and a metal foil layer laminated on one side of the inner sealing layer; The amount of the lubricant on the surface of the third non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

[6] An exterior material for a power storage device, comprising: a heat-resistant resin layer of an outer layer; an inner sealing layer formed by the sealing film of the above item 1; and a metal foil layer disposed between the two layers; The amount of the lubricant on the surface of the second non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

[7] An exterior material for a power storage device, comprising: a heat-resistant resin layer of an outer layer; an inner sealing layer formed by a sealing film according to the above item 2 or 3; and a metal foil layer disposed between the two layers The amount of the lubricant present on the surface of the third non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

[8] An outer casing for an electrical storage device, which is characterized in that the molded article of the outer casing described in any one of the above items 4 to 7 is formed.

[9] A method of producing an exterior material for a power storage device, comprising: a step of preparing a layer formed by laminating a sealing film and a metal foil according to any one of Items 1 to 3 of the first adhesive layer. And an aging step of heat-treating the laminate to obtain an exterior material for a storage device.

[10] The method for producing an exterior material for a storage battery device according to the above aspect, wherein the first adhesive is a thermosetting adhesive.

[11] A method of producing an exterior material for a power storage device, comprising: preparing a step of laminating a surface on one side of the metal foil with a heat-resistant resin film via a second adhesive; and the other side of the metal foil A laminate comprising a first sealing agent and a sealing film layer according to any one of the above items 1 to 3; and an aging step of heat-treating the laminate to obtain an exterior material for a storage device.

[12] The method for producing an exterior material for a storage battery device according to the above aspect, wherein the first adhesive is a thermosetting adhesive, and the second adhesive is a thermosetting adhesive.

The method for producing an exterior material for a power storage device according to any one of the preceding claims, wherein the amount of the lubricant present on the surface of the innermost layer of the exterior material for the electrical storage device obtained by the heat treatment is obtained. It is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .

According to the inventions of [1] and [2], since the amount of the lubricant which is present (precipitated) on the inner surface of the exterior material after the aging treatment (the surface of the innermost layer of the inner seal layer) is suppressed, the formation can be ensured. When it has good slidability, it is excellent in formability, and it is difficult for white powder to appear on the inner surface of the exterior material (the surface of the innermost layer of the inner seal layer), so that sufficient sealing strength can be obtained. Further, since the amount of the lubricant on the surface 7a of the first non-stretched film layer on the metal foil side in the inner seal layer of the exterior material after the aging treatment is small, sufficient lamination strength (metal foil and inner seal) can be ensured. Lamination strength of the layer). Further, the amount of the lubricant existing on the surface of the outer material after the aging treatment (the surface of the innermost layer of the inner seal layer) does not change even when subjected to heat history such as transportation or storage, so that an outer casing can be provided. The material has excellent formability in stability.

According to the invention of [3], the concentration of the lubricant in the second non-stretched film layer is 1.0 to 5.0 times the concentration of the lubricant in the third non-stretched film layer forming the innermost layer of the exterior material, and the aging is performed. At the time of the treatment, the lubricant is prevented from being oriented toward the interface of the lubricant concentration gradient from the third non-extended film layer 9 of the innermost layer to the second non-stretched film layer 8 (two film layers 8, 9). The interface is concentrated, and by 5.0 times or less, the lubricant is prevented from being oriented toward the interface of the lubricant concentration gradient from the second non-stretched film layer 8 to the third unstretched film layer 9 of the innermost layer (two film layers) The interface of 8, 9 is concentrated, and the amount of lubricant present on the surface 9a of the third non-stretched film layer which forms the innermost layer of the outer material after the aging treatment can be controlled at 0.1 μg/cm ² to 1.0 μg/cm ^{2 .} Within the scope. Thereby, the formability can be further improved.

According to the inventions of [4], [5], [6] and [7], it is possible to provide an exterior material for an electricity storage device which is excellent in formability, is less likely to be white powder on the surface, and can obtain sufficient lamination strength and sufficient Sealing strength.

Further, according to the inventions of [6] and [7], the heat-resistant resin layer as the outer layer is further provided, and the insulation of the inner sealing layer and the opposite side in the metal foil layer can be sufficiently ensured, and the exterior material for the electricity storage device can be improved. Physical strength and impact resistance.

According to the invention of [8], it is possible to provide an outer casing for an electricity storage device which is formed by good molding, and the surface of the outer casing (the surface of the innermost layer of the inner sealing layer) is hard to be white powder and can be sufficiently obtained. Lamination strength and sufficient sealing strength.

According to the inventions of [9] to [12], an exterior material for an electricity storage device can be produced, which is excellent in formability, has a white powder on the surface, and has sufficient lamination strength and sufficient sealing strength.

Further, according to the inventions of [11] and [12], since the heat-resistant resin layer as the outer layer is further provided, the insulation of the inner seal layer and the opposite side in the metal foil layer can be sufficiently ensured, and the physical strength of the exterior material can be improved. And impact resistance.

According to the invention of [13], since the amount of the lubricant present on the surface of the innermost layer of the exterior material is in the range of 0.1 μg/cm ² to 1.0 μg/cm ^{2 ,} it is possible to produce a smoothness which is more excellent in forming. An exterior material for a storage device that can further prevent good formability and further prevent the occurrence of white powder. In addition, the amount of lubricant (0.1 μg/cm ² to 1.0 μg/cm ² ) existing on the surface of the innermost layer of the obtained exterior material for a storage battery device does not change during the transportation or storage, and thus the thermal history does not change. An exterior material for a storage device having stable and excellent formability is provided.

1‧‧‧External materials for power storage devices

2‧‧‧Heat resistant resin layer (outer layer)

3‧‧‧Inner sealing layer (sealing film) (inside layer)

4‧‧‧metal foil layer

5‧‧‧2nd adhesive layer (outer adhesive layer)

6‧‧‧1st adhesive layer (inside adhesive layer)

7‧‧‧1st unstretched film layer (metal foil layer side)

7a‧‧‧ Surface of the metal foil layer side in the inner seal layer

8‧‧‧2nd stretchless film layer

8a‧‧‧The innermost surface

9‧‧‧3rd unstretched film layer

9a‧‧‧The innermost surface

10‧‧‧Outer casing (formed body) for power storage device

Fig. 1 is a cross-sectional view showing an embodiment of an exterior material for a storage battery device according to the present invention.

Fig. 2 is a cross-sectional view showing another embodiment of the exterior material for a storage battery device of the present invention.

Fig. 3 is a cross-sectional view showing an embodiment of a power storage device of the present invention.

FIG. 4 is a perspective view showing a state in which the outer surface of the power storage device of FIG. 3 (planar shape) is sealed, and the main body portion of the power storage device and the outer casing (formed into a three-dimensional molded body) are heat-sealed.

An embodiment of the sealing film 3 for an external electrical storage device according to the first aspect of the invention is as shown in Fig. 1 . The sealing film 3 is made of a laminate of two or more layers, and includes a first non-stretched film layer 7 and a second non-stretched film layer 8 in which a surface on one side of the first non-stretched film layer 7 is laminated. The first non-stretched film layer 7 is disposed on a layer closest to the metal foil 4 side of the sealing film 3, and the first non-stretched film layer contains a random copolymer, and the random copolymerization system contains a copolymerization component. In the copolymerizable component other than propylene and propylene, the first non-stretched film layer 7 is a structure which does not contain a lubricant or contains a lubricant, and the second non-stretched film layer 8 contains a propylene-based copolymer. , and lubricants.

In addition, an embodiment of the sealing film for an external electrical storage device according to the second aspect of the invention is as shown in FIG. 2 . The sealing film 3 is made of a laminate of three or more layers, and includes a second non-stretched film layer 8, a first non-stretched film layer 7 on which a surface on one side of the second non-stretched film layer 8 is laminated, and The third non-stretched film layer 9 laminated on the other surface of the second non-stretched film layer 8 is disposed on the layer closest to the metal foil 4 side of the sealing film 3 The first unstretched film layer 7 contains a random copolymer, and the random copolymerization system contains a copolymerization component other than propylene and propylene, and the first non-stretched film layer 7 does not contain lubrication. The composition of the agent or the composition containing the lubricant, the second non-stretched film layer 8 contains a propylene-based copolymer and a lubricant, and the third non-stretched film layer 9 contains a random copolymer and a lubricant. This random copolymerization system contains a copolymerization component other than propylene and propylene as a copolymerization component.

The random copolymer comprising the first unstretched film layer 7 and the third non-stretched film layer 9 contains a random copolymer of "propylene" and "other copolymer components other than propylene" as a copolymerization component. In the above-mentioned random copolymer, the "copolymerization component other than propylene" is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1- An olefin component such as pentene, and butadiene.

The propylene-based polymer constituting the second non-stretched film layer 8 is a polymer containing at least propylene as a polymerization component. The propylene-based polymer is not particularly limited, and examples thereof include a homopolypropylene and a block copolymer including "propylene" and a copolymerization component other than propylene as a copolymerization component. In particular, the propylene-based polymer is preferably a resin selected from the group consisting of homopolypropylene and the above-mentioned block copolymer.

In the above-mentioned block copolymer, the "copolymerization component other than propylene" is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene, and 4-methyl-1. An olefin component such as pentene or the like, butadiene or the like.

The second non-stretched film layer 8 preferably contains a structure of the propylene-based polymer, the elastomer component, and the lubricant. Among them, a type (fine structure) in which the above-described elastomer component is added to the propylene polymer and is microphase-separated is preferable. In other words, the elastomer-denatured propylene-based polymer having an island-like phase-separated island structure in which the elastomer component is in the sea of the propylene-based polymer is preferable, and in this case, the whitening phenomenon can be more difficult to occur, and further Improve insulation after sealing. The elastomer component is not particularly limited, and examples thereof include EPR (ethylene propylene rubber), propylene-butene elastomer, propylene-butylene-ethylene elastomer, EPDM (ethylene-propylene-diene rubber), and the like. The elastomer component is preferably EPR (ethylene propylene rubber).

Further, in the sealing film 3 of the first aspect of the invention, the first non-stretched film layer 7 is a structure which does not contain a lubricant, or a composition containing a lubricant of more than 0 ppm and not more than 250 ppm, and is lubricated in the second non-stretched film layer. It is extremely important that the concentration of the agent is set at 500 ppm to 5000 ppm. By satisfying these conditions, when the aging treatment is performed for curing the adhesive, the lubricant existing in the second non-extended film layer 8 can be prevented from moving into the first non-extended film layer 7, and the exterior material 1 can be secured. The amount of lubricant deposited on the surface 8a of the innermost layer (the second non-stretched film layer) ensures good slidability during molding of the exterior material, excellent formability, and the innermost layer (second The surface 8a of the stretched film layer 8) is hard to be white powder, and sufficient lamination strength and sufficient sealing strength are ensured. When the concentration of the lubricant in the first non-stretched film layer 7 exceeds 250 ppm, the amount of lubricant present on the surface 7a on the side of the metal foil layer 4 in the first non-stretched film layer 7 increases, and sufficient lamination strength cannot be ensured (metal Lamination strength of the foil and the inner sealing layer). Further, when the concentration of the lubricant in the second non-stretched film layer 8 is less than 500 ppm, the amount of the lubricant existing on the surface 8a of the innermost layer of the exterior material 1 does not become aging after the adhesive is cured. When the amount is more than 5,000 ppm, the lubricant is easily moved from the second non-stretched film layer 8 to the first non-stretched film layer 7 after the aging treatment for curing the adhesive, and the first non-stretched film layer is removed. The amount of lubricant present on the surface 7a of the side of the metal foil layer 4 in 7 is increased, so that sufficient lamination strength (laminating strength of the metal foil and the inner sealing layer) cannot be ensured, and the innermost layer (the second non-stretched film layer 8) The surface 8a is remarkably susceptible to white powder.

In the sealing film 3 of the first aspect of the invention, the first non-stretched film layer 7 is preferably a structure containing no lubricant or a lubricant containing more than 0 ppm and not more than 150 ppm. Further, in the sealing film 3 of the first aspect of the invention, the first non-stretched film layer 7 preferably contains 10 ppm to 90 ppm of a lubricant, and particularly preferably contains 20 ppm to 60 ppm of a lubricant. Further, the second non-stretched film layer 8 preferably contains 700 ppm to 4500 ppm of a lubricant, and more preferably contains 800 ppm to 4000 ppm of a lubricant, and particularly preferably contains 1000 ppm to 2700 ppm of a lubricant.

In the case where the third non-stretched film layer is further provided (the second invention), the first non-stretched film layer 7 is not contained in a lubricant, or contains a lubricant exceeding 0 ppm and 250 ppm or less. In the second non-stretched film layer 8, the concentration of the lubricant is set to 500 ppm to 5000 ppm, and it is extremely important that the concentration of the lubricant in the third non-stretched film layer 9 is 200 ppm to 3,000 ppm.

By satisfying these conditions, the lubricant existing in the third non-stretched film layer 9 can be suppressed from flowing into the second non-stretched film layer 8 or the first non-stretched film layer 7 when the aging treatment is performed for curing the adhesive. By moving, the amount of the lubricant deposited on the surface 9a of the innermost layer (the third non-stretched film layer) of the exterior material 1 can be ensured, thereby ensuring good slidability in the formation of the exterior material and obtaining excellent formability. The surface 9a of the innermost layer (the third non-stretched film layer 9) is less likely to have white powder, and sufficient lamination strength and sufficient sealing strength can be ensured. When the concentration of the lubricant in the first non-stretched film layer 7 exceeds 250 ppm, the amount of lubricant present on the surface 7a on the side of the metal foil layer 4 in the first non-stretched film layer 7 increases, and sufficient lamination strength cannot be ensured (metal Lamination strength of the foil and the inner sealing layer). Further, when the concentration of the lubricant in the second non-stretched film layer 8 is less than 500 ppm, the lubricant is easily removed from the third non-extended film layer 9 of the innermost layer to the second without aging treatment for curing the adhesive. When the stretched film layer 8 moves, the amount of lubricant existing on the surface 9a of the innermost layer is insufficient, and the slidability at the time of molding is deteriorated. When it exceeds 5000 ppm, the lubricant is easily removed from the aging treatment for curing the adhesive. 2 The non-stretched film layer 8 moves to the first non-stretched film layer 7, and the amount of the lubricant on the surface 7a of the first non-stretched film layer 7 on the side of the metal foil layer 4 increases, and sufficient lamination strength cannot be ensured (metal foil and Lamination strength of the inner sealing layer). In addition, when the concentration of the lubricant in the third non-stretched film layer 7 is less than 200 ppm, the amount of the lubricant present on the surface 9a of the innermost layer is insufficient after the aging treatment for curing the adhesive. When the moldability is more than 3,000 ppm, the surface of the innermost layer 9a is remarkably whitened after the aging treatment for curing the adhesive, and the step of cleaning and removing the white powder is required to cause a problem of deterioration in productivity.

In the sealing film 3 of the second aspect of the invention, the first non-stretched film layer 7 is preferably a structure containing no lubricant or a lubricant containing more than 0 ppm and not more than 150 ppm. Further, in the sealing film 3 of the second aspect of the invention, the first non-stretched film layer 7 preferably contains 10 ppm to 90 ppm of a lubricant, and particularly preferably contains 20 ppm to 60 ppm of a lubricant. Further, in the sealing film 3 of the second aspect of the invention, the second non-stretched film layer 8 preferably contains 700 ppm to 4500 ppm of a lubricant, and more preferably contains 800 ppm to 4000 ppm of a lubricant, and contains 1000 ppm to 2700 ppm of a lubricant. good. Further, in the sealing film 3 of the second aspect of the invention, the third non-stretched film layer 9 preferably contains a lubricant of 300 ppm to 2700 ppm, more preferably contains 500 ppm to 2000 ppm of a lubricant, and contains 800 ppm to 1200 ppm of a lubricant. good.

In the sealing film 3 of the second aspect of the invention, the lubricant concentration of the second non-stretched film layer 8 is preferably 1.0 to 5.0 times the concentration of the lubricant of the third non-stretched film layer 9. In the aging treatment, by 1.0 times or more, it is possible to suppress the lubricant from being oriented toward the interface of the lubricant concentration gradient from the third non-extended film layer 9 to the second non-stretch film layer 8 of the innermost layer (two film layers 8, The interface of 9) is concentrated, and by 5.0 times or less, the lubricant is prevented from being oriented toward the interface of the lubricant concentration gradient from the second non-stretched film layer 8 to the third non-stretched film layer 9 of the innermost layer (two films) The interface of the layers 8 and 9 is formed by concentrated movement, and the amount of lubricant present on the surface 9a of the third non-stretched film layer of the innermost layer of the exterior material after the aging treatment can be controlled to be 0.1 μg/cm ² to 1.0 μg/cm ^{2 .} Within the range, the formability can be further improved. The concentration of the lubricant in the second non-stretched film layer 8 is preferably 1.0 to 4.5 times the concentration of the lubricant in the third non-stretched film layer 9, and more preferably 1.0 to 4.0 times.

The lubricant is not particularly limited, and examples thereof include a saturated fatty acid decylamine, an unsaturated fatty acid decylamine, a substituted decylamine, a hydroxymethyl decylamine, a saturated fatty acid bis decylamine, an unsaturated fatty acid bis decylamine, and a fatty acid ester. Indoleamine, aromatic bis-amine, and the like.

The saturated fatty acid decylamine is not particularly limited, and examples thereof include decyl laurate, decyl palmitate, decylamine stearate, decyl behenate, and hydroxystearic acid decylamine. The unsaturated fatty acid decylamine is not particularly limited, and examples thereof include decyl oleate and erucamide.

The substituted guanamine is not particularly limited, and examples thereof include N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, and N-oleyl hard. Decylamine, N-stearyl erucamide, and the like. Further, the hydroxymethylguanamine is not particularly limited, and examples thereof include hydroxymethylstearate and the like.

The above-mentioned saturated fatty acid bis-guanamine is not particularly limited, and examples thereof include decyl methylenebisstearate, decyl ammonium bismuth decanoate, decyl ammonium bislaurate, and ethylene bis-hard fat. Acid amide, ethylene bishydroxy stearate decylamine, ethylene bis-decanoate decylamine, hexamethylene bis-stearate decylamine, hexamethylene bis-docosic acid amide, six Methyl hydroxy hydroxystearic acid amide, N, N'-distearate decyl decanoate, N, N'-distearoyl sebacate and the like.

The unsaturated fatty acid bis-guanamine is not particularly limited, and examples thereof include decyl ethylene bisoleate, decyl ammonium erucic acid, decyl hexamethylene oleate, and N, N'- Dioleyl sebacate and the like.

The fatty acid ester decylamine is not particularly limited, and examples thereof include stearylamine stearate and the like. The aromatic bis-indoleamine is not particularly limited, and examples thereof include m-xylene bis-stearate decylamine, m-xylene bishydroxystearate decylamine, and N,N'-distearate isophthalic acid. Indole amide or the like.

The thickness of the sealing film 3 is preferably set to 10 μm to 100 μm. When it is 10 μm or more, the occurrence of pinholes can be sufficiently prevented, and when it is set to 100 μm or less, the amount of resin used can be reduced, and the cost can be reduced.

In the case where the sealing film 3 has the two-layer laminated structure of FIG. 1, the ratio of the thickness of the two layers is set to the thickness of the first non-extended film layer 7 / the thickness of the second non-extended film layer 8 = 5 to 90 / The range of 95 to 10 is preferable, and the thickness of the first non-stretched film layer 7 / the thickness of the second non-extended film layer 8 = 5 to 40 / 95 to 60 is particularly preferable.

Further, in the case where the sealing film 3 is formed of a three-layer laminate of Fig. 2, the ratio of the thickness of the three layers is set to the thickness of the first non-extended film layer 7 / the thickness of the second non-extended film layer 8 / the third The thickness of the non-stretched film layer 9 is preferably in the range of 5 to 45/90 to 10/5 to 45, and the thickness of the first non-stretched film layer 7 / the thickness of the second non-extended film layer 8 / the third is set. The thickness of the non-stretched film layer 9 = 5~20/90~60/5~20 is particularly good.

In the case where the sealing film 3 is formed by laminating two layers of FIG. 1, the second non-extended film layer 8 of the innermost layer is formed, and an anti-blocking agent may be further contained. Further, when the sealing film 3 is formed by laminating three layers of Fig. 2, the third non-stretched film layer 9 of the innermost layer is formed, and an anti-blocking agent may be further contained. The anti-blocking agent is not particularly limited, and examples thereof include cerium oxide particles, acrylic resin particles, and aluminum silicate particles. The particle diameter of the anti-blocking agent is preferably in the range of 0.1 μm to 10 μm, and the average particle diameter is preferably in the range of 1 μm to 5 μm. The anti-blocking agent is preferably contained in the second non-stretched film layer 8 forming the innermost layer or the third non-stretched film layer 9 forming the innermost layer, and is preferably contained in an amount of 100 ppm to 5000 ppm.

By including the anti-adhesion agent (particles) in the innermost layer, fine protrusions are formed on the surface of the innermost layer (Fig. 1 is 8a, Fig. 2 is 9a), and the contact area between the films is reduced, so that the sealing film can be suppressed. Adhesion between. Further, by including the anti-blocking agent (particles) together with the lubricant described above, the smoothness at the time of the formation can be further improved.

The sealing film 3 is preferably produced by a molding method such as multilayer extrusion molding, inflation molding, or T-die film molding.

The exterior material 1 for a storage battery device of the present invention is produced by using the sealing film 3 having the above configuration.

A first manufacturing method (manufacturing method of an exterior material for a storage battery device) according to the present invention will be described. First, a laminate in which the sealing film 3 of the present invention (the first invention or the second invention) and the metal foil 4 are laminated by a first adhesive (inner adhesive) 6 is prepared. At this time, the first non-stretched film layer 7 of the sealing film 3 is connected to the first adhesive 6 . Then, the obtained laminate is subjected to heat treatment (aging treatment) to obtain the exterior material 1 for a storage battery device of the present invention.

Next, a second manufacturing method (method of manufacturing an exterior material for a storage battery device) according to the present invention will be described. The surface on one side of the prepared metal foil 4 is laminated with a heat-resistant resin film (outer layer) 2 via a second adhesive (outer adhesive) 5, and the other side of the metal foil 4 is interposed with a first adhesive ( The inner side adhesive agent 6 is a laminate body formed by laminating the sealing film 3 of the present invention (the first invention or the second invention). At this time, the first non-stretched film layer 7 of the sealing film 3 is connected to the first adhesive (inner adhesive) 6 (see FIGS. 1 and 2). Then, the laminate (the aging treatment) obtained by the heat treatment is used, whereby the exterior material 1 for a storage battery device of the present invention having the configuration shown in Figs. In other words, the exterior material 1 for a storage battery device of the present invention obtained by the aging treatment has a surface on one side of the metal foil layer 4 via a second adhesive layer (outer adhesive layer) 5 and a heat resistant resin layer. (Outer layer) 2 is integrated in layers, and the other side surface of the metal foil layer 4 is integrated with the first adhesive layer (inner adhesive layer) 6 and the inner sealing layer (sealing film) (inner layer) 3 The composition of the formation (see Figures 1, 2). In the sealing film 3, when the sealing film of the first invention is used, the second non-stretched film layer 8 of the sealing film 3 is formed as the innermost layer (see Fig. 1). Further, in the sealing film 3, when the sealing film of the second invention is used, the third non-stretched film layer 9 of the sealing film 3 is formed as the innermost layer (see Fig. 2).

The first adhesive (inside adhesive) 6 is not particularly limited, and examples thereof include a thermosetting adhesive. In addition, the second adhesive (outer adhesive) 5 is not particularly limited, and examples thereof include a thermosetting adhesive. The thermosetting adhesive is not particularly limited, and examples thereof include an olefin-based adhesive, an epoxy-based adhesive, and an acrylic adhesive.

The heating temperature of the aging treatment is preferably set to 65 ° C or lower, and is set at 35 ° C from the viewpoint of the degree of hardening of the adhesive and the amount of the lubricant remaining in the innermost layer of the exterior material. 45 ° C is better. Further, in the heating time of the aging treatment, since the curing time changes depending on the type of the adhesive, it is sufficient to obtain a sufficient bonding strength for the type of the bonding agent, but the heating time is taken into consideration in consideration of the pre-step time. It is preferable to be as short as possible under the condition that sufficient adhesion strength can be obtained.

In the sealing film 3 used for the production of the sealing material 3 for the electrical storage device obtained by the aging treatment, the sealing film of the present invention (the first invention or the second invention) is used, so that the moldability is excellent and the surface is less likely to be white powder. A sufficient lamination strength and sufficient sealing strength can be obtained.

In the exterior material 1 for an electrical storage device obtained by the aging treatment, the amount of the lubricant present on the surface of the innermost layer is preferably in the range of 0.1 μg/cm ² to 1.0 μg/cm ² . In the sealing film 3, when the sealing film of the first invention is used, the amount of lubricant present on the surface 8a of the second non-stretched film layer 8 is preferably in the range of 0.1 μg/cm ² to 1.0 μg/cm ² . (see Fig. 1), when the sealing film of the second invention is used as the sealing film 3, the amount of lubricant present on the surface 9a of the third non-stretched film layer 9 is 0.1 μg/cm ² to 1.0 μg/cm ^{2 .} It is better within the range (see Figure 2). In the exterior material 1 for an electrical storage device obtained by the aging treatment, the amount of the lubricant present on the surfaces 8a and 9a of the innermost layer is preferably in the range of 0.1 μg/cm ² to 0.6 μg/cm ² .

In the exterior material 1 for a storage battery device of the present invention, the inner seal layer (inner layer) 3 has excellent chemical resistance to an electrolytic solution or the like which is highly corrosive to a lithium ion secondary battery, and serves as an external material. The function of heat sealing.

Further, the heat-resistant resin layer (base material layer; outer layer) 2 is not necessarily a constituent layer, but is applied to the other surface of the metal foil layer 4 (the surface opposite to the inner sealing layer). The second adhesive layer (outer adhesive layer) 5 is preferably laminated with the heat-resistant resin layer 2 (see FIGS. 1 and 2). By providing such a heat-resistant resin layer 2, it is possible to sufficiently ensure the insulation of the other side of the surface of the metal foil layer 4 (the surface opposite to the inner sealing layer), and to improve the exterior material 1 for a storage device. Physical strength and impact resistance.

The heat-resistant resin constituting the heat-resistant resin layer (base material layer; outer layer) 2 is a heat-resistant resin that does not melt at a heat-sealing temperature when heat-sealing the exterior material. In the heat-resistant resin, the heat-resistant resin having a melting point higher than the melting point of the resin constituting the second non-stretched film layer 8 by 10 ° C or higher is preferable, and the second invention is used in comparison with the above-mentioned second invention. It is preferred that the resin constituting the third non-stretched film layer 9 has a heat-resistant resin having a melting point of 10 ° C or higher.

The heat-resistant resin layer (outer layer) 2 is not particularly limited, and examples thereof include a polyamide film such as a nylon film, a polyester film, and the like, and a stretched film of these is preferably used. Wherein, the heat resistant resin layer 2 is a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially oriented polyethylene terephthalate (PET) film or a biaxially stretched polyethylene naphthalate B. A biaxially stretched polyimide film such as a biaxially stretched nylon film such as a diester (PEN) film is particularly preferable. The nylon film is not particularly limited, and examples thereof include a nylon film, a 6,6 nylon film, and an MXD nylon film. Further, the heat-resistant resin layer 2 may be formed in a single layer, or may be formed, for example, by a multi-layer (a laminate of a PET film/nylon film) composed of a polyester film/polyamide film.

The thickness of the heat resistant resin layer (outer layer) 2 is preferably 2 μm to 50 μm. In the case of using a polyester film, the thickness is preferably from 2 μm to 50 μm; and in the case of using a nylon film, the thickness is preferably from 7 μm to 50 μm. By setting it to the above-mentioned appropriate lower limit or more, it is possible to ensure sufficient strength of the exterior material, and by setting it below the above-mentioned appropriate upper limit value, it is possible to reduce the stress during molding such as bulging molding and extension molding, and to improve the molding. Sex.

The metal foil layer 4 serves as a function of imparting air shielding properties against the intrusion of oxygen or moisture in the exterior material 1. The metal foil layer 4 is not particularly limited, and examples thereof include an aluminum foil, a SUS foil (stainless steel foil), and a copper foil. Among them, an aluminum foil or a SUS foil (stainless steel foil) is preferably used. The thickness of the metal foil layer 4 is preferably 5 μm to 120 μm. By making it 5 μm or more, it is possible to prevent the occurrence of pinholes which are delayed in the production of the metal foil, and by 120 μm or less, the stress during molding such as bulging molding and extension molding can be reduced, and the moldability can be improved. The thickness of the metal foil layer 4 is preferably from 10 μm to 80 μm.

It is preferable that the metal foil layer 4 is subjected to a chemical conversion treatment on at least the inner surface (the surface on the inner seal layer 3 side). By performing such a chemical conversion treatment, corrosion of the surface of the metal foil due to the contents (electrolyte of the battery, etc.) can be sufficiently prevented. For example, the metal foil can be subjected to a chemical conversion treatment by the following treatment. In other words, for example, on the surface of the metal foil subjected to the degreasing treatment, the aqueous solution is applied by applying an aqueous solution of any one of the following 1) to 3), and drying is carried out to apply a chemical conversion treatment:

1) an aqueous solution mixture of at least one compound comprising phosphoric acid, chromic acid, and a metal salt selected from the group consisting of a metal salt of a fluoride and a fluoride;

2) at least one of phosphoric acid, at least one selected from the group consisting of an acrylic resin, a chitosan derivative resin, and a phenol resin, and at least one selected from the group consisting of chromic acid and chromium (III) salt. An aqueous solution of a mixture of compounds.

3) a resin containing at least one selected from the group consisting of phosphoric acid, an acrylic resin, a chitosan derivative resin, and a phenol resin, and at least one selected from the group consisting of chromic acid and chromium (III) salt And an aqueous solution of a mixture of at least one compound selected from the group consisting of a metal salt of a fluoride and a non-metal salt of a fluoride.

The chemical conversion film is preferably 0.1 mg/m ² to 50 mg/m ^{2 in terms} of chromium adhesion (per side), and particularly preferably 2 mg/m ² to 20 mg/m ² .

The thickness of the second adhesive layer (outer adhesive layer) 5 is preferably 1 μm to 5 μm. Among them, from the viewpoint of thinning and weight reduction of the exterior material 1, the thickness of the outer adhesive layer 5 is particularly preferably set to 1 μm to 3 μm.

The thickness of the first adhesive layer (inner adhesive layer) 6 is preferably 1 μm to 5 μm. Among them, from the viewpoint of thinning and weight reduction of the exterior material 1, the thickness of the inner adhesive layer 6 is particularly preferably set to 1 μm to 3 μm.

The exterior material 1 for an electrical storage device of the present invention is used, for example, as an exterior material for a lithium ion secondary battery. The exterior material 1 for the electrical storage device can be used as an exterior material (see FIG. 4) without being molded, and can be used as the outer casing 10 by, for example, deep-stretching or bulging molding (refer to Figure 4).

An embodiment of the power storage device 30 configured by using the exterior material 1 for a storage battery device of the present invention is as shown in FIG. This power storage device 30 is a lithium ion battery. In the present embodiment, as shown in Figs. 3 and 4, the exterior casing 10 obtained by molding the exterior material 1 and the planar exterior material 1 constitute the exterior member 15. In the housing recessed portion of the outer casing 10 which is formed by molding the outer material 1 of the present invention, the main body portion (electrochemical element or the like) 31 of the power storage device having a substantially rectangular parallelepiped shape is accommodated in the main body portion 31 of the electric storage device Above, the exterior material 1 of the present invention is not formed, and the inner seal layer 3 side is disposed inside (lower side), the peripheral portion of the inner seal layer 3 of the planar exterior material 1 and the outer casing The inner seal layer 3 of the flange portion (the peripheral portion for the seal) of the outer casing 10 is sealed by heat sealing and sealing, and constitutes the power storage device 30 of the present invention (see Figs. 3 and 4). The inner surface of the housing recessed portion of the outer casing 10 is the inner seal layer 3, and the outer surface of the housing recess is a heat-resistant resin layer (outer layer) 2 (see FIG. 4). Moreover, when the exterior material of the exterior case 10 is used, when the exterior material shown in FIG. 1 is used, the surface of the inner side of the accommodating recess is the 2nd non-extension film layer 8 of the innermost layer, and the outer casing 10 is formed. When the exterior material shown in Fig. 2 is used as the material, the inner surface of the housing recess is the third innermost stretched film layer 9 of the innermost layer.

In Fig. 3, reference numeral 39 denotes a heat seal portion in which a peripheral portion of the exterior material 1 and a flange portion (a peripheral portion of the seal) of the outer casing 10 are joined (fused). Further, the power storage device 30 is connected to the front end portion of the power storage device main body portion 31 before being led out of the exterior member 15, but is omitted from the drawings.

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

The width of the heat seal portion 39 is preferably set to 0.5 mm or more. By making it 0.5 mm or more, sealing can be performed reliably. Preferably, the width of the heat seal portion 39 is set to be 3 mm to 15 mm.

Further, in the above-described embodiment, the exterior member 15 is composed of the outer casing 10 obtained by molding the exterior material 1 and the planar outer casing 1 (see Figs. 3 and 4), but there is no particular In addition to such a combination, for example, the exterior member 15 may be composed of a pair of planar outer materials 1 or may be composed of an outer casing 10.

[Examples]

Hereinafter, specific embodiments of the present invention will be described, and the present invention is not particularly limited to the embodiments.

<Example 1>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol is applied to both surfaces of the aluminum foil 4 having a thickness of 40 μm, and then dried at 180 ° C to form a chemical conversion film. . The chromium adhesion amount of this chemical conversion film was 10 mg/m ² per one side.

Then, on the side of one side of the aluminum foil 4 on which the chemical conversion treatment was completed, a two-axis stretch 6 nylon film 2 having a thickness of 25 μm was dry-laminated (bonded) via a two-liquid-curable polyurethane-based adhesive 5 .

Next, a first unstretched film 7 having a thickness of 12 μm containing an ethylene-propylene random copolymer and 100 ppm of erucylamine erucamide was contained, and an ethylene-propylene block copolymer, 2,500 ppm of erucamide and 2000 ppm were contained. a second unstretched film 8 having a thickness of 28 μm formed by cerium oxide particles (anti-blocking agent; average particle diameter: 2 μm), and two layers are laminated and co-extruded using a T-die to obtain a thickness of the two-layer laminated layer. After the 40 μm sealing film (the first unstretched film 7 / the second unstretched film 8) 3, the first unstretched film 7 of the sealing film 3 is coated with a two-liquid hardening type maleic acid-denatured polypropylene adhesive. 6. The other side of the aluminum foil 4 after the dry lamination is superposed, and is dry laminated by being sandwiched between a rubber nip roll and a laminating roll heated to 100 ° C, and then, by 40 After aging for 10 days at ° C (heating), the exterior material 1 for a storage battery device having the configuration shown in Fig. 1 was obtained.

Further, the two-liquid-curable maleic acid-denatured polypropylene adhesive is 100 parts by mass of a maleic acid-modified polypropylene (melting point: 80 ° C, an acid value of 10 mgKOH/g) using a main component, and a hexamethylene group of a hardener. 8 parts by mass of an isocyanurate isocyanurate (NCO content: 20% by mass), and an adhesive solution prepared by further mixing a solvent to form a solid coating amount of 2 g/m. ² , the surface of the other side of the aluminum foil 4 is coated, heated and dried, and then laminated on the surface of the first non-stretched film 7 of the sealing film 3.

In the exterior material 1 for an electrical storage device, the amount of lubricant present on the surface 8a of the innermost layer (the second non-stretched film 8) of the exterior material 1 is 0.27 μg/cm ² , which is present in the sealing film of the exterior material. The amount of lubricant of the surface of the metal foil layer 4 side (the surface of the first non-stretched film layer 7) 7a in 3 was 0.38 μg/cm ² (refer to Table 1).

<Example 2>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 0 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 3000 ppm. In the same manner as in the first embodiment, the exterior material 1 for a storage battery device having the configuration shown in Fig. 1 was obtained.

<Example 3>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water, and ethanol is applied to both surfaces of the aluminum foil 4 having a thickness of 40 μm, and then dried at 180 ° C to form a chemical conversion film. . The chromium adhesion amount of this chemical conversion film was 10 mg/m ² per one side.

Then, on the side of one side of the aluminum foil 4 on which the chemical conversion treatment was completed, a two-axis stretch 6 nylon film 2 having a thickness of 25 μm was dry-laminated (bonded) via a two-liquid-curable polyurethane-based adhesive 5 .

Next, a 6 μm-thick first stretch-free film 7 comprising an ethylene-propylene random copolymer and 100 ppm of erucylamine amide was sequentially contained, and an ethylene-propylene block copolymer and 2500 ppm of erucylamine were used. The second non-stretched film 8 having a thickness of 28 μm contains an ethylene-propylene random copolymer, 1000 ppm of erucamide and 2000 ppm of cerium oxide particles (anti-blocking agent; average particle diameter of 2 μm) and a thickness of 6 μm. No stretch film 9 or 3 layers were laminated and co-extruded using a T-die to obtain a three-layer laminated film having a thickness of 40 μm (first unstretched film 7 / second unstretched film 8 / third unstretched film 9) After 3, the first non-stretched film 7 of the sealing film 3 is laminated on the other side of the dry-laminated aluminum foil 4 via a two-liquid-hardened maleic acid-modified polypropylene adhesive 6. It is dry-laminated by pressing between a rubber nip roll and a laminating roll heated to 100 ° C, and then aged by aging at 40 ° C for 10 days (heating) to obtain a composition as shown in FIG. 2 . The exterior material 1 for the electrical storage device.

Further, the two-liquid-curable maleic acid-denatured polypropylene adhesive is 100 parts by mass of a maleic acid-modified polypropylene (melting point: 80 ° C, an acid value of 10 mgKOH/g) using a main component, and a hexamethylene group of a hardener. 8 parts by mass of an isocyanurate isocyanurate (NCO content: 20% by mass), and an adhesive solution prepared by further mixing a solvent to form a solid coating amount of 2 g/m. ² , the surface of the other side of the aluminum foil 4 is coated, heated and dried, and then laminated on the surface of the first non-stretched film 7 of the sealing film 3.

In the exterior material 1 for an electrical storage device, the amount of the lubricant present on the surface 9a of the innermost layer (the third non-stretched film 9) of the exterior material is 0.25 μg/cm ² , and is present in the sealing film 3 of the exterior material. The amount of the lubricant on the surface of the intermediate metal foil layer 4 side (the surface of the first non-stretched film layer 7) 7a was 0.25 μg/cm ² (refer to Table 1).

<Example 4>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 60 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 1000 ppm. In the same manner as in the third embodiment, the exterior material 1 for a storage battery device having the configuration shown in Fig. 2 was obtained.

<Example 5>

The exterior material 1 for a storage battery device having the configuration shown in Fig. 2 was obtained in the same manner as in the third embodiment except that the concentration of the erucic acid amide contained in the third non-stretched film layer 9 before the lamination was set to 500 ppm.

<Example 6>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 60 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 1000 ppm, and before lamination In the third non-stretched film layer 9 of the third unstretched film layer 9, the content of the erucic acid amide is set to 2000 ppm, and the exterior material 1 for a storage battery device having the structure shown in Fig. 2 is obtained in the same manner as in the third embodiment.

<Example 7>

In addition to the use of behenic acid decylamine in place of the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9, as a lubricant, erucamide, and the first before the lamination In the same manner as in the third embodiment, the exterior material 1 for a storage battery device having the composition shown in Fig. 2 was obtained in the same manner as in the example 3 except that the concentration of the octadecylamine in the extended film layer 7 was changed to 50 ppm.

<Example 8>

The same as Example 7 except that oleic acid amide was used instead of erucamide as a lubricant in the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9. An exterior material 1 for a storage battery device having the configuration shown in Fig. 2 is obtained.

<Example 9>

The same as Example 7 except that decylamine stearate was used instead of the erucamide as the lubricant in the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9. An exterior material 1 for a storage battery device having the configuration shown in Fig. 2 is obtained.

<Example 10>

The exterior material 1 for a storage battery device having the configuration shown in Fig. 2 was obtained in the same manner as in the third embodiment except that the concentration of the erucic acid amide contained in the second non-stretched film layer 8 before the layering was set to 4,500 ppm.

<Example 11>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 0 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before the lamination was set to 2000 ppm. In the same manner as in the third embodiment, the exterior material 1 for a storage battery device having the configuration shown in Fig. 2 was obtained.

<Comparative Example 1>

The exterior material for a storage battery device was obtained in the same manner as in Example 1 except that the concentration of the erucic acid amide contained in the first unstretched film layer 7 before the lamination was set to 400 ppm.

<Comparative Example 2>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination is set to 50 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before the lamination is set to 6000 ppm. In the same manner as in the first embodiment, an exterior material for a storage battery device was obtained.

<Comparative Example 3>

The exterior material for a storage battery device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide contained in the first unstretched film layer 7 before the lamination was set to 500 ppm.

<Comparative Example 4>

The concentration of erucamide in the first unstretched film layer 7 before the lamination is set to 400 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination is set to 1000 ppm. In the same manner as in the third embodiment, an exterior material for a storage battery device was obtained.

<Comparative Example 5>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 500 ppm, and the concentration of erucamide in the third non-stretched film layer 9 before lamination was set to 500 ppm. In the same manner as in the third embodiment, an exterior material for a storage battery device was obtained.

<Comparative Example 6>

The concentration of erucamide in the first non-stretched film layer 7 before lamination was set to 360 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 1000 ppm, and before lamination In the third non-stretched film layer 9 of the third non-stretched film layer 9, the content of the erucic acid amide was set to 2000 ppm, and the exterior material for the electricity storage device was obtained in the same manner as in the third embodiment.

<Comparative Example 7>

In addition to the use of behenic acid decylamine in place of the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9, as a lubricant, erucamide, and the first before the lamination In the extension film layer 7, the concentration of the octadecylamine was set to 320 ppm, and the exterior material for the electricity storage device was obtained in the same manner as in the third embodiment.

<Comparative Example 8>

The same as Comparative Example 7 except that oleic acid amide was used instead of the erucamide as the lubricant in the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9. An exterior material for a power storage device is obtained.

<Comparative Example 9>

The same as Comparative Example 7 except that decylamine stearate was used instead of the erucamide as the lubricant in the first non-stretched film layer 7, the second non-stretched film layer 8, and the third non-stretched film layer 9. The exterior material for the electrical storage device is obtained.

<Comparative Example 10>

The concentration of erucamide in the first unstretched film layer 7 before the lamination is set to 400 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before the lamination is set to 4,500 ppm. In the same manner as in the third embodiment, an exterior material for a storage battery device was obtained.

<Comparative Example 11>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 60 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 100 ppm. In the same manner as in the third embodiment, an exterior material for a storage battery device was obtained.

<Comparative Example 12>

The exterior material for a storage battery device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide contained in the second non-stretched film layer 8 before the lamination was set to 5,500 ppm.

<Comparative Example 13>

The exterior material for a storage battery device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide contained in the third non-stretched film layer 9 before the lamination was set to 100 ppm.

<Comparative Example 14>

The concentration of erucamide in the first non-stretched film layer 7 before the lamination was set to 60 ppm, and the concentration of erucamide in the second non-stretched film layer 8 before lamination was set to 1000 ppm, and before lamination In the third non-stretched film layer 9 of the third non-stretched film layer 9, the content of the erucic acid amide was set to 4000 ppm, and the exterior material for the electricity storage device was obtained in the same manner as in the third embodiment.

The exterior materials for each electrical storage device obtained as described above (completed aging treatment) were evaluated based on the following evaluation method. The results are shown in Tables 1 and 2.

In addition, the dynamic friction coefficient described in Tables 1 and 2 is based on JIS K7125-1995, and the dynamic friction coefficient is measured on the surface of the innermost layer of each exterior material for electrical storage device (completed aging treatment) (see Figs. ). The surface of the innermost layer, the surfaces 8a of the second non-stretched film layer of Examples 1, 2 and Comparative Examples 1 and 2, and the surface 9a of the third non-stretched film layer of Examples 3 to 11 and Comparative Examples 3 to 14 (Refer to Figures 1 and 2).

<Evaluation method of the amount of lubricant present on the surface of the innermost layer of the exterior material>

After cutting out two rectangular test pieces of 100 mm in length × 100 mm in width from the exterior materials for the respective electrical storage devices, the peripheral portions of the inner sealing layers of the two test pieces superposed on each other were heat-sealed at a temperature of 200 ° C. The heat is sealed underneath to make the bag body. 1 mL of acetone was injected into the inner space of the bag using a syringe. After the surface of the innermost layer of the inner seal layer was placed in contact with acetone for 3 minutes, acetone in the bag was taken out. The amount of the lubricant contained in the extracted liquid was measured and analyzed by a gas chromatograph to determine the amount of lubricant (μg/cm ² ) present on the surface of the innermost layer of the exterior material. That is, the amount of lubricant per 1 cm ² of the surface of the innermost layer is obtained.

<Evaluation method of the amount of lubricant present on the surface 7a of the first non-stretched film layer in the exterior material>

In each of the examples and the comparative examples, the sealing film 3 formed by co-extrusion was cut into a rectangle having a length of 200 mm × a width of 200 mm, and then aged at 40 ° C for 10 days. After the test piece having a rectangular shape of 100 mm in length × 100 mm in width was cut out from the film after aging, the first stretched film layers 7 of the test pieces of the two test pieces were brought into contact with each other, and the peripheral portion was covered with a nylon film. The bag body was prepared by heat sealing at a heat sealing temperature of 200 °C. 1 mL of acetone was injected into the inner space of the bag body using a syringe, and after leaving the surface of the first non-stretched film layer (the inner side surface of the bag body) in contact with acetone for 3 minutes, acetone in the bag body was taken out. The amount of lubricant (μg/cm ² ) present on the surface 7a of the first non-stretched film layer was determined by measuring and analyzing the amount of the lubricant contained in the extract using a gas chromatograph. That is, the amount of lubricant per 1 cm ² of the surface of the first non-stretched film layer.

<Formability Evaluation Method>

Using a straight mold which is formed into a deep free form, the outer material is subjected to deep drawing and one-stage forming under the following molding conditions, and the formability is evaluated for each forming depth (9 mm, 8 mm, 7 mm, 6 mm, 5 mm, 4 mm, 3 mm, 2 mm). The corner portion has no maximum forming depth (mm) at which pinholes can be formed well. When it is judged that the maximum forming depth is 5 mm or more, the mark is "○", the maximum forming depth is 2 mm or more, the case where the maximum forming depth is less than 5 mm is marked as "△", and the case where the maximum forming depth is less than 2 mm is marked as "x". Further, the presence or absence of pinholes was investigated by visually observing the presence or absence of transmitted light through the pinholes.

(forming conditions)

Forming die... Punch: 33.3mm × 53.9mm, die: 80mm × 120mm, corner R: 2mm, punch R: 1.3mm, die R: 1mm

Anti-wrinkle pressure... gauge pressure: 0.475MPa, actual pressure (calculated value): 0.7MPa

Material...SC (carbon steel) material, only punch R chrome plated.

<The evaluation of the presence or absence of white powder>

A rectangular test piece of 600 mm in length × 100 mm in width was cut out from the exterior material for each electrical storage device, and the inner sealing layer 3 surface of the obtained test piece (that is, the surface 8a or 9a of the innermost layer) was placed on the upper side. On the top of the test piece, the SUS hammer (the mass of 1.3 kg and the size of the grounding surface is 55 mm × 50 mm) in which the surface of the black cloth is placed in black is placed in the state with the test piece. The horizontal direction parallel thereto was stretched at a stretching speed of 4 cm/sec, and was stretched and moved over the test piece over a length of 400 mm in a contact state. The cloth (tank) of the contact surface of the hammer after the stretching movement was observed with the naked eye, and the surface of the white powder on the surface of the cloth (black color) was marked "×", and the white powder was marked "△" by the general degree (middle degree). White powder is almost no or white powder is not observed as "○". Moreover, the above-mentioned black cloth used "static discharge sheet S SD2525 3100" manufactured by TRUSCO Corporation.

<Sealing strength evaluation method>

After the test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained exterior material, the test pieces of the two test pieces were brought into contact with each other by the inner seal layers, and the test industry shares were limited. The company's heat sealing device (TP-701-A) is heat-sealed by one-side heating at a heat sealing temperature of 200 ° C, a sealing pressure of 0.2 MPa (instrument display pressure), and a sealing time of 2 seconds.

Next, one of the above-mentioned inner sealing layers is heat-sealed to each other, and the outer casing (test body) is manufactured by using a precision universal testing machine (AGS-5kNX) manufactured by Shimadzu Corporation based on JIS Z0238-1998. The peeling strength at the time of the peeling speed of 100 mm/min and 90 degree peeling of each inner side sealing layer of the sealing part was measured, and it was set as the sealing intensity (N / 15 mm width).

This sealing strength is marked as "○" (passed) for 30N/15mm or more, and "X" for those less than 30N/15mm wide.

<Evaluation method of agglutination degree of peeling interface>

After the sealing strength (peeling strength) was measured, both sides of the peeling portion (destructive portion) of the inner sealing layer of the outer material were visually observed, and the presence or absence of whitening of both sides of the peeling portion (destructive portion) was determined (the whitening strength was judged to be stronger) The greater the degree of agglutination, the evaluation was performed according to the following criteria.

(judgment basis)

Whitening occurs remarkably, and those with a large degree of agglutination are marked as "○", whitening occurs to a certain extent, and the degree of agglutination is marked as "△", and no whitening or whitening is observed, and those with low agglutination are marked as "X".

<Lamination strength evaluation method>

A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained exterior material, and the inner seal layer 3 and the metal foil layer (aluminum foil layer) 4 were peeled off by immersing the end portion of the test body in the longitudinal direction with an alkaline peeling liquid. . Based on JIS K6854-3 (1999), a precision universal testing machine (AGS-5kNX) manufactured by Shimadzu Corporation was used, and a laminate containing a metal foil layer (aluminum foil layer) 4 was clamped and fixed by a chuck on one side. The chuck on one side was sandwiched and fixed by the peeling sealing layer 3, and the peeling strength at the time of T-peeling at an extension speed of 100 mm/min in this state was measured, and this was used as a layer of the inner seal layer 3 and the metal foil layer 4. Compressive strength (follow strength) (N/15 mm wide). The peel strength was measured at 25 ° C. The evaluation was performed according to the following criteria.

(judgment basis)

Those whose lamination strength is "5.0N/15mm width" or more are marked as "○", and those whose lamination strength is less than "5.0N/15mm width" are marked as "X".

As is clear from Table 1, the exterior materials for electrical storage devices of the present invention of Examples 1 to 11 which are formed by using the sealing film of the present invention have excellent moldability, and it is difficult for white powder to appear on the surface of the innermost layer of the exterior material. A sufficient lamination strength and sufficient sealing strength can be obtained.

On the other hand, in Comparative Examples 1 to 10 which were out of the range defined by the present invention, sufficient laminate strength could not be obtained. Further, in Comparative Examples 2 and 8, the sealing strength was also insufficient. Further, Comparative Examples 11 and 13 which deviated from the scope of the present invention were inferior in formability, and Comparative Example 14 produced white powder on the surface of the innermost layer, and in Comparative Example 12, white powder was formed on the surface of the innermost layer, and the sealing strength was insufficient. The lamination strength is also insufficient.

[Industry Utilization]

The exterior material for a power storage device produced by using the sealing film of the present invention, the exterior material for a power storage device of the present invention, and the exterior material for a power storage device obtained by the production method of the present invention can be used, for example, as follows:

. Power storage device such as lithium battery (lithium ion battery, lithium polymer battery, etc.)

. Lithium ion capacitor

. Electric double layer capacitor

. All solid state battery

And other types of power storage devices are installed outside.

The present application claims priority to Japanese Patent Application No. 2017-53012, the entire disclosure of which is incorporated herein by reference.

The terms and descriptions used herein are for describing embodiments of the invention, but the invention is not limited thereto. Various modifications within the scope of the invention should be construed as being acceptable.

Claims (13)

 A sealing film for a material other than a power storage device, which is a sealing film formed by a laminate of two or more layers, wherein the two or more layers include a first non-extended film layer and one side of the first non-stretch film layer The second non-stretched film layer laminated on the surface is characterized in that the first non-stretched film layer is disposed on a layer closest to the metal foil side of the sealing film; and the first non-stretched film layer contains random copolymerization In combination, the random copolymerization system contains propylene and propylene as a copolymerization component, and the first non-stretched film layer contains no lubricant or contains more than 0 ppm and less than 250 ppm of lubricant. The second non-stretched film layer contains a propylene-based copolymer and a lubricant; and the concentration of the lubricant in the second non-stretched film layer is 500 ppm to 5000 ppm.    The sealing film for a power storage device according to the first aspect of the invention, further comprising a third non-stretch film layer, wherein the third non-stretch film layer is laminated on the second non-stretch film layer The side of the first laminate without the stretched film layer is the opposite side, and the third stretchless film layer contains a random copolymer and a lubricant, and the random copolymerization system contains propylene and propylene other than the copolymerization component. The other copolymerization component; the concentration of the lubricant in the third non-stretched film layer is 200 ppm to 3000 ppm.    The sealing film for a power storage device according to the second aspect of the invention, wherein the concentration of the lubricant in the second non-stretched film layer is 1.0, and the concentration of the lubricant in the third non-stretched film layer is 1.0. Times ~ 5.0 times.   An exterior material for a power storage device, comprising: an inner sealing layer formed by the sealing film according to the first aspect of the patent application; and a metal foil layer laminated on one side of the inner sealing layer; The amount of the lubricant on the surface of the non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² . An exterior material for a power storage device, comprising: an inner sealing layer formed by a sealing film according to claim 2 or 3, and a metal foil layer laminated on one side of the inner sealing layer; The amount of the lubricant on the surface of the third non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² . An exterior material for a power storage device, comprising: a heat-resistant resin layer on the outer layer; an inner seal layer formed by the seal film described in claim 1; and a metal foil layer disposed between the two layers; The amount of the lubricant present on the surface of the second non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² . An exterior material for a power storage device, comprising: a heat-resistant resin layer of an outer layer; an inner sealing layer formed by a sealing film according to claim 2 or 3; and a metal foil disposed between the two layers The amount of the lubricant present on the surface of the third non-stretched film layer is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .  An outer casing for an electrical storage device, which is characterized by being formed of a molded article of the outer casing described in any one of claims 4 to 7.    A method for producing an exterior material for a power storage device, comprising: a preparation step of laminating a sealing film and a metal foil according to any one of claims 1 to 3 of the first adhesive layer application; And an aging step of heat-treating the laminate to obtain an exterior material for a storage device.    The method for producing an exterior material for a storage battery device according to claim 9, wherein the first adhesive is a thermosetting adhesive.    A method for producing an exterior material for a power storage device, comprising the step of preparing a surface on one side of a metal foil via a second adhesive and a heat-resistant resin film, and a surface of the other side of the metal foil is interposed A laminated body comprising a laminate of a sealing film according to any one of the first to third aspects of the invention, and an aging step of heat-treating the laminate to obtain an exterior material for a storage device.    The method for producing an exterior material for a storage battery device according to the invention, wherein the first adhesive is a thermosetting adhesive, and the second adhesive is a thermosetting adhesive.   The method for producing an exterior material for a power storage device according to any one of the first aspect of the invention, wherein the amount of the lubricant present on the surface of the innermost layer of the exterior material for the electrical storage device obtained by the heat treatment is obtained. It is in the range of 0.1 μg/cm ² to 1.0 μg/cm ² .