KR20180106893A - Sealant film for exterior material of electric storage device, exterior material for electric storage device and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a sealant film for an exterior material of an electricity storage device, which comprises a laminate of two or more layers, including a first non-stretched film layer (7) disposed on the most metal foil side and a second non-stretched film layer (8) stacked on one side of the first non-stretched film layer. The first non-stretched film layer (7) contains propylene as a copolymerization component and a random copolymer containing another copolymerization component other than propylene, and is configured not to contain a lubricant or configured to contain the lubricant greater than 0 ppm and equal to or less than 250 ppm. The second non-stretched film layer (8) contains a propylene-based polymer and a lubricant, wherein a concentration of the lubricant in the second non-stretched film layer (8) is 500 to 5,000 ppm. Accordingly, molding properties are excellent, white powder is difficult to be exhibited on a surface, and sufficient strength of a laminate and a seal can be obtained.

Description

TECHNICAL FIELD [0001] The present invention relates to a sealant film for an exterior material of an electric storage device, an exterior material for an electric storage device, and a manufacturing method thereof. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention constitutes a casing of a battery device such as a battery or a condenser used for a battery used in a portable device such as a smart phone or a tablet, a condenser, a hybrid car, an electric car, a wind power generator, A sealant film to be used, and a method for manufacturing an outer casing for a power storage device using the sealant film.

Description of the Related Art [0002] In recent years, as mobile electrical appliances such as smart phones and tablet terminals have become thinner and lighter in weight, they have been used as exterior materials for electric storage devices such as lithium ion secondary batteries, lithium polymer secondary batteries, lithium ion capacitors, A laminate composed of a heat resistant resin layer / adhesive layer / metal foil layer / adhesive layer / thermoplastic resin layer (inner sealant layer) is used in place of the conventional metal can. Also, power sources for electric vehicles, large-sized power sources for electric power storage, and capacitors have also been increasingly externally enclosed in the laminated body (outer casing). As the extrusion molding or deep drawing molding is performed on the laminate, the molded body is molded into a three-dimensional shape such as a substantially rectangular parallelepiped shape. By molding the battery into the three-dimensional shape, it is possible to secure a space for accommodating the power storage device main body portion.

In order to form such a three-dimensional shape in a good state without pinholes or fractures, it is required to improve slidability of the surface of the inner sealant layer. A laminate obtained by sequentially laminating an exterior resin film, a first adhesive layer, a chemically treated aluminum foil, a second adhesive layer, and a sealant film in order to improve the slidability of the surface of the inner sealant layer to secure good moldability , The sealant film is made of a random copolymer of propylene and an? -Olefin having an α-olefin content of 2 to 10% by weight, and a lubricant is contained in an amount of 1000 to 5000 ppm in the laminated material for a secondary battery container (See Patent Document 1).

Patent Document 1: JP-A-2003-288865

However, in the above-mentioned conventional technique, it is difficult to control the amount of lubricant deposition on the innermost layer surface (the inner surface of the inner sealant layer) of the casing according to the heating holding time and the storage period in the production process of the casing (laminate) However, since the lubricant is excessively deposited on the surface, the lubricant adheres to the molding surface of the molding die during the molding of the casing, and white powder (white powder by lubricant) is generated. When such a white powder is adhered to and deposited on the molding surface, it is difficult to perform good molding. Therefore, it is necessary to clean the white powder every time the white powder adheres and deposits to remove the white powder. There is a problem that the productivity of the exterior material deteriorates.

Further, the liner strength (laminate strength with the metal foil and the inner sealant layer) is lowered due to the large amount of lubricant bleeding on the side of the metal foil side in the inner sealant layer, and peeling easily occurs between the metal foil and the inner sealant layer There is also a problem.

Of course, when the addition amount of the lubricant (the content of the lubricant) is reduced, it is possible to suppress deposition and accumulation of white powder and decrease the laminate strength, but in this case, there arises a problem that the amount of deposition of surface lubricant is insufficient, . Thus, in the past, it has been difficult to achieve both "excellent moldability" and "suppression of whitewashing on the surface of the exterior material and ensuring sufficient laminate strength".

The present invention has been made in view of such a technical background, and it is an object of the present invention to provide a sealant film for exterior materials of electric storage devices and a storage device for electric storage devices which are excellent in moldability, And a method for manufacturing the same.

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

[1] A sealant film comprising a laminate of two or more layers comprising a first non-stretched film layer and a second non-stretched film layer laminated on one surface of the first non-stretched film layer,

The first non-stretchable film layer is a layer disposed on the most metal foil side in the sealant film,

Wherein the first non-stretched film layer contains a random copolymer containing a copolymerization component other than propylene and propylene as a copolymerization component,

Wherein the first non-tear film layer is composed of no lubricant, or contains a lubricant of more than 0 ppm and not more than 250 ppm,

Wherein the second non-tear film layer contains a propylene polymer and a lubricant, and the concentration of the lubricant in the second non-extensible film layer is 500 ppm to 5000 ppm.

[2] The recording medium according to [1], further comprising a third non-rolled film layer laminated on the surface of the second non-rolled film layer opposite to the side on which the first non-rolled film layer is laminated, , A random copolymer containing a copolymer component other than propylene and propylene as a copolymerization component, and a lubricant, wherein the content concentration of the lubricant in the third non-oriented film layer is from 200 ppm to 3000 ppm, Sealant film for exterior materials.

[3] The sealant film for a casing of a power storage device according to item 2, wherein the concentration of the lubricant contained in the second non-rolled film layer is 1.0 to 5.0 times the concentration of the lubricant in the third non-rolled film layer.

[4] A laminate film comprising an inner sealant layer made of the sealant film described in the above 1, and a metal foil layer laminated on one surface side of the inner sealant layer, wherein the amount of the lubricant present on the surface of the second non- Cm < 2 > to 1.0 g / cm < 2 >.

[5] A rubber composition comprising an inner sealant layer made of the sealant film described in the above 2 or 3, and a metal foil layer laminated on one surface side of the inner sealant layer, wherein the amount of the lubricant present on the surface of the third non- / Cm < 2 > to 1.0 g / cm < 2 >.

[6] A multilayer film comprising a heat-resistant resin layer as an outer layer, an inner sealant layer comprising a sealant film described in the preceding paragraph 1, and a metal foil layer disposed between the two layers, Wherein the lubricating amount is in the range of 0.1 / / ㎠ to 1.0 / / ㎠.

[7] A laminate film comprising a heat-resistant resin layer as an outer layer, an inner sealant layer comprising a sealant film described in the above 2 or 3, and a metal foil layer disposed between the two layers, Wherein the lubricant amount is in the range of 0.1 占 퐂 / cm2 to 1.0 占 퐂 / cm2.

[8] An external case for an electric storage device comprising a molded article of an exterior material according to any one of items 4 to 7 above.

[9] A process for producing a laminate comprising the sealant film described in any one of the above items 1 to 3 and a laminate obtained by laminating a metal foil with a first adhesive,

And an aging step of subjecting the laminate to a heat treatment to obtain an exterior material for a power storage device.

[10] The method for manufacturing an exterior material for an electric storage device according to the item 9, wherein the first adhesive is a thermosetting adhesive.

[11] A heat-resistant resin film laminated on one surface of a metal foil through a second adhesive, and a sealant film according to any one of the above items 1 to 3 laminated on the other surface of the metal foil, A step of preparing a laminate,

And an aging step of subjecting the laminate to a heat treatment to obtain an exterior material for a power storage device.

[12] The method for manufacturing an exterior member for an electric storage device according to the item 11, wherein the first adhesive is a thermosetting adhesive and the second adhesive is a thermosetting adhesive.

[13] Manufacturing of a casing for electric storage devices according to any one of items 9 to 12, wherein the amount of lubricant present on the surface of the innermost layer of the casing material for a power storage device obtained by the heat treatment is in the range of 0.1 μg / cm 2 to 1.0 μg / Way.

(1) and (2), it is possible to suppress the decrease in the amount of the lubricant present on the inner surface (the surface of the innermost layer of the inner sealant layer) of the outer casing after the aging treatment, And the moldability is excellent, and it is difficult to express white powder on the inner surface (the surface of the innermost layer of the inner sealant layer) of the casing member, and sufficient room strength can be obtained. Further, since the amount of the lubricant present on the surface 7a of the first non-stretchable film layer on the metal foil side in the inner sealant layer of the outer sealant after the aging treatment is small, a sufficient laminate strength (laminate strength with the metal foil and the inner sealant layer) . The amount of lubricant present on the surface of the exterior material after the aging treatment (the surface of the innermost layer of the inner sealant layer) does not fluctuate even when subjected to thermal hysteresis during transportation or storage, It becomes possible to provide an exterior material.

In the invention of [3], the concentration of the lubricant contained in the second non-rolled film layer is 1.0 to 5.0 times the concentration of the lubricant in the third non-rolled film layer forming the innermost layer of the casing, The film thickness of the interface between the third non-tear film layer 9 of the innermost layer and the second non-tear film layer 8 (the two film layers 8 , 9) can be suppressed, and the concentration of the lubricant of the lubricant from the second non-rolled film layer (8) to the innermost third non-rolled film layer (9) (The interface between the two film layers 8 and 9) due to the gradient can be suppressed and it is possible to prevent the agglomeration of the surface of the third non-stretched film layer 9a It is possible to control the amount of lubricant to fall within a range of 0.1 / / cm 2 to 1.0 / / cm 2. As a result, the moldability can be further improved.

The invention of [4], [5], [6] and [7] provides an outer casing for a power storage device that is excellent in moldability, hardly shows white powder on its surface, and has sufficient laminate strength and sufficient room strength .

Further, since the heat-resistant resin layer as the outer layer is provided in the inventions of [6] and [7], it is possible to sufficiently secure insulation on the opposite side of the inner sealant layer in the metal foil layer, Strength and impact resistance can be improved.

According to the invention of [8], it is possible to provide a battery case for an electric power storage device which is capable of satisfactory molding and which is difficult to express white powder on the surface of the outer case (the innermost layer of the inner sealant layer) Can be provided.

According to the inventions of [9] to [12], it is possible to manufacture a jacket for an electric power storage device that is excellent in moldability, hardly displays white powder on its surface, and has sufficient laminate strength and sufficient room strength.

In addition, since the heat-resistant resin layer as the outer layer is provided in the inventions of [11] and [12], it is possible to sufficiently secure insulation on the opposite side of the inner sealant layer in the metal foil layer, The impact resistance can be improved.

According to the invention of [13], since the amount of lubricant present on the surface of the innermost layer of the casing is in the range of 0.1 μg / cm 2 to 1.0 μg / cm 2, better slipperiness is exhibited during molding and more excellent moldability is ensured It is possible to manufacture an exterior material for a power storage device which can further prevent the appearance of white powder. Further, the amount of lubricant (0.1 μg / cm 2 to 1.0 μg / cm 2) present on the surface of the innermost layer of the outer covering material for the electrical storage device obtained does not fluctuate even when subjected to thermal history during transport or storage, It is possible to provide an exterior material for a power storage device.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing one embodiment of a casing for a power storage device according to the present invention. Fig.
2 is a cross-sectional view showing another embodiment of a casing material for a power storage device according to the present invention.
3 is a cross-sectional view showing one embodiment of a power storage device according to the present invention.
Fig. 4 is a perspective view showing a casing (planar shape) constituting the power storage device of Fig. 3, a power storage device main body part, and an outer case (formed body molded in a three-dimensional shape) before being heat-sealed.

Fig. 1 shows an embodiment of a sealant film 3 for a casing of a power storage device according to the first invention. The sealant film 3 comprises a first non-extensible film layer 7 and a second non-extensible film layer 8 laminated on one surface of the first non-extensible film layer 7, Wherein the first non-rolled film layer (7) is a layer disposed on the side of the metal foil (4) in the sealant film (3), and the first non-rolled film layer comprises propylene And a random copolymer containing a copolymer component other than propylene, wherein the first non-stretched film layer (7) has a constitution containing no lubricant or a constituent containing a lubricant, and the second non-extrudable film The layer (8) contains a propylene polymer and a lubricant.

Fig. 2 shows an embodiment of a sealant film for a casing of a power storage device according to the second invention. This sealant film 3 comprises a second non-extensible film layer 8, a first non-extensible film layer 7 laminated on one surface of the second non-extensible film layer 8, And a third non-stretched film layer (9) laminated on the other surface of the non-stretched film layer (8), wherein the first non-stretched film layer (7) 3), and the first non-stretchable film layer (7) contains a random copolymer containing a copolymerization component other than propylene and propylene as a copolymerization component, and the first non-stretchable film layer The first non-extensible film layer (7) contains a lubricant or a lubricant. The second non-extensible film layer (8) contains a propylene polymer and a lubricant. The non-oriented film layer (9) contains a random copolymer containing a copolymerization component other than propylene and propylene as a copolymerization component, It contains a lubricant.

The random copolymer constituting the first non-tear film layer 7 and the third non-extensible film layer 9 may be a random copolymer containing "propylene" and "another copolymer component other than propylene" to be. With respect to the random copolymer, the "other copolymer component excluding propylene" is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene and 4-methyl- An olefin component, and butadiene.

The propylene polymer constituting the second lead-free 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 homopolypropylene and block copolymers containing "propylene" and "another copolymerizable component other than propylene" as a copolymerization component. Among them, as the propylene-based polymer, it is preferable to use at least one resin selected from the group consisting of homopolypropylene and the block copolymer.

With regard to the block copolymer, the "other copolymer component excluding propylene" is not particularly limited, and examples thereof include ethylene, 1-butene, 1-hexene, 1-pentene and 4-methyl- An olefin component, and butadiene.

The second non-stretchable film layer (8) is preferably a composition containing the propylene polymer, the elastomer component, and the lubricant. Among them, it is more preferable that the elastomer component is added to the propylene polymer to show a morphology (microstructure) separated by a microphase. That is, the elastomer-modified propylene polymer is preferably an elastomer-modified propylene polymer exhibiting a sea-island structure in which an elastomer component is separated into islands in the sea of the propylene polymer, The whitening phenomenon can be made less likely to occur and the insulating property after yarn can be further improved. Examples of the elastomer component include, but are not limited to, EPR (ethylene propylene rubber), propylene-butene elastomer, propylene-butene-ethylene elastomer, EPDM (ethylene-propylene-diene rubber) Among them, it is preferable to use EPR (ethylene propylene rubber) as the elastomer component.

The sealant film (3) according to the first aspect of the present invention is such that the first non-stretchable film layer (7) contains no lubricant or contains no more than 250 parts by weight of the lubricant, It is important that the content concentration of the lubricant in the two non-oriented film layers is set to 500 ppm to 5000 ppm. By satisfying this condition, it is possible to suppress the movement of the lubricant present in the second non-extension film layer 8 into the first non-extension film layer 7 when the aging treatment for curing the adhesive is performed It is possible to ensure the amount of lubricant to be deposited on the surface 8a of the innermost layer (second non-extruded film layer) of the casing member 1, so that good slippery property can be secured during molding of the casing member, And it is difficult to express white powder on the surface 8a of the innermost layer (second non-extension film layer 8), and sufficient laminate strength and sufficient yarn strength can be ensured. If the content of the lubricant in the first non-tear film layer 7 exceeds 250 ppm, the amount of lubricant present on the surface 7a of the first non-tear film layer 7 on the metal foil layer 4 becomes large , And sufficient laminate strength (laminate strength with the metal foil and the inner sealant layer) can not be secured. When the content concentration of the lubricant in the second non-tear film layer 8 is less than 500 ppm, the amount of lubricant present on the surface 8a of the innermost layer of the casing 1 after aging treatment for curing the adhesive The second non-tear film layer 8 is not sufficiently lengthened from the second non-tear film layer 8 to the first non-stretch film layer 7 after the aging treatment for curing the adhesive is performed. On the other hand, The amount of lubricant present on the surface 7a on the metal foil layer 4 side in the first non-lead-in extended film layer 7 becomes large and the sufficient laminate strength (laminate strength with the metal foil and the inner sealant layer) And the surface 8a of the innermost layer (the second non-tear film layer 8) is liable to produce a white powder remarkably.

Among them, in the sealant film (3) according to the first invention, the first non-stretchable film layer (7) is constituted not to contain a lubricant, or the composition preferably contains a lubricant of more than 0 ppm and not more than 150 ppm Do. In the sealant film (3) according to the first invention, it is more preferable that the first non-tear film layer (7) contains 10 ppm to 90 ppm of a lubricant, particularly preferably 20 to 60 ppm of a lubricant Do. The second non-tear film layer 8 preferably contains 700 ppm to 4500 ppm of lubricant, more preferably 800 ppm to 4000 ppm of lubricant, and particularly preferably 1000 ppm to 2700 ppm of lubricant .

In addition, in the case of employing the configuration (the second invention) for providing the third non-extension film layer, the first non-extension film layer 7 does not contain a lubricant, And the content of the lubricant in the second non-tear film layer (8) is set to 500 ppm to 5000 ppm, and the concentration of the lubricant in the third non-stretch film layer (9) It is important to set it to ~ 3000ppm.

By satisfying this condition, when the aging treatment for curing the adhesive is carried out, the lubricant present in the third non-extensible film layer 9 is prevented from leaking out from the second non-extensible film layer 8 or the first non-extensible film It is possible to secure an amount of lubricant to be deposited on the surface 9a of the innermost layer (third non-extruded film layer) of the casing member 1, It is possible to obtain slippery property and to obtain excellent moldability and to prevent the appearance of white powder on the surface 9a of the innermost layer (the third non-tear film 9), and to provide a sufficient laminate strength and a sufficient yarn strength . If the content of the lubricant in the first non-tear film layer 7 exceeds 250 ppm, the amount of lubricant present on the surface 7a of the first non-tear film layer 7 on the metal foil layer 4 becomes large , And sufficient laminate strength (laminate strength with the metal foil and the inner sealant layer) can not be secured. When the concentration of the lubricant contained in the second non-tear film layer 8 is less than 500 ppm, when the aging treatment for curing the adhesive is carried out, the third non-tear film layer 9 of the innermost layer, The lubricant is liable to move to the layer 8 and the amount of lubricant present on the surface 9a of the innermost layer becomes insufficient and the slipping property at the time of molding deteriorates. When the amount exceeds 5,000 ppm, aging treatment for hardening the adhesive is performed The lubricant is likely to move from the second non-rolled film layer 8 to the first non-rolled film layer 7 and the surface 7a of the first non-rolled film layer 7 on the side of the metal foil layer 4, The amount of the lubricant present in the laminate is increased, and sufficient laminate strength (laminate strength with the metal foil and the inner sealant layer) can not be secured. When the concentration of the lubricant in the third non-tear film layer 7 is less than 200 ppm, the amount of lubricant present on the surface 9a of the innermost layer is insufficient after the aging treatment for curing the adhesive, If the amount exceeds 3000 ppm, after the aging treatment for curing the adhesive is performed, a white powder is remarkably formed on the surface 9a of the innermost layer, and a work for cleaning and removing the white powder becomes necessary There is a problem that the productivity is lowered.

Among them, in the sealant film (3) according to the second invention, the first non-stretchable film layer (7) is constituted not to contain a lubricant, or the composition preferably contains a lubricant of more than 0 ppm and not more than 150 ppm Do. In the sealant film (3) according to the second invention, the first non-tear 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 Do. In the sealant film (3) according to the second invention, the second non-stretchable film layer (8) preferably contains 700 ppm to 4500 ppm of lubricant, more preferably 800 ppm to 4000 ppm of lubricant, It is particularly preferable that the lubricant contains 1000 ppm to 2700 ppm. In the sealant film (3) according to the second aspect of the present invention, the third non-tear film layer (9) preferably contains 300 to 2700 ppm of lubricant, more preferably 500 to 2000 ppm of lubricant, It is particularly preferable that 800 ppm to 1200 ppm of lubricant is contained.

In the sealant film (3) according to the second invention, the concentration of the lubricant contained in the second non-tear film layer (8) is 1.0 to 5.0 times the concentration of the lubricant in the third non-tear film layer . (Both film layers 8 and 9) due to an active agent concentration gradient of the lubricant from the innermost third non-rolled film layer 9 to the second non-rolled film layer 8, (The interface between the second non-stretchable film layer 8 and the third non-stretchable film layer 9), which is 5.0 times or less, (The interface between the two film layers 8 and 9) can be suppressed, and the amount of lubricant present on the surface 9a of the third non-extensible film layer forming the innermost layer of the outer casing after the aging treatment Can be controlled within the range of 0.1 占 퐂 / cm2 to 1.0 占 퐂 / cm2, and the moldability can be further improved. Among them, the concentration of the lubricant in the second non-tear film layer (8) is preferably 1.0 to 4.0 times as large as the concentration of the lubricant in the third non-stretch film layer (9). More preferably from 1.0 times to 4 times, and further more preferably from 1.0 times to 4 times. 0 < / RTI >

Examples of the lubricant include, but are not limited to, saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid ester amides, aromatic bisamides, .

Examples of the saturated fatty acid amide include, but are not limited to, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide. Examples of the unsaturated fatty acid amide include, but are not limited to, oleic acid amide and erucic acid amide.

Examples of the substituted amide include, but are not limited to, N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleate, N-oleyl stearamide, N-stearyl erucic acid amide, Amides and the like. The methylol amide is not particularly limited, and for example, methylol stearamide amide and the like can be given. Examples of the saturated fatty acid bisamide include, but are not limited to, methylene bisstearic acid amide, ethylene biscaprylic acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, Hexamethylenebisbenzoic acid amide, hexamethylene hydroxystearic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl sebacic acid amide, and the like. have.

Examples of the unsaturated fatty acid bisamide include, but are not limited to, ethylenbis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl sebacic acid amide and the like .

The fatty acid ester amide is not particularly limited, and for example, stearoamide ethyl stearate and the like can be mentioned. Examples of the aromatic bisamide include, but are not limited to, m-xylene bisstearic acid amide, m-xylene bishydroxystearic acid amide, and N, N'-cystearylisophthalic acid amide.

The thickness of the sealant film 3 is preferably set to 10 to 100 m. By setting the thickness to 10 mu m or more, the occurrence of pinholes can be sufficiently prevented, and by setting the thickness to 100 mu m or less, the amount of resin used can be reduced and the cost can be reduced.

1 is adopted as the sealant film 3, the ratio of the thickness of the two layers is set so that the thickness of the first non-stretched film layer 7 / the thickness of the second non-stretched film layer 8, The thickness of the first non-rolled film layer 7 / the thickness of the second non-rolled film layer 8 = 5 to 40/95 to 10, And particularly preferably in the range of 95 to 60.

In the case of employing the three-layer laminated structure of Fig. 2 as the sealant film 3, the ratio of the thickness of the three layers is preferably set such that the thickness of the first non-stretched film layer 7 / And the thickness of the third non-tear film layer 9 is preferably set in the range of 5 to 45/90 to 10/5 to 45, It is particularly preferable that the thickness / the thickness of the second non-stretchable film layer 8 / the thickness of the third non-stretchable film layer 9 = 5 to 20/90 to 60/5 to 20.

In the case of employing the two-layer laminated structure of Fig. 1 as the sealant film 3, the second non-stretchable film layer 8 forming the innermost layer may further contain an anti-blocking agent. When the three-layer laminated structure of Fig. 2 is employed as the sealant film 3, the third non-stretched film layer 9 forming the innermost layer may further contain an anti-blocking agent. The anti-blocking agent is not particularly limited, and examples thereof include silica particles, acrylic resin particles, aluminum silicate particles, and the like. The average particle diameter of the anti-blocking agent is preferably in the range of 0.1 to 10 占 퐉, and more preferably in the range of 1 to 5 占 퐉. When the anti-blocking agent is contained in the second non-stretchable film layer 8 forming the innermost layer or the third non-stretchable film layer 9 forming the innermost layer, the content thereof is set to 100 ppm to 5000 ppm .

By containing the anti-blocking agent (particles) in the innermost layer, fine protrusions are formed on the surface of the innermost layer (8a in Fig. 1, 9a in Fig. 2) to reduce the contact area between the films, Blocking can be suppressed. In addition, by containing an anti-blocking agent (particle) together with the lubricant, slipperiness during molding can be further improved.

It is preferable that the sealant film 3 is produced by a molding method such as multilayer extrusion molding, inflation molding, T-die cast film molding and the like.

The casing (1) for a battery device according to the present invention is manufactured by using the sealant film (3) having the above-described structure.

A first manufacturing method (manufacturing method of an exterior material for a power storage device) according to the present invention will be described. First, a laminate having a structure in which the sealant film 3 of the present invention (the first invention or the second invention) and the metal foil 4 are laminated via a first adhesive (inner adhesive) 6 is prepared. At this time, the first non-extensible film layer 7 of the sealant film 3 is in contact with the first adhesive 6. Next, the outer cover material (1) for a power storage device of the present invention can be obtained by heat treatment (aging treatment) of the obtained laminate.

Next, a second manufacturing method (a method for manufacturing an exterior material for an electric storage device) according to the present invention will be described. A heat-resistant resin film (outer layer) 2 is laminated on one surface of the metal foil 4 through a second adhesive (outer adhesive) 5 and a first adhesive (inner side) is laminated on the other surface of the metal foil 4 A laminate having a structure in which the sealant film 3 of the present invention (the first invention or the second invention) is laminated is prepared through the adhesive 6). At this time, the first non-stretch film layer 7 of the sealant film 3 abuts against the first adhesive (inner adhesive) 6 (see FIGS. 1 and 2). Next, by applying the heat treatment (aging treatment) to the obtained laminate, the casing member 1 for a power storage device of the present invention having the structure shown in Figs. 1 and 2 can be obtained. That is, the casing member 1 for an electrical storage device of the present invention obtained through such an aging treatment is formed in such a manner that the heat-resistant resin layer (outer adhesive layer) 5 is formed on one surface of the metal foil layer 4 through the second adhesive layer (Inner layer) 3 (inner layer) 2 is integrally laminated on the other surface of the metal foil layer 4 through a first adhesive layer (inner adhesive layer) 6, ) Are laminated and integrated (see Figs. 1 and 2). When the sealant film of the first invention is used as the sealant film 3, the second non-stretchable film layer 8 of the sealant film 3 forms the innermost layer (see FIG. 1). When the sealant film of the second invention is used as the sealant film 3, the third non-extensible film layer 9 of the sealant film 3 forms the innermost layer (see Fig. 2).

The first adhesive (inner adhesive) 6 is not particularly limited, and for example, a thermosetting adhesive may be used. 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 olefin adhesives, epoxy adhesives, acrylic adhesives, and the like. The heating temperature of the aging treatment is preferably set to 65 DEG C or less and from the viewpoints of curing degree of the adhesive and maintenance of an appropriate amount of the lubricant present in the innermost layer of the casing, It is more preferable to set it. As to the heating time of the aging treatment, the curing time varies depending on the type of the adhesive. Therefore, it is sufficient that the heating time of the aging treatment is not less than the time required to obtain sufficient adhesive strength in accordance with the kind of the adhesive. However, Should be as short as possible as long as sufficient adhesive strength can be obtained.

Since the sealant film of the present invention (the first invention or the second invention) described above is used as the sealant film 3 used in the production of the outer casing 1 for power storage device obtained through the aging treatment, It is possible to obtain a sufficient laminate strength and a sufficient yarn strength.

In the casing (1) for an electrical storage device obtained via the aging treatment, it is preferable that the amount of lubricant present on the surface of the innermost layer is in the range of 0.1 μg / cm 2 to 1.0 μg / cm 2. That is, when the sealant film of the first invention is used as the sealant film 3, the amount of lubricant present on the surface 8a of the second non-extruded film layer 8 is preferably 0.1 μg / cm 2 to 1.0 μg / cm 2 In the case where the sealant film of the second invention is used as the sealant film 3 (refer to Fig. 1), the sealant film is present on the surface 9a of the third lead- (See Fig. 2). ≪ tb > < TABLE > Among them, in the casing (1) for an electrical storage device obtained via the aging treatment, it is preferable that the amount of lubricant present in the surface (8a, 9a) of the innermost layer is in the range of 0.1 μg / cm 2 to 0.6 μg / desirable.

In the casing material 1 for an electric storage device of the present invention, the inner sealant layer (inner layer) 3 is provided with excellent chemical resistance against a corrosive electrolyte or the like used in a lithium ion secondary battery or the like, It plays a role of giving a hit reality.

The heat-resistant resin layer (base layer; outer layer) 2 is not an essential constituent layer, but a second adhesive (not shown) is provided on the other surface (the surface opposite to the inner sealant layer) It is preferable to employ a configuration in which the heat resistant resin layer 2 is laminated via a layer (outer adhesive layer) 5 (see FIGS. 1 and 2). By providing such a heat-resistant resin layer 2, it is possible to sufficiently secure the insulation on the other surface (the surface opposite to the inner sealant layer) side of the metal foil layer 4, Physical strength and impact resistance can be improved.

As the heat-resistant resin constituting the heat-resistant resin layer (base layer: outer layer) 2, a heat-resistant resin which does not melt at the heat room temperature at the time of heat sealing is used. In the first invention, it is preferable to use a heat-resistant resin having a melting point higher by at least 10 캜 than the melting point of the resin constituting the second non-tear film layer (8). In the second invention, It is preferable to use a heat-resistant resin having a melting point higher than the melting point of the resin constituting the third non-stretched film layer 9 by at least 10 캜.

The heat resistant resin layer (outer layer) 2 is not particularly limited, and for example, a polyamide film such as a nylon film, a polyester film, and the like are preferably used. As the heat resistant resin layer 2, a biaxially oriented polyamide film such as a biaxially oriented nylon film, a biaxially oriented polybutylene terephthalate (PBT) film, a biaxially oriented polyethylene terephthalate (PET) film, or a biaxially oriented poly It is particularly preferred to use a biaxially oriented polyethylene naphthalate (PEN) film. The nylon film is not particularly limited, and examples thereof include 6 nylon film, 6,6 nylon film, and MXD nylon film. The heat resistant resin layer 2 may be formed of a single layer or may be formed of a multilayer (eg, PET film / nylon film multilayer) formed of a polyester film / polyamide film.

The thickness of the heat resistant resin layer (outer layer) 2 is preferably 2 m to 50 m. When a polyester film is used, the thickness is preferably 2 to 50 mu m, and in the case of using a nylon film, the thickness is preferably 7 to 50 mu m. By setting the upper limit to a value not lower than the appropriate lower limit value, sufficient strength can be ensured as an outer sheath, and the stress at the time of molding such as extrusion molding and drawing can be reduced by setting the upper limit value or less.

The metal foil layer 4 plays a role of imparting gas barrier properties to the exterior material 1 so as to prevent the intrusion of oxygen and moisture. The metal foil layer 4 is not particularly limited. Examples of the metal foil layer 4 include aluminum foil, SUS foil (stainless steel foil) and copper foil. Among them, aluminum foil and SUS foil (stainless foil) . The thickness of the metal foil layer 4 is preferably 5 to 120 mu m. It is possible to prevent occurrence of pinholes at the time of rolling at the time of producing the metal foil and to reduce the stress at the time of forming such as extrusion molding and drawing by making it 120 탆 or less, have. In particular, the thickness of the metal foil layer 4 is more preferably from 10 탆 to 80 탆.

It is preferable that the metal foil layer 4 is chemically treated at least on the inner surface (the surface on the inner sealant layer 3 side). Since such a chemical treatment is carried out, the corrosion of the surface of the metal foil by the contents (electrolytic solution of the battery, etc.) can be sufficiently prevented. For example, the metal foil is subjected to a chemical conversion treatment by the following process. That is, for example, on the surface of the metal foil subjected to the degreasing treatment,

1) phosphoric acid,

Chromic acid,

An aqueous solution of a mixture containing at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides

2)

At least one resin selected from the group consisting of an acrylic resin, a chitosan derivative resin and a phenol resin,

An aqueous solution of a mixture containing at least one compound selected from the group consisting of chromic acid and chromium (III) salts

3)

At least one resin selected from the group consisting of an acrylic resin, a chitosan derivative resin and a phenol resin,

At least one compound selected from the group consisting of chromic acid and chromium (III) salt,

An aqueous solution of a mixture containing at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides

One of the above-mentioned 1) to 3) is subjected to a chemical conversion treatment by applying an aqueous solution and then drying it.

The above-mentioned chemical conversion film is preferably from 0.1 mg / m 2 to 50 mg / m 2, particularly preferably from 2 mg / m 2 to 20 mg / m 2 as the chromium adhering amount (per one side).

The thickness of the second adhesive layer (outer adhesive layer) 5 is preferably set to 1 m to 5 m. Particularly, from the viewpoint of thinning and lightening of the facer material 1, it is particularly preferable that the thickness of the outer adhesive layer 5 is set at 1 mu m to 3 mu m.

The thickness of the first adhesive layer (inner adhesive layer) 6 is preferably set to 1 m to 5 m. Particularly, from the viewpoint of thinning and lightening of the facer material 1, it is particularly preferable that the thickness of the inner adhesive layer 6 is set to 1 탆 to 3 탆.

The casing (1) for an electric storage device of the present invention is used, for example, as a casing for a lithium ion secondary battery. The exterior material 1 for the power storage device may be used as an exterior material without being subjected to molding (see Fig. 4), provided for molding such as deep drawing molding or extrusion molding, (See FIG. 4).

Fig. 3 shows an embodiment of the electrical storage device 30 constructed using the casing member 1 for a power storage device of the present invention. This electric storage device 30 is a lithium ion secondary battery. In the present embodiment, as shown in Figs. 3 and 4, the outer case 10 is formed by molding the outer case 1, and the outer case 15 is formed by the outer case 1 having a flat shape. An electric storage device main body (electrochemical device or the like) 31 having an approximately rectangular parallelepiped shape is accommodated in the housing recessed portion of the outer case 10 obtained by molding the exterior material 1 of the present invention, The outer sealant 1 of the present invention is disposed on the inner sealant layer 3 of the planar outer casing 1 without forming the inner sealant layer 3 on the inner sealant layer 31, And the inner sealant layer 3 of the flange portion (sealing periphery portion) 29 of the outer case 10 are sealed and sealed by the heat seal so that the power storage device 30 of the present invention is configured (See Figs. 3 and 4). The inner surface of the receiving recessed portion of the outer case 10 is made of the inner sealant layer 3 and the outer surface of the receiving recessed portion is made of the heat resistant resin layer (outer layer) 2 (see FIG. 4). In the case of using the case shown in Fig. 1 as the case for forming the case 10, the inside surface of the receiving concave portion is the innermost layer of the second lead-free film layer 8, 2, the inner surface of the accommodating concave portion is the innermost layer of the third non-stretched film layer 9, as shown in Fig.

3, reference numeral 39 denotes a heat seal portion in which the periphery of the casing member 1 is joined (welded) to the flange portion (sealing periphery portion) 29 of the casing member 10. In the electrical storage device 30, the leading end of the tab lead connected to the power storage device main body portion 31 is led out to the exterior of the exterior member 15, but illustration thereof is omitted.

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

In the above embodiment, the exterior member 15 is constituted by the exterior case 10 obtained by molding the exterior material 1 and the exterior material 1 having a flat shape (see FIGS. 3 and 4) The present invention is not limited to the same combination. For example, the exterior member 15 may be constituted by a pair of planar exterior materials 1, or may be constituted by a pair of exterior cases 10 .

[Example]

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

<Example 1>

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water (water) and alcohol was applied to both surfaces of an aluminum foil 4 having a thickness of 40 탆 and then dried at 180 캜 To form a chemical conversion film. The deposition amount of chromium in this chemical conversion coating is 10 mg / m 2 per one side.

Next, biaxially stretched 6 nylon film 2 having a thickness of 25 占 퐉 was dry-laminated (bonded) to one surface of the chemically treated aluminum foil 4 through a two-liquid curing type urethane adhesive 5, .

Next, a 12 mu m-thick first non-oriented film (7) containing ethylene-propylene random copolymer and 100 ppm of erucic acid amide, an ethylene-propylene block copolymer, 2500 ppm of erucic acid amide and 2000 ppm of silica Extruded using a T-die so as to laminate two layers of the second non-extensible film 8 having a thickness of 28 占 퐉 and containing particles (anti-blocking agent; average particle size of 2 占 퐉) The first non-stretched film layer 7 of the sealant film 3 was obtained after obtaining a sealant film (the first non-stretched film layer 7 / the second non-stretched film layer 8) Surface was overlaid on the other surface of the aluminum foil 4 after the dry lamination through a two-liquid curing type maleic acid-modified polypropylene adhesive 6, and the surface of the rubber nip roll and the laminate roll heated to 100 캜 And then dry-laminated by pressing, and then After that, by 10 days-aging also (heating box) with 40 ℃, to obtain a packaging material (1) for electrical storage devices of the configuration shown in FIG.

As the two-component curing type maleic acid-modified polypropylene adhesive, 100 parts by weight of a maleic acid-modified polypropylene (melting point 80 ° C, acid value 10 mgKOH / g) as a main agent, 100 parts by weight of isocyanuric diisocyanate , 8 parts by mass of an amorphous material (NCO content: 20% by mass), and an adhesive solution in which a solvent was mixed, the adhesive solution was applied to the other face of the aluminum foil 4 so that the solid content application amount was 2 g / , And the film was stacked on the first non-stretched film layer (7) side of the sealant film (3) after heating and drying.

In the thus obtained electrical storage device casing material 1, the amount of lubricant present on the surface 8a of the innermost layer (second non-extruded film layer 8) of the casing material 1 was 0.27 占 퐂 / cm2, 3), the amount of lubricant present on the surface (the surface of the first non-tear film layer 7) 7a on the metal foil layer 4 side was 0.38 g / cm2 (see Table 1).

<Practical Example 2>

The content concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 0 ppm, the concentration of the erucic acid amide in the second non-extending film layer 8 before lamination was set to 3000 ppm 1 was obtained in the same manner as in Example 1, except that the outer casing 1 for a power storage device shown in Fig. 1 was obtained.

&Lt; Example 3 >

A chemical conversion treatment liquid composed of phosphoric acid, polyacrylic acid (acrylic resin), chromium (III) salt compound, water and alcohol was applied to both surfaces of an aluminum foil 4 having a thickness of 40 탆 and then dried at 180 캜, To form a film. The deposition amount of chromium in this chemical conversion coating is 10 mg / m 2 per one side.

Next, biaxially stretched 6 nylon film 2 having a thickness of 25 占 퐉 was dry-laminated (bonded) to one surface of the chemically treated aluminum foil 4 through a two-liquid curing type urethane adhesive 5, .

Next, a first unleaded film (7) having a thickness of 6 占 퐉 and containing ethylene-propylene random copolymer and 100 ppm of erucic acid amide, an ethylene-propylene block copolymer and 2500 ppm of erucic acid amide A 6 mu m-thick (2 mu m thick) layer made of a second non-extensible film 8 having a thickness of 28 mu m, an ethylene-propylene random copolymer, 1000 ppm of erucic acid amide and 2000 ppm of silica particles Extruded using a T-die so as to laminate three layers in this order to form a sealant film (the first non-extension film layer 7) having a thickness of 40 占 퐉, (7) surface of the sealant film (3) is formed into a two-liquid curing type film (7) after obtaining the first lead-free film layer Of maleic acid-modified polypropylene adhesive (6), the dry-laminated alumina The other surface of the nickel ribbon 4 was overlaid and sandwiched between a rubber nip roll and a laminate roll heated to 100 캜 and subjected to dry lamination by pressing and then aging at 40 캜 for 10 days To obtain a jacket 1 for an electric storage device having the structure shown in Fig.

As the two-component curing type maleic acid-modified polypropylene adhesive, 100 parts by mass of a maleic acid-modified polypropylene (melting point 80 ° C, acid value 10 mgKOH / g) as a main component and 100 parts by mass of an isocyanurate of hexamethylene diisocyanate NCO content: 20% by mass), and the adhesive solution mixed with a solvent was applied to the other surface of the aluminum foil 4 so that the amount of the solid content to be applied was 2 g / m 2, After the film was heated and dried, the first non-oriented film layer (7) side of the sealant film (3) was overlapped.

In the thus obtained electrical storage device casing material 1, the amount of lubricant present on the surface 9a of the innermost layer (third non-extensible film layer 9) of the casing material was 0.25 占 퐂 / cm2, (The surface of the first non-tear film layer 7) 7a of the metal foil layer 4 side was 0.25 占 퐂 / cm2 (see Table 1).

<Example 4>

The content concentration of the erucic acid amide in the first non-extension film layer 7 before lamination was set to 60 ppm, the concentration of the erucic acid amide in the second non-extension film layer 8 before lamination was set to 1000 ppm , The outer casing 1 for a power storage device having the structure shown in Fig. 2 was obtained in the same manner as in Example 3.

&Lt; Example 5 >

The outer casing 1 for the power storage device shown in Fig. 2 was produced in the same manner as in Example 3 except that the concentration of the erucic acid amide in the third non-tear film layer 9 before lamination was set to 500 ppm. .

&Lt; Example 6 >

The content concentration of the erucic acid amide in the first non-extension film layer 7 before lamination was set to 60 ppm, the concentration of the erucic acid amide in the second non-extension film layer 8 before lamination was set to 1000 ppm And the containing concentration of the erucic acid amide in the third non-tear film film layer 9 before lamination was set to 2000 ppm. In the same manner as in Example 3, except that the outer casing 1 for power storage device 1 ).

&Lt; Example 7 >

The behenic acid amide was used as a lubricant in place of the erucic acid amide in the first non-extension film layer 7, the second non-extensible film layer 8 and the third non-extensible film layer 9, A casing (1) for a power storage device shown in Fig. 2 was obtained in the same manner as in Example 3 except that the concentration of behenic amide in the non-drawn film layer (7) was set to 50 ppm.

&Lt; Example 8 >

Examples 7 and 8 were prepared in the same manner as in Example 7 except that oleic acid amide was used instead of the erucic acid amide as the lubricant in the first non-extension film layer 7, the second non-extension film layer 8 and the third non- In the same manner, the casing member 1 for the power storage device shown in Fig. 2 was obtained.

&Lt; Example 9 &

Examples 7 and 8 were prepared in the same manner as in Example 7 except that stearic acid amide was used in place of erucic acid amide as a lubricant in the first non-extension film layer 7, the second non-extension film layer 8 and the third non- In the same manner, the casing member 1 for the power storage device shown in Fig. 2 was obtained.

&Lt; Example 10 &

The outer casing 1 for the power storage device shown in Fig. 2 was produced in the same manner as in Example 3 except that the concentration of the erucic acid amide in the second non-tear film layer 8 before lamination was set to 4500 ppm. .

<Example 11>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 0 ppm and the concentration of the erucic acid amide in the second non-extensible film layer 8 before lamination was set to 2000 ppm , The outer casing 1 for a power storage device having the structure shown in Fig. 2 was obtained in the same manner as in Example 3.

<Comparative Example 1>

An outer sheath for an electric storage device was obtained in the same manner as in Example 1 except that the concentration of the erucic acid amide in the first non-extension film layer (7) before lamination was set to 400 ppm.

<Comparative Example 2>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 50 ppm, and the concentration of the erucic acid amide in the second non-extending film layer 8 before lamination was set to 6000 ppm A casing for a power storage device was obtained in the same manner as in Example 1 except for the above.

<Comparative Example 3>

An outer sheath for an electric storage device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide in the first non-oriented film layer (7) before lamination was set to 500 ppm.

<Comparative Example 4>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 400 ppm, the concentration of the erucic acid amide in the second non-extensible film layer 8 before lamination was set to 1000 ppm A casing for a power storage device was obtained in the same manner as in Example 3 except for the following.

<Comparative Example 5>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 500 ppm, the concentration of the erucic acid amide in the third non-extensible film layer 9 before lamination was set to 500 ppm A casing for a power storage device was obtained in the same manner as in Example 3 except for the following.

<Comparative Example 6>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 360 ppm, the concentration of the erucic acid amide in the second non-extending film layer 8 before lamination was set to 1000 ppm And the containing concentration of the erucic acid amide in the third non-tear film layer 9 before lamination was set to 2000 ppm. Thus, the outer casing for the power storage device was obtained.

<Comparative Example 7>

The behenic acid amide was used as a lubricant in place of the erucic acid amide in the first non-extension film layer 7, the second non-extensible film layer 8 and the third non-extensible film layer 9, A casing for electric storage devices was obtained in the same manner as in Example 3 except that the concentration of behenic amide in the non-oriented film layer 7 was set to 320 ppm.

<Comparative Example 8>

Comparative Example 7 and Comparative Example 7 were repeated except that oleic acid amide was used instead of the erucic acid amide as the lubricant in the first non-extrudable film layer 7, the second non-extrudable film layer 8, Thus, a jacket for a power storage device was obtained.

<Comparative Example 9>

Comparative Example 7 and Comparative Example 7 were repeated except that stearic acid amide was used instead of the erucic acid amide as the lubricant in the first non-stretch film layer 7, the second non-stretch film layer 8, Thus, a jacket for a power storage device was obtained.

<Comparative Example 10>

The concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 400 ppm, the concentration of the erucic acid amide in the second non-extensible film layer 8 before lamination was set to 4500 ppm A casing for a power storage device was obtained in the same manner as in Example 3 except for the following.

<Comparative Example 11>

The content concentration of the erucic acid amide in the first non-tear film layer 7 before lamination was set to 60 ppm, the concentration of the erucic acid amide in the second non-extending film layer 8 before lamination was set to 100 ppm A casing for a power storage device was obtained in the same manner as in Example 3 except for the following.

<Comparative Example 12>

An outer sheath for an electric storage device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide in the second non-tear film layer 8 before lamination was set to 5500 ppm.

<Comparative Example 13>

A casing for a power storage device was obtained in the same manner as in Example 3 except that the concentration of the erucic acid amide in the third non-tear film layer (9) before lamination was set to 100 ppm.

<Comparative Example 14>

The content concentration of the erucic acid amide in the first non-extension film layer 7 before lamination was set to 60 ppm, the concentration of the erucic acid amide in the second non-extension film layer 8 before lamination was set to 1000 ppm And the containing concentration of the erucic acid amide in the third non-tear film layer 9 before lamination was set to 4000 ppm, a casing for electric storage devices was obtained in the same manner as in Example 3.

[Table 1]

[Table 2]

Each of the outer casing materials (aged finishes) obtained as described above was evaluated on the basis of the following evaluation methods. The results are shown in Tables 1 and 2.

The coefficient of dynamic friction shown in Tables 1 and 2 is a coefficient of dynamic friction measured with respect to the surface of the innermost layer of the outer casing (aged) for each power storage device in accordance with JIS K7125-1995 (see Figs. 1 and 2) . The surface of the innermost layer is the surface 8a of the second unstretched film layer in Examples 1 and 2 and Comparative Examples 1 and 2, and in Examples 3 to 11 and Comparative Examples 3 to 14, (See Figs. 1 and 2).

&Lt; Evaluation method of the amount of lubricant present on the surface of the innermost layer of the exterior material &

Two pieces of test pieces of square shape having a length of 100 mm and a width of 100 mm were cut out from the casing for each power storage device, and these two test pieces were put together, and the rims of the inner sealant layers of each other were heat- A bag was made. 1 ml of acetone was injected using a syringe in the inner space of the bag, and the surface of the innermost layer of the inner sealant layer was left in contact with acetone for 3 minutes, and acetone in the bag was taken out. The amount of lubricant contained in the withdrawn liquid was measured and analyzed by gas chromatography to determine the amount of lubricant (占 퐂 / cm2) existing on the surface of the innermost layer of the casing. That is, the amount of lubricant per 1 cm 2 of the surface of the innermost layer was determined.

&Lt; Evaluation method of the amount of lubricant present on the surface 7a of the first unstretched film layer in the exterior material >

In each of the examples and comparative examples, the sealant film 3 produced by co-extrusion was cut out into a rectangular shape having a length of 200 mm and a width of 200 mm, followed by aging at 40 ° C for 10 days. Two sheets of rectangular test pieces having a length of 100 mm and a width of 100 mm were cut out from the film after the aging and then these two test pieces were overlapped with each other so that the first non-stretch film layers 7 were in contact with each other and the peripheral portion was covered with a nylon film And the surrounding was hit at a heat room temperature of 200 ° C to prepare a bag body. 1 ml of acetone was injected using a syringe in the inner space of the bag, and after standing for 3 minutes in a state in which acetone and the surface of the first non-tear film layer (inner surface of the bag) were in contact with each other, . The amount of lubricant contained in the withdrawn liquid was measured and analyzed by gas chromatography to determine the amount of lubricant (占 퐂 / cm2) present on the surface 7a of the first non-extruded film layer. Namely, the lubricant amount per 1 cm 2 of the surface of the first non-stretched film layer was determined.

<Moldability Evaluation Method>

Deep drawing one-stage molding was performed on the exterior material using the straight-mold-free molding depths under the following molding conditions, and each molding depth (9 mm, 8 mm, 7 mm, 6 mm, 5 mm, Mm, 2 mm), and the maximum molding depth (mm) capable of performing good molding without causing any pinhole at the corner portion was investigated. The determination was made such that the maximum molding depth was 5 mm or more, &quot;? &Quot;, the maximum molding depth was 2 mm or more and less than 5 mm was &quot; DELTA &quot;, and the maximum molding depth was less than 2 mm. The presence or absence of pinholes was examined by visually observing the presence or absence of the transmitted light passing through the pinhole.

(Molding conditions)

Molding 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:

Blank holding pad (blank holding pad) Gauge pressure: 0.475 MPa, actual pressure (calculated value): 0.7 MPa

material … SC (carbon steel) material, Punch R chrome plating only.

<Method of evaluating the presence /

A rectangular test piece having a length of 600 mm and a width of 100 mm was cut out from the outer sheath for each power storage device and the obtained test piece was placed on the inner sealant layer 3 surface (that is, the innermost layer surface 8a or 9a) And a weight made of SUS (mass 1.3 kg, ground surface size of 55 mm x 50 mm) whose surface was blackened by winding a black wess on the upper surface of the test piece The weight was pulled in a horizontal direction parallel to the upper surface of the test piece at a tensile speed of 4 cm / sec. In this state, the weight was pulled over a length of 400 mm in contact with the upper surface of the test piece. (Black) of the contact surface of the weight after the movement was pulled and observed with the naked eye. A sample in which white powder was remarkably formed on the surface of wax (black) was evaluated as &quot; X &quot; &Quot; DELTA &quot;, and those with little or no white spots were determined as &quot; Good &quot;. As the black wes, "static electricity removing sheet S SD25253100" manufactured by TRUSCO Co., Ltd. was used.

<Actual Strength Evaluation Method>

Two pieces of test specimens each having a width of 15 mm and a length of 150 mm were cut out from the obtained outer sheaths. The two test specimens were placed in contact with each other so that the inner sealant layers were in contact with each other. -A) was used to perform heat sealing by one-side heating under conditions of a heat room temperature of 200 占 폚, a real pressure of 0.2 MPa (gauge display pressure), and a real time of 2 seconds.

Next, with respect to a pair of outer sheaths in which the inner sealant layers were heat-sealed to each other as described above, a stencil (AGS-5kNX) manufactured by Shimadzu Corporation in accordance with JIS Z0238-1998 was used and the outer sheath The peel strength at the time when the inner sealant layers of the seal portion were peeled off 90 degrees at a tensile speed of 100 mm / min was measured, and this was regarded as the actual strength (N / 15 mm width).

The yarn strength of 30 N / 15 mm width or more was defined as &quot;? &Quot; (acceptable), and the yarn having a width of 30 N / 15 mm or less was defined as &quot; x &quot;.

&Lt; Evaluation method of cohesion degree of peeling interface &

Both sides of the peeled portion (broken portion) of the inner sealant layer of the jacket after the measurement of the actual strength (peel strength) were visually observed to determine whether or not whitening occurred on both sides of the peeled portion (broken portion) The greater the degree of coagulation) can be judged based on the following criteria.

(Criteria)

, &Quot; C &quot;, &quot; C &quot;, &quot; B &quot;, &quot; C &quot;, &quot; .

&Lt; Evaluation method of laminate strength &

The inner sealant layer 3 and the metal foil layer (aluminum foil layer) 4 were peeled off by dipping a test piece having a width of 15 mm and a length of 150 mm out of the outer cover thus obtained and immersing the longitudinal end portion of the test piece in an alkaline peeling liquid . A laminate including a metal foil layer (aluminum foil layer) 4 was sandwiched and fixed with a chuck on one side using a stencil (AGS-5kNX) manufactured by Shimadzu Corporation according to JIS K6854-3 (1999) The peeled sealant layer 3 was sandwiched between the inner sealant layer 3 and the metal foil layer 3 at a pulling rate of 100 mm / (Adhesive strength) (N / 15 mm width). The peel strength was measured at 25 캜. And evaluated based on the following criteria.

(Criteria)

Quot ;, and those with a laminate strength of &quot; 5.0 N / 15 mm width &quot; or more and those with a laminate strength of less than &quot; 5.0 N / 15 mm width &quot;

As apparent from Table 1, the outer sheath of the battery device according to Examples 1 to 11 constructed using the sealant film of the present invention is excellent in moldability and hardly shows white powder on the surface of the innermost layer of the outer sheath A sufficient laminate strength and a sufficient yarn strength were obtained.

On the other hand, in Comparative Examples 1 to 10 deviating from the scope of the present invention, sufficient laminate strength was not obtained. In Comparative Examples 2 and 8, the actual strength was also insufficient. In comparative examples 11 and 13 deviating from the scope of the present invention, moldability was poor. In comparative example 14, white powder appeared on the surface of the innermost layer. In comparative example 12, white powder appeared on the surface of the innermost layer, The yarn strength was insufficient and the laminate strength was insufficient.

[Industrial applicability]

As a concrete example, the exterior material for a power storage device manufactured using the sealant film according to the present invention, the exterior material for a power storage device according to the present invention, and the exterior material for an electric storage device obtained by the manufacturing method of the present invention,

· Power storage devices such as lithium secondary batteries (lithium ion batteries, lithium polymer batteries, etc.)

· Lithium ion capacitor

· Electric double layer condenser

· All solid cells

And the like.

This application is a continuation of Japanese Patent Application No. 2017-53012, filed on March 17, 2017, which claims the priority of the present application and is incorporated herein by reference in its entirety.

The terms and explanations used here are used for explaining the embodiments of the present invention, and the present invention is not limited thereto. It is intended that the present invention not be limited by any of the details of the description provided herein except as defined in the appended claims.

1: Outer material for power storage device
2: Heat resistant resin layer (outer layer)
3: Inner sealant layer (sealant film) (inner layer)
4: metal foil layer
5: Second adhesive layer (outer adhesive layer)
6: First adhesive layer (inner adhesive layer)
7: First non-oriented film layer (metal foil layer side)
7a: surface on the metal foil layer side in the inner sealant layer
8: second undrawn film layer
8a: Surface of innermost layer
9: Third unleaded film layer
9a: surface of innermost layer
10: External case for power storage device (molded product)

Claims (13)

A sealant film comprising a laminate of two or more layers comprising a first non-extensible film layer and a second non-extensible film layer laminated on one surface of the first non-extensible film layer,
The first non-stretchable film layer is a layer disposed on the most metal foil side in the sealant film,
Wherein the first non-stretched film layer contains a random copolymer containing a copolymerization component other than propylene and propylene as a copolymerization component,
Wherein the first non-tear film layer is composed of no lubricant, or contains a lubricant of more than 0 ppm and not more than 250 ppm,
Wherein the second non-stretched film layer contains a propylene polymer and a lubricant,
Wherein the concentration of the lubricant in the second non-toughened film layer is 500 ppm to 5000 ppm. The method according to claim 1,
Wherein the third non-stretched film layer further comprises a third non-stretched film layer laminated on a surface of the second non-stretched film layer opposite to the side on which the first non-stretched film layer is laminated, Characterized in that it contains a random copolymer containing a copolymerization component other than propylene and propylene and a lubricant and the content concentration of the lubricant in the third non-extensible film layer is 200 ppm to 3000 ppm, film. 3. The method of claim 2,
Wherein the concentration of the lubricant in the second non-stretchable film layer is 1.0 to 5.0 times the concentration of the lubricant in the third non-stretchable film layer. An inner sealant layer comprising the sealant film according to claim 1 and a metal foil layer laminated on one surface side of the inner sealant layer, wherein the amount of lubricant present on the surface of the second non-tear film layer is 0.1 mu g / Mu] g / cm &lt; 2 &gt;. An inner sealant layer made of the sealant film according to claim 2 or 3 and a metal foil layer laminated on one surface side of the inner sealant layer, wherein the amount of the lubricant present on the surface of the third non-tear film layer is 0.1 mu g / 1.0 mu g / cm &lt; 2 &gt;. A heat-resistant resin layer as an outer layer, an inner sealant layer composed of the sealant film described in claim 1, and a metal foil layer disposed between the both layers, wherein the amount of the lubricant present on the surface of the second non- / Cm &lt; 2 &gt; to 1.0 g / cm &lt; 2 &gt;. A heat-resistant resin layer as an outer layer, an inner sealant layer composed of the sealant film according to claim 2 or 3, and a metal foil layer disposed between the both layers, Wherein the lubricant amount is in the range of 0.1 占 퐂 / cm2 to 1.0 占 퐂 / cm2. An external case for a power storage device, characterized by comprising a molded body of a casing according to any one of claims 4 to 7. A process for producing a laminate comprising the sealant film according to any one of claims 1 to 3 and a laminate obtained by laminating a metal foil with a first adhesive agent,
And an aging step of subjecting the laminate to a heat treatment to obtain an exterior material for a power storage device. 10. The method of claim 9,
Wherein the first adhesive is a thermosetting adhesive. A heat-resistant resin film is laminated on one surface of a metal foil through a second adhesive, and a sealant film according to any one of claims 1 to 3 is laminated on the other surface of the metal foil through a first adhesive agent A step of preparing a laminate,
And an aging step of subjecting the laminate to a heat treatment to obtain an exterior material for a power storage device. 12. The method of claim 11,
Wherein the first adhesive is a thermosetting adhesive, and the second adhesive is a thermosetting adhesive. 13. The method according to any one of claims 9 to 12,
Wherein the amount of lubricant present on the surface of the innermost layer of the jacket for a power storage device obtained by the heat treatment is in the range of 0.1 μg / cm 2 to 1.0 μg / cm 2.

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