JP2013101764A - External facing material for secondary battery and secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external facing material for a secondary battery having excellent productivity and moldability in which a lubricant is less likely to migrate to a molding die during cold molding, and the outermost surface and the innermost surface have high blocking resistance and slipperiness, and to provide a secondary battery including the external facing material for secondary battery.SOLUTION: An external facing material 1 for a secondary battery includes, from the outside, a base material protection layer 17, a base material layer 11, a first adhesive layer 12, a metal foil layer 13, a corrosion prevention treatment layer 14, a second adhesive layer 15, and a sealant layer 16 provided with a sealant, laminated sequentially. The external facing material 1 for a secondary battery has a contour curve maximum height (Rz) of the innermost surface in the range of 100-2000 nm measured in conformity to JIS B0601-1982, and an average length (Rsm) of a contour curve element in the range of 100-1500 μm, and a contour curve maximum height (Rz) of the outermost surface in the range of 500-2000 nm, and an average length (Rsm) of a contour curve element in the range of 100-1500 μm. A secondary battery including the external facing material 1 for a secondary battery is also provided.

Description

  The present invention relates to a packaging material for a secondary battery and a secondary battery.

  As secondary batteries, lithium-ion batteries that can be reduced in weight with high energy density are often used in connection with downsizing of portable devices such as mobile phones and notebook computers. The secondary battery exterior material (hereinafter sometimes referred to simply as “exterior material”) is different from the can type that has been conventionally used in secondary battery applications particularly for large equipment, and has a degree of freedom in shape and a thin film. A laminate-type exterior material (for example, a structure such as a base material layer / adhesive layer / aluminum foil layer / adhesive resin layer / sealant layer) has been attracting attention because of its advantages in terms of weight reduction, weight reduction, and heat dissipation.

  A secondary battery using a laminate-type exterior material is: (1) One side that remains after a bag is made so that one side is open, and battery contents such as a positive electrode, a negative electrode, a separator, and an electrolytic solution are housed therein. Forms such as three-side seal type, four-side seal type, pillow pouch type, etc. for heat-sealing, and (2) forming a recess by deep-drawing the exterior material by cold molding, and storing the battery contents in the recess A form such as an embossed type in which the peripheral portion is heat sealed by heat sealing is known. In the secondary battery of the form (2), the storage amount of the battery contents increases and the energy density increases as the concave portion formed in the exterior material by cold forming is deepened.

  In the cold molding, the exterior material is drawn into the molding part of the molding die and is stretched to some extent to form a recess. At this time, if the exterior material is not sufficiently drawn into the molding part of the molding die, the exterior material is excessively stretched and thinning of the metal foil layer occurs. As a result, cracks and pinholes are formed in the metal foil layer. There is a problem that occurs. In particular, this problem is more likely to occur as the forming depth in cold forming becomes deeper.

  Therefore, attempts have been made to improve the slipperiness of the surface of the exterior material so that the exterior material is stably drawn into the molding part of the molding die and excellent moldability is obtained. For example, the exterior material (for example, patent document 1) by which the lubricant was apply | coated to the surface of a base material layer (outermost layer), a lubricant is contained in a sealant layer (innermost layer), and this lubricant is made into the sealant layer surface (outermost surface). Known is a bleed-out exterior material (for example, Patent Document 2), an exterior material (Patent Documents 3 and 4) in which friction is reduced by providing irregularities on the surface (the innermost surface) of the sealant layer.

JP 2002-216713 A JP 2003-288866 A Japanese Patent No. 4580079 JP 2006-318685 A

However, the exterior material of Patent Document 1 may not have sufficient blocking resistance and slipperiness even when a lubricant is present on the outermost surface.
The exterior material of Patent Document 2 does not have sufficient blocking resistance and slipperiness on the outermost surface. In addition, excessive powder spraying of the lubricant occurs on the innermost surface, the lubricant accumulates excessively on the contact portion with the molding die on the innermost surface, and a large amount of lubricant moves to the molding die, resulting in stable production. Sexuality may not be obtained.
Moreover, the exterior materials of Patent Documents 3 and 4 have insufficient blocking resistance and slipperiness on the outermost surface, and it is difficult to obtain excellent moldability.

  The present invention suppresses excessive accumulation of the lubricant at the contact portion with the molding die on the innermost layer surface, makes it difficult for the lubricant to transfer to the molding die, and has blocking resistance and slipperiness on the outermost surface and the innermost surface. An object of the present invention is to provide a secondary battery outer packaging material that is high and has excellent productivity and moldability, and a secondary battery including the secondary battery outer packaging material.

The outer packaging material for a secondary battery of the present invention includes, from the outside, at least a base material layer, a first adhesive layer, a metal foil layer, a corrosion prevention treatment layer, a second adhesive layer, and a sealant layer provided with a lubricant on the innermost surface sequentially. Laminated,
The maximum height (Rz) of the contour curve of the innermost surface measured according to JIS B0601-1982 is 100 nm to 2000 nm, the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm, and the contour of the outermost surface. The maximum curve height (Rz) is 500 nm to 2000 nm, and the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm.

In the exterior material for a secondary battery of the present invention, the base material layer is preferably a layer made of a polyamide film.
Moreover, it is preferable that the base material protective layer which protects the said base material layer is laminated | stacked on the outer side of the said base material layer.
Moreover, it is preferable that the said base material protective layer contains the polyurethane resin formed from the polyester resin or 1 or more types chosen from the group which consists of a polyester polyol and an acrylic polyol, and an aliphatic isocyanate hardening | curing agent.

  The secondary battery of this invention is a secondary battery provided with the exterior material for secondary batteries of this invention.

The outer packaging material for a secondary battery of the present invention suppresses excessive accumulation of lubricant at the contact portion with the molding die on the innermost layer surface, makes it difficult for the lubricant to migrate to the molding die, and the outermost and innermost surfaces. The anti-blocking property and slipperiness are high, and excellent productivity and moldability can be obtained.
Further, in the secondary battery of the present invention, excessive accumulation of the lubricant at the contact portion with the molding die on the innermost layer surface is suppressed, the lubricant is hardly transferred to the molding die, and the outermost and innermost surfaces are It has a secondary battery exterior material that has high blocking resistance and slipperiness, and that provides excellent productivity and moldability.

It is sectional drawing which showed an example of the exterior material for secondary batteries of this invention. It is sectional drawing which showed the other example of the exterior material for secondary batteries of this invention. It is sectional drawing which showed the other example of the exterior material for secondary batteries of this invention.

<Exterior material for secondary battery>
Hereinafter, an example of the packaging material for a secondary battery according to the present invention will be described in detail. FIG. 1 is a cross-sectional view showing a secondary battery exterior material 1 (hereinafter referred to as “exterior material 1”) which is an example of a secondary battery exterior material of the present invention.
As shown in FIG. 1, the exterior material 1 includes a base material protective layer 17, a base material layer 11, a first adhesive layer 12, a metal foil layer 13, a corrosion prevention treatment layer 14, a second adhesive layer 15, and a sealant from the outside. Layers 16 are sequentially stacked. The packaging material 1 is used with the base material protective layer 17 as the outermost layer and the sealant layer 16 as the innermost layer.

[Base material protective layer]
The base material protective layer 17 is a layer provided for the purpose of protecting the base material layer 11 having low electrolytic solution resistance and high hygroscopicity. By providing the base material protective layer 17 outside the base material layer 11, the electrolyte solution adheres to the base material layer 11 and deteriorates in the sealing process from injection of the electrolytic solution at the time of manufacturing the secondary battery. Or the moldability of the base material layer 11 due to moisture absorption in a highly humid environment is suppressed. Moreover, the pinhole resistance at the time of processing and distribution of the exterior material, the insulation between the metal foil layer 13 and the other metal in the secondary battery, and the heat resistance at the time of heat sealing the exterior material in battery production are also improved.

As a material for forming the base material protective layer 17, one or more selected from the group consisting of a polyester resin, or a polyester polyol and an acrylic polyol (hereinafter sometimes collectively referred to as “polyol”) and an aliphatic group. A polyurethane resin formed from an isocyanate curing agent is preferred, and a polyester resin is more preferred from the viewpoint of improving pinhole resistance.
Examples of the polyester resin include polyethylene terephthalate and polyethylene naphthalate. When forming the base material protective layer 17 using a polyester resin, it is more preferable to use a polyester film.

As the polyester polyol, a polyester polyol having a hydroxyl group in the side chain (hereinafter referred to as “polyester polyol (a1)”) is preferable. The polyester polyol (a1) is a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit.
Examples of the polyester polyol (a1) include polyester polyols obtained by reacting at least one dibasic acid with at least one compound having three or more hydroxyl groups. Of the hydroxyl groups of the compound having three or more hydroxyl groups, the unreacted ones become the hydroxyl groups in the side chain of the polyester polyol (a1).
Examples of the dibasic acid include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid; isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc. And aromatic dibasic acids.
Examples of the compound having three or more hydroxyl groups include hexanetriol, trimethylolpropane, pentaerythritol and the like.

Further, the polyester polyol (a1) may be obtained by reacting a diol as necessary in addition to the compound having three or more dibasic acids and hydroxyl groups.
Examples of the diol include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol; cyclohexanediol, Examples thereof include alicyclic diols such as hydrogenated xylylene glycol; aromatic diols such as xylylene glycol and the like.

As the acrylic polyol, an acrylic polyol having a hydroxyl group in the side chain (hereinafter referred to as “acrylic polyol (a2)”) is preferable. The acrylic polyol (a2) is an acrylic polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the terminal of the repeating unit.
Examples of the acrylic polyol (a2) include a copolymer having as a main component a repeating unit derived from (meth) acrylic acid, which is obtained by copolymerizing at least a hydroxyl group-containing acrylic monomer and (meth) acrylic acid. .
Examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
As a component copolymerized with a hydroxyl group-containing acrylic monomer and (meth) acrylic acid, an alkyl (meth) acrylate monomer (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group). Group, i-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.); (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide (alkyl) Examples of the group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group. -Alkoxy (meth) acrylamide, N, N-dialkoxy (meth) acrylamide (the alkoxy group includes And amide group-containing monomers such as N-methylol (meth) acrylamide and N-phenyl (meth) acrylamide; glycidyl (meth) acrylate, allyl glycidyl ether, etc. Glycidyl group-containing monomers; silane-containing monomers such as (meth) acryloxypropyltrimethoxysilane and (meth) acryloxypropyltriethoxylane; and isocyanate group-containing monomers such as (meth) acryloxypropyl isocyanate.
A polyol can be used according to the function and performance calculated | required, 1 type may be used independently, and 2 or more types may be used together.

The aliphatic isocyanate curing agent is a bifunctional or higher functional isocyanate compound having no aromatic ring. Since it does not have an aromatic ring, quinoid formation of the benzene ring due to ultraviolet rays does not occur, and yellowing can be suppressed, which is suitable for the outermost layer. Aliphatic isocyanate curing agents include methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone Diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate and the like can be mentioned. Moreover, you may use the adduct body, burette body, and isocyanurate body of these isocyanate compounds.
As the aliphatic isocyanate curing agent, 1,6-hexamethylene diisocyanate and isophorone diisocyanate are preferable because the resistance to electrolytic solution is improved. Since 1,6-hexamethylene diisocyanate has higher reactivity with a hydroxyl group than isophorone diisocyanate, 1,6-hexamethylene diisocyanate is particularly preferable in view of suitability for mass production.
One aliphatic isocyanate curing agent may be used alone, or two or more aliphatic isocyanate curing agents may be used in combination.

  When forming the base material protective layer 17 using the said urethane resin, the molar ratio (NCO / OH) of the isocyanate group which the aliphatic isocyanate hardening | curing agent has with respect to the hydroxyl group which a polyol has is preferably 0.5-50. ~ 20 is more preferred. When the molar ratio (NCO / OH) is 0.5 or more, the electrolytic solution resistance is improved. If the molar ratio (NCO / OH) is 50 or less, the adhesion between the base material layer 11 and the base material protective layer 17 can be easily maintained.

  The thickness of the base material protective layer 17 is preferably 1 to 30 μm and more preferably 1 to 12 μm in consideration of processability.

[Base material layer]
The base material layer 11 is a layer provided for the purpose of preventing breakage of the metal foil layer 13 during cold forming, in addition to countermeasures against pinholes that may occur during processing and distribution. Moreover, when making a base material layer into an outermost layer, the insulation between the metal foil layer 13 and the other metal in a secondary battery and the heat resistance at the time of heat sealing of the exterior material at the time of battery manufacture are calculated | required.
The base material layer 11 is preferably a polyamide film from the viewpoint of moldability. The polyamide film may be a stretched film or an unstretched film. Among these, a stretched polyamide film is more preferable from the viewpoint of improving moldability.
Examples of the polyamide resin forming the polyamide film include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, and the like. Among these, nylon 6 is preferable from the viewpoint of improving moldability.
The thickness of the base material layer 11 is preferably 6 to 40 μm and more preferably 10 to 25 μm in consideration of pinhole resistance and workability.

[First adhesive layer]
The first adhesive layer 12 is a layer that bonds the base material layer 11 and the metal foil layer 13 together. In order to suppress the metal foil layer 13 from being broken at the time of cold forming, in addition to the adhesion to sufficiently adhere the base material layer 11 and the metal foil layer 13 to the first adhesive layer 12, Followability to movement is required.
The adhesive component constituting the first adhesive layer 12 is a two-component curable type in which a bifunctional or higher functional aromatic or aliphatic isocyanate is allowed to act as a curing agent on a main component such as polyester polyol, polyether polyol, and acrylic polyol. A urethane-based adhesive is preferred.

  When using the said urethane type adhesive agent, 1-40 are preferable and, as for the molar ratio (NCO / OH) of the isocyanate group which the hardening | curing agent has with respect to the hydroxyl group which a main ingredient has, 20-35 are more preferable. When the molar ratio (NCO / OH) is 1 or more, sufficient adhesion is easily obtained. In particular, when the molar ratio (NCO / OH) is 20 or more, not only urethane bonds but also urea bonds, burette bonds, and allophanate bonds are promoted, and in a high-temperature environment at a portion that is stretched during cold forming. It is easy to suppress a decrease in adhesion. Further, if the molar ratio (NCO / OH) is 40 or less, it is possible to suppress the ratio of urea bond, burette bond, and allophanate bond to urethane bond from being excessively increased, and the flexibility of the first adhesive layer 12 is maintained. It is easy to ensure a sufficient amount of elongation of the exterior material 1.

  The thickness of the first adhesive layer 12 is preferably 1 to 10 μm and more preferably 3 to 7 μm from the viewpoints of adhesive strength, followability, workability, and the like.

[Metal foil layer]
As the metal foil layer 13, various metal foils such as aluminum and stainless steel can be used. Of these, aluminum foil is preferable from the viewpoints of workability such as moisture resistance and spreadability, and cost.
As the aluminum foil, a general soft aluminum foil can be used, and a degreased aluminum foil is preferable. Moreover, the aluminum foil containing iron is preferable from the point which can provide pinhole resistance and the extensibility at the time of shaping | molding. In this case, the content of iron in the aluminum foil (100% by mass) is preferably 0.1 to 9.0% by mass, and more preferably 0.5 to 2.0% by mass. When the iron content is 0.1% by mass or more, pinhole resistance and spreadability are improved. If the iron content is 9.0% by mass or less, flexibility is improved.
The thickness of the metal foil layer 13 is preferably 9 to 200 μm, more preferably 15 to 100 μm, from the viewpoint of barrier properties, pinhole resistance, and workability.

[Corrosion prevention treatment layer]
The corrosion prevention treatment layer 14 improves the adhesion between the metal foil layer 13 and the second adhesive layer 15 and suppresses the corrosion of the metal foil layer 13 due to the electrolytic solution or hydrofluoric acid generated by the reaction between the electrolytic solution and moisture. To play a role.
The corrosion prevention treatment layer 14 is preferably a coating film formed by a coating type or immersion type acid resistant corrosion prevention treatment agent. If the corrosion prevention treatment layer 14 is the coating film, the effect of preventing corrosion of the metal foil layer 13 with respect to acid is improved. Furthermore, the anchor is formed on the metal foil layer 13, whereby the adhesion between the metal foil layer 13 and the second adhesive layer 15 becomes stronger, and the resistance to the battery contents such as the electrolytic solution is improved.
As the coating film, for example, ceriazol treatment with a corrosion prevention treatment agent comprising cerium oxide, phosphate and various thermosetting resins; corrosion prevention comprising chromate, phosphate, fluoride and various thermosetting resins Examples thereof include a coating film formed by a chromate treatment with a treating agent.

Moreover, the corrosion prevention process layer 14 will not be limited to the coating film formed by the said process, if the corrosion resistance of the metal foil layer 13 is fully obtained. For example, a coating film formed by phosphate treatment, boehmite treatment, or the like may be used.
The thickness of the corrosion prevention treatment layer 14 is preferably 10 nm to 5 μm, more preferably 20 nm to 500 nm, considering the corrosion prevention function and the function as an anchor.

[Second adhesive layer]
The second adhesive layer 15 is a layer that bonds the sealant layer 16 and the metal foil layer 13 on which the corrosion prevention treatment layer 14 is formed.
As an adhesive component constituting the second adhesive layer 15, a thermoplastic resin is preferable. Examples thereof include polyolefin resins and acid-modified polyolefin resins obtained by graft-modifying acids such as maleic anhydride to polyolefin resins. Among these, an acid-modified polyolefin resin is preferable from the viewpoint of excellent adhesion with the metal foil layer 13.

  Examples of the polyolefin resin include low density, medium density, and high density polyethylene; ethylene-α olefin copolymer; homo, block or random polypropylene; propylene-α olefin copolymer. These polyolefin resins may be used individually by 1 type, and may use 2 or more types together. The polyolefin-based resin and the acid-modified polyolefin-based resin are excellent in resistance to electrolytic solution, and even when hydrofluoric acid is generated in the battery, a decrease in adhesion due to deterioration of the second adhesive layer 15 is easily suppressed.

Moreover, it is preferable to add an elastomer resin to the second adhesive layer 15 formed of the polyolefin resin and the acid-modified polyolefin resin. As a result, whitening due to cracks occurring in the second adhesive layer 15 during cold forming is easily suppressed, adhesion is improved by improving wettability, and film-forming properties, heat seal strength, and the like are improved by reducing anisotropy. To do.
Examples of the elastomer resin include styrene-based or olefin-based thermoplastic elastomers.

  1-40 micrometers is preferable and, as for the thickness of the 2nd contact bonding layer 15 formed with the said thermoplastic resin, 5-20 micrometers is more preferable. If the thickness of the 2nd contact bonding layer 15 is 1 micrometer or more, sufficient adhesive strength will be easy to be obtained. If the thickness of the 2nd contact bonding layer 15 is 40 micrometers or less, it will be easy to reduce the moisture content which permeate | transmits into a battery inside from a seal end surface.

  The second adhesive layer 15 may be a layer formed by a technique such as dry lamination. As the adhesive component in this case, the two-component curable polyurethane adhesive mentioned in the first adhesive layer 12 is preferable.

[Sealant layer]
The sealant layer 16 is the innermost layer of the exterior material 1 and is a layer that is heat sealed when the battery is assembled. That is, the sealant layer 16 is a layer made of a heat-weldable film.
The film component constituting the sealant layer 16 is preferably a thermoplastic resin, and more preferably an olefin resin such as polyethylene or polypropylene, because of excellent impact resistance and heat sealing properties. Polypropylene includes homo, block, or random polypropylene.
The sealant layer 16 may be a layer made of a single layer film or a layer made of a multilayer film. For example, for the purpose of imparting moisture resistance, a multilayer film in which a resin such as an ethylene-cyclic olefin copolymer or polymethylpentene is interposed may be used.

  The sealant layer 16 is provided with a lubricant on the surface. Examples of the mode of applying a lubricant to the surface of the sealant layer 16 include a mode of applying a lubricant to the surface of the sealant layer 16, a mode of containing a lubricant in the sealant layer 16, and bleeding out the lubricant to the surface of the sealant layer 16 by aging. Is mentioned.

  Examples of the lubricant include fatty acid amides (oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, etc.) and the like.

When applying a lubricant to the sealant layer 16 surface, the coating amount of the lubricant is preferably from ^{0.5~25.0mg / m 2, 1.0~10.0mg / m} 2 is more preferable. If the amount of lubricant applied is equal to or greater than the lower limit, slipperiness is easily obtained. If the application amount of the lubricant is less than or equal to the upper limit value, it is easy to suppress the powdering of the lubricant and excessive transfer to the molding die.

  When the lubricant is contained in the sealant layer 16, the content of the lubricant in the sealant layer 16 is preferably 0.001 to 0.5% by mass, and more preferably 0.01 to 0.2% by mass. If the content of the lubricant is not less than the lower limit, slipperiness is easily obtained. If the content of the lubricant is not more than the upper limit value, it is easy to suppress the powdering of the lubricant due to bleeding and excessive transfer to the molding die.

  The thickness of the sealant layer 16 is preferably 25 to 100 μm. When the thickness of the sealant layer 16 is 25 μm or more, excellent heat sealability is easily obtained. If the thickness of the sealant layer 16 is 100 μm or less, it is easy to reduce the amount of moisture that permeates from the seal end surface into the battery.

[Surface roughness]
The exterior material 1 has a contour curve maximum height (Rz) on the innermost surface, that is, the surface of the sealant layer 16, of 100 nm to 2000 nm, and an average length (Rsm) of the contour curve elements is 100 μm to 1500 μm. In addition, the surface contour curve maximum height (Rz) and the average length (Rsm) of the contour curve element in the present invention mean values measured in accordance with JIS B0601-1982.
The contour curve maximum height (Rz) on the surface of the sealant layer 16 and the average length (Rsm) of the contour curve elements are within the above ranges, so that the surface of the sealant layer 16 exhibits excellent blocking resistance and slipperiness. Excellent moldability is obtained. Moreover, since it is suppressed that the lubricant provided by application | coating or bleed-out accumulates in the contact part with the molding die in the sealant layer 16 surface, it becomes difficult for a lubricant to transfer to a molding die.

Specifically, the maximum contour curve height (Rz) on the surface of the sealant layer 16 is 100 nm or more, so that blocking due to winding or the like can be suppressed, and the lubricant applied to the surface of the sealant layer 16 by coating or bleed-out. A part of the surface is accumulated in the concave portion of the surface unevenness, and the lubricant in the concave portion comes out on the surface at the time of molding stretching, so that it becomes possible to keep the slipping property at the time of molding.
In addition, since the maximum contour curve height (Rz) is 2000 nm or less, the lubricant applied to the recesses formed on the surface of the sealant layer 16 is likely to come out from the recesses during molding stretching, and slipping during molding. It becomes possible to keep sex.
Further, the average length (Rsm) of the contour curve element is 100 μm or more, so that an excessively large contact portion with the molding die on the surface of the sealant layer 16 is suppressed, and while exhibiting blocking resistance, Sufficient slipperiness is obtained by the lubricant present on the convex portions of the surface irregularities. Moreover, it is suppressed that the contact surface with the molding die in the sealant layer 16 becomes too small, suppressing the fall of blocking resistance because the average length (Rsm) of a contour curve element is 1500 micrometers or less. Sufficient slipperiness can be obtained.

  The maximum contour curve height (Rz) on the surface of the sealant layer 16 is preferably 500 nm or more because the anti-lubricant powder blowing property is improved and the blocking resistance is improved. Further, the contour curve maximum height (Rz) on the surface of the sealant layer 16 is preferably 1500 nm or less because the slipping property at the time of molding stretching is improved.

  The average length (Rsm) of the contour curve element on the surface of the sealant layer 16 is preferably 300 μm or more because the blocking resistance of the surface of the sealant layer 16 is improved. In addition, the average length (Rsm) of the contour curve element on the surface of the sealant layer 16 is preferably 1000 μm or less because blocking resistance and slipperiness are improved.

  As a method of adjusting the maximum contour curve height (Rz) and the average length (Rsm) of the contour curve elements of the sealant layer 16 within the above ranges, (1) transferring irregularities on the surface of the sealant layer 16 by embossing A method, and (2) a method of containing fine particles in the sealant layer 16. Among these, the method (1) is preferable because the lubricant is likely to bleed out on the surface of the sealant layer 16 and the heat seal strength at the time of heat sealing is improved.

Examples of the fine particles used in the method (2) include organic fine particles such as polyolefin resin, phenolic resin, acrylic resin, and polycarbonate resin, silicon dioxide, titanium oxide, calcium carbonate, talc, clay, calcined kaolin, and calcium phosphate. Inorganic fine particles such as These fine particles may be used alone or in combination of two or more.
The average particle diameter of the fine particles is preferably 250 to 4000 nm, and more preferably 500 to 2000 nm. The average particle size of the fine particles means a value measured by a particle size distribution measuring device.

  When the method (2) is used for the surface treatment of the sealant layer 16, the content of the fine particles in the sealant layer 16 is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. When the content of the fine particles is equal to or higher than the lower limit, blocking resistance and slipperiness are improved. When the content of the fine particles is not more than the upper limit value, the blocking resistance and the slipping property are improved, and it is difficult to prevent the lubricant from bleeding.

The exterior material 1 has a contour curve maximum height (Rz) of 500 nm to 2000 nm on the outermost surface, that is, the surface of the base material protective layer 17, and an average length (Rsm) of contour curve elements is 100 μm to 1500 μm. Thereby, the surface of the base material protective layer 17 exhibits excellent blocking resistance and slipperiness, and excellent moldability is obtained.
Since the exterior material is usually stored in a wound state after manufacturing, the outermost surface and the innermost surface are in contact with each other during storage. However, in the conventional exterior material, a lubricant is applied to the surface of the sealant layer on the innermost surface. Even when the lubricant is transferred to the outermost surface, the slipperiness of the outermost surface cannot be sufficiently obtained. On the other hand, in the exterior material 1, the contour curve maximum height (Rz) of the surface of the base material protective layer 17 and the average length (Rsm) of the contour curve elements are within the above range. The contact surface with the molding die is small, and the lubricant transferred to the surface of the base material protective layer 17 by contact with the sealant layer 16 is sufficiently effective at the contact portion with the molding die (protrusion tip surface). At the same time, the lubricant in the recesses acts even during molding and stretching, and excellent slipperiness is obtained on the surface of the base material protective layer 17.
That is, it is possible to sufficiently secure the slipperiness of the surface of the base material protective layer 17 without applying a lubricant directly on the surface of the base material protective layer 17 or including a lubricant in the base material protective layer 17. The work process at the time can be reduced.

  The maximum contour curve height (Rz) on the surface of the base material protective layer 17 is 1000 nm because the transferability of the lubricant from the surface of the sealant layer 16 to the irregularities on the surface of the base material protective layer 17 is improved and the slip property is improved. The above is preferable. In addition, the contour curve maximum height (Rz) on the surface of the base material protective layer 17 improves the transferability of the lubricant from the surface of the sealant layer 16 to the concavo-convex portion on the surface of the base material protective layer 17 and improves the slipperiness. 1500 nm or less is preferable.

  The average length (Rsm) of the contour curve element on the surface of the base material protective layer 17 is preferably 300 μm or more because blocking resistance is improved. The average length (Rsm) of the contour curve element on the surface of the base material protective layer 17 is preferably 800 μm or less because blocking resistance is improved.

Examples of the method for adjusting the contour curve maximum height (Rz) and the average length (Rsm) of the contour curve elements of the base material protective layer 17 within the above range include the method (1) and the method (2). Can be mentioned. Of these, the method (1) is preferable in view of resistance to the electrolyte.
Examples of the fine particles in the method (2) include the same fine particles as those exemplified in the surface treatment of the sealant layer 16. Among these, organic fine particles are preferable because transferability of the lubricant to the contact portion with the molding die on the surface of the base material protective layer 17 is improved.

  When the method (2) is used for the surface treatment of the base material protective layer 17, the content of the fine particles in the base material protective layer 17 is preferably 0.1 to 50% by mass, and 0.5 to 30% by mass. More preferred. When the content of the fine particles is at least the lower limit value, the blocking resistance is improved. When the content of the fine particles is not more than the upper limit value, the transparency of the base material protective layer 17 is improved, and the electrolyte resistance can be maintained.

[Production method]
Hereinafter, the manufacturing method of the exterior material 1 is demonstrated. However, the manufacturing method of the exterior material 1 is not limited to the method described below. As a manufacturing method of the exterior material 1, the method which has the following process (1)-(3) is mentioned, for example.
(1) A step of forming a corrosion prevention treatment layer 14 on the metal foil layer 13.
(2) The base material layer 11 is laminated via the first adhesive layer 12 on the side opposite to the side on which the corrosion prevention treatment layer 14 is formed in the metal foil layer 13, and the base material protective layer 17 is further formed on the base material layer 11. Forming.
(3) A step of laminating the sealant layer 16 via the second adhesive layer 15 on the corrosion prevention treatment layer 14 side in the metal foil layer 13.

(Process (1))
For example, the corrosion prevention treatment layer 14 is formed by applying and drying a corrosion prevention treatment agent on one surface of the metal foil layer 13.
Examples of the anti-corrosion treatment agent include the above-described anti-corrosion treatment agent for ceriazole treatment and anti-corrosion treatment agent for chromate treatment.
The coating method of the corrosion inhibitor is not particularly limited, and various methods such as gravure coating, reverse coating, roll coating, and bar coating can be employed.

(Process (2))
On the opposite side of the metal foil layer 13 to the side where the corrosion prevention treatment layer 14 is formed, the base material layer 11 is bonded and laminated by a technique such as dry lamination using an adhesive that forms the first adhesive layer 12, Further, a base material protective layer 17 is laminated on the base material layer 11.
When the base material protective layer 17 is formed of a polyester film, for example, the same adhesive as that used for the first adhesive layer 12 is used, and the polyester film is bonded onto the base material layer 11 by a technique such as dry lamination. A method is mentioned.
Moreover, when forming the base material protective layer 17 with the said polyacryl polyol and an aliphatic isocyanate hardening | curing agent, the base material protective layer 17 is apply | coated and dried on the base material layer 11, and the base material protective layer 17 is made to dry. The method of forming is mentioned. It does not specifically limit as a coating method of the said base material protective agent, For example, the method quoted by the coating method of the said corrosion prevention processing agent is mentioned.
Also, a method of producing a multilayer film by co-extrusion of the resin for forming the base material layer 11 and the base material protective layer 17 and laminating the laminated film on the corrosion prevention treatment layer 14 side in the metal foil layer 13 by thermal lamination. But you can.
In the step (2), an aging treatment may be performed in the range of room temperature to 100 ° C. for the purpose of improving adhesion.

(Process (3))
The second adhesive layer 15 is provided on the corrosion prevention treatment layer 14 side of the laminate in which the substrate protective layer 17, the substrate layer 11, the first adhesion layer 12, the metal foil layer 13, and the corrosion prevention treatment layer 14 are laminated in this order. The sealant layer 16 is laminated.
When using the thermoplastic resin mentioned above as the 2nd contact bonding layer 15, the method of carrying out the sandwich lamination by extruding the thermoplastic resin on the corrosion prevention process layer 14, bonding the sealant layer 16, and bonding is preferable. Further, a multilayer film may be produced by co-extrusion of the resin that forms the second adhesive layer 15 and the sealant layer 16, and the laminated film may be laminated on the corrosion prevention treatment layer 14 of the laminate by thermal lamination. .
Alternatively, a urethane-based adhesive may be used as the second adhesive layer 15, and the sealant layer 16 may be bonded to the corrosion prevention treatment layer 14 side of the laminate by a technique such as dry lamination, non-solvent lamination, wet lamination. .
In the step (3), for the purpose of improving adhesion, aging treatment or thermal lamination may be performed in the range of room temperature to 100 ° C.

The exterior material 1 is obtained by the steps (1) to (3) described above.
In addition, the manufacturing method of the exterior material 1 is not limited to the method of implementing the said process (1)-(3) sequentially. For example, step (1) may be performed after performing step (2).

  Since the outer packaging material 1 described above has a predetermined surface roughness on the outermost surface and the innermost surface, excessive powdering of the lubricant is suppressed on the innermost layer surface, and a large amount of the lubricant is transferred to the molding die. It is suppressed. Moreover, since the blocking agent and the slipperiness which were excellent in both the outermost surface and the innermost surface are expressed because the lubricant of the innermost surface is transferred to the outermost surface, excellent productivity and moldability can be obtained.

In addition, the exterior material for secondary batteries of the present invention is not limited to the exterior material 1 described above. For example, as shown in FIG. 2, it may be a secondary battery exterior material 1 </ b> A (hereinafter referred to as “exterior material 1 </ b> A”) in which a corrosion prevention treatment layer 14 is formed on both sides of a metal foil layer 13. The same parts as those of the exterior material 1 in the exterior material 1A are denoted by the same reference numerals, and description thereof is omitted.
The exterior material 1A can prevent corrosion of the metal foil layer 13 not only from the inner layer side but also from the outer layer side. The packaging material 1A can be manufactured by forming the corrosion prevention treatment layers 14 on both surfaces of the metal foil layer 13 in the step (1).

Moreover, as shown in FIG. 3, the base material protective layer 17 is not provided outside the base material layer 11, but from the outside, the base material layer 11, the first adhesive layer 12, the metal foil layer 13, the corrosion prevention treatment layer 14, It may be a secondary battery exterior material 1B (hereinafter referred to as “exterior material 1B”) in which the second adhesive layer 15 and the sealant layer 16 are laminated. The same parts as those of the exterior material 1 in the exterior material 1B are denoted by the same reference numerals and description thereof is omitted. The exterior material 1 </ b> B has the same laminated structure as the exterior material 1 except that the exterior material protection layer 17 is not provided.
In the case of the exterior material 1B, the contour curve maximum height (Rz) of the surface of the base material layer 11 that is the outermost surface is 500 nm to 2000 nm, and the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm.

<Secondary battery>
The secondary battery of this invention is a secondary battery provided with the exterior material for secondary batteries of this invention. The secondary battery of the present invention can employ a known battery configuration except that the secondary battery has the secondary battery exterior material of the present invention.
As the secondary battery of the present invention, for example, a positive electrode, a separator, a negative electrode, and an electrolytic solution are housed in a recess formed by cold forming in the outer packaging material for the secondary battery of the present invention, and the tab is placed from the interior to the outside. A secondary battery that is heat-sealed in the derived state can be given.

The secondary battery is obtained as follows, for example. A recess is formed by cold molding in a part of the outer packaging material for a lithium ion battery of the present invention, and a positive electrode, a separator, and a negative electrode are placed inside the concave portion, and another outer packaging material for a lithium ion battery of the present invention. Are stacked so that the sealant layers face each other, and the three sides are heat-sealed. Thereafter, in a vacuum state, an electrolytic solution is injected from the remaining one side, and the remaining one side is heat-sealed and sealed.
In addition, the secondary battery of this invention is not limited to what was manufactured by the said method.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
<Materials used>
The materials used in this example are shown below.
[Base material protective layer]
Base material protective agent A-1: An acrylic polyol (manufactured by Toray Fine Chemical Co., Ltd.) and an aliphatic isocyanate curing agent (manufactured by Nippon Polyurethane Co., Ltd.) are dissolved in toluene so that the molar ratio (NCO / OH) is 10. A coating liquid to which fine particles of an acrylic resin (average particle size 1.0 μm, manufactured by Sekisui Plastics Co., Ltd.) are added. In order to obtain a desired contour curve height (Rz) and an average length (Rsm) of contour curve elements, the content of the fine particles is based on the total mass of the acrylic polyol, the aliphatic isocyanate curing agent, and the fine particles. In the range of 0.1 to 50% by mass.

[Base material layer]
Base film B-1: Nylon 6 film (thickness 25 μm).

[First adhesive layer]
Adhesive C-1: Polyurethane adhesive (manufactured by Mitsui Chemicals Polyurethanes).

[Aluminum foil layer]
Metal foil D-1: Soft aluminum foil 8079 (Toyo Aluminum Co., Ltd., thickness 40 μm).

[Corrosion prevention treatment layer]
Treatment agent E-1: “Sodium polyphosphate-stabilized cerium oxide sol” using distilled water as a solvent and adjusted to a solid concentration of 10% by mass. The phosphate was 10 parts by mass with respect to 100 parts by mass of cerium oxide.

[Second adhesive layer]
Adhesive resin F-1: Maleic anhydride-modified polypropylene resin (Mitsui Chemicals).

[Sealant layer]
Sealant film G-1: An unstretched polypropylene film (thickness 40 μm) containing 0.1% by mass of erucamide as a lubricant.

<Production of exterior material>
The treatment agent E-1 was applied to both surfaces of the metal foil D-1 and dried to form a corrosion prevention treatment layer on both surfaces of the metal foil layer. Next, the base film B-1 is bonded to one surface side of the corrosion prevention treatment layer by an adhesive C-1 by a dry laminating method, and the base film B-1 is formed through the first adhesive layer (thickness 3 μm). Material layers were laminated. Then, the base material protective agent A-1 was apply | coated by the dry lamination method on the said base material layer, and the base material protective layer (thickness 3 micrometers) was formed by making it dry. Thereafter, aging was performed at 60 ° C. for 6 days. The maximum contour curve height (Rz) and the average length (Rsm) of the contour curve elements on the surface of the base material protective layer adjust the content of fine particles of the acrylic resin in the base material protective agent A-1. Adjusted.
Next, the second adhesive layer (thickness 20 μm) is formed by extruding the adhesive resin F-1 with an extrusion device on the other corrosion prevention treatment layer side, bonding the sealant film G-1 together, and sandwiching lamination. A sealant layer was laminated. Thereafter, the obtained laminated body was melted at 160 ° C., 4 kg / cm ² , 2 m / min with the second adhesive layer and the sealant layer, and the corrosion prevention treatment layer formed on the metal foil layer. And thermocompression bonded. In the molten state, the surface treatment of the sealant layer is performed by passing between cooling rolls having irregularities, and the contour curve maximum height (Rz) and the average length (Rsm) of the contour curve elements shown in Table 1 and Table 2 are shown. A sealant layer having the following surface was formed.

<Evaluation method>
[Surface roughness evaluation method]
Using a high-precision fine shape measuring instrument SUREFCORDER ET4000A (conforming to JIS B0601-1982) manufactured by Kosaka Laboratory, the contour curve maximum height (Rz) and contour curve of the surface of the sealant layer and the base material protective layer The average element length (Rsm) was measured.

[Evaluation of blocking resistance]
In the evaluation of the blocking resistance of the sealant layer, two 10 cm × 10 cm square test pieces were cut out from the exterior materials obtained in each example, and the surface of the innermost layer (sealant layer) of these test pieces was isopropyl alcohol (IPA). The innermost layers were overlapped with each other and left standing for 1 day under a load of ² kg / cm ^{2 in} an atmosphere of 60 ° C., and then peeled to confirm the surface of the sealant layer.
In the evaluation of blocking resistance of the base material protective layer, two 10 cm × 10 cm square test pieces were cut out from the exterior material in the same manner as described above, and the surface of the outermost layer (base material protective layer) of these test pieces was wiped with IPA. After that, the outermost layers were overlapped with each other and left for 1 day in a 60 ° C. atmosphere while applying a load of ² kg / cm ² , and then peeled to check the surface of the base material protective layer.
The blocking resistance was evaluated according to the following criteria.
“◎”: There is no blocking part.
“×”: There is a blocking part.

[Evaluation of slipperiness of innermost surface]
The exterior material obtained in each example was aged at 40 ° C. for 6 days, and the lubricant contained in the sealant layer was bleeded out to the surface, and then the dynamic friction coefficient of the sealant layer surface (the innermost surface) was changed to JIS K-7125. Measured in conformity. The evaluation of the slipperiness of the innermost surface was performed according to the following criteria.
“A”: The coefficient of dynamic friction is less than 0.3.
“◯”: The dynamic friction coefficient is 0.3 or more and less than 0.4.
"X": A dynamic friction coefficient is 0.4 or more.

[Evaluation of anti-lubricant powder blowing]
The exterior material obtained in each example was aged at 40 ° C. for 6 days, the lubricant contained in the sealant layer was bleeded out to the surface, and the appearance inspection on the sealant layer side was visually performed. The evaluation of the anti-lubricant powder blowing property was performed according to the following criteria.
“◎”: No powder blowing is observed.
“X”: The lubricant was excessively deposited on the surface of the sealant layer, and powder blowing was observed.

[Evaluation of slipperiness of outermost surface]
After wrapping the outer packaging material obtained in each example at 40 ° C. for 6 days, the lubricant contained in the sealant layer is bleed on the surface, and the lubricant is transferred to the base material protective layer, and then the base material is protected. The dynamic friction coefficient of the layer surface (outermost surface) was measured according to JIS K-7125. The evaluation of the slipperiness of the outermost surface was performed according to the following criteria.
“A”: The coefficient of dynamic friction is less than 0.3.
“◯”: The dynamic friction coefficient is 0.3 or more and less than 0.4.
"X": A dynamic friction coefficient is 0.4 or more.

[Evaluation of moldability]
After aging at 40 ° C. for 6 days in a state in which the outer packaging material obtained in each example is wound, a blank test piece of 150 mm × 190 mm is cut out from the outer packaging material, cold molding is performed on the test piece, and the moldability is increased. Evaluated. A punch having a shape of 100 mm × 150 mm, a punch corner R of 1.5 mm, a punch shoulder R of 0.75 mm, and a die shoulder R of 0.75 mm was used. The moldability was evaluated according to the following criteria.
“◎”: Deep drawing with a molding depth of 5 mm or more is possible without causing breakage and cracks.
“X”: Breaking and cracking occur in deep drawing with a molding depth of less than 5 mm.

[Examples 1 to 16 and Comparative Examples 1 to 20]
By the manufacturing method, an exterior material including a sealant layer having a surface having a maximum contour curve height (Rz) and an average length (Rsm) of the contour curve elements shown in Table 1 was manufactured.
Table 1 shows the evaluation results of blocking resistance, slipping property, and anti-slippery powder blowing property on the surface of the sealant layer of the obtained exterior material.

As shown in Table 1, the contour material maximum height (Rz) of the sealant layer surface is 100 nm to 2000 nm, and the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm. It had excellent blocking resistance, slipperiness and anti-lubricant powder blowing properties.
On the other hand, since the exterior material of Comparative Examples 1 to 6 having the maximum contour curve height (Rz) of the sealant layer surface of less than 100 nm has a shallow unevenness on the surface of the sealant layer and is almost smooth, even if the lubricant bleeds out to the surface. Blocking occurred. Further, in the exterior material, since the surface area of the sealant layer was too small, lubricant powder was sprayed on the surface of the sealant layer.
Further, in the exterior materials of Comparative Examples 15 to 20 where the contour curve maximum height (Rz) on the surface of the sealant layer exceeds 2000 nm, the surface unevenness of the sealant layer is deep, and most of the bleed-out lubricant is accumulated in the recesses on the surface of the sealant layer. As a result, the effect of improving slipperiness was not exhibited, so that sufficient slipperiness was not exhibited.
Further, the contour curve maximum height (Rz) of the surface of the sealant layer is in the range of 100 nm to 2000 nm, but the average length (Rsm) of the contour curve elements is less than 100 μm in Comparative Examples 7, 9, 11, and 13. In the exterior material, the contact portion with the other material of the sealant layer (protruding portion tip surface) became too large, and blocking occurred.
The maximum contour curve height (Rz) on the surface of the sealant layer is in the range of 100 nm to 2000 nm, but the outer lengths of the comparative examples 8, 10, 12, and 14 in which the average length (Rsm) of the contour curve elements exceeds 1500 μm. In the material, the surface area of the sealant layer became too small, and the lubricant bleeded out from inside the sealant layer was deposited to cause powder blowing.

[Examples 17 to 32 and Comparative Examples 21 to 38]
An exterior material having a configuration shown in Table 2 was produced by the production method. Table 2 shows the evaluation results of blocking resistance of the base material protective layer, transferability of the lubricant to the base material protective layer, and moldability.

As shown in Table 2, the exterior material of Examples 17 to 32, in which the contour curve maximum height (Rz) on the surface of the base material protective layer is 500 to 2000 nm and the average length (Rsm) of the contour curve elements is 100 to 1500 μm. Were excellent in blocking resistance of the base material protective layer, transferability of the lubricant and moldability.
On the other hand, the packaging material of Comparative Examples 21 to 26 having a contour curve maximum height (Rz) of less than 500 nm on the surface of the base material protective layer had good transferability and moldability, but the surface of the base material protective layer had irregularities. Blocking occurred because it was shallow and almost smooth.
Moreover, since the unevenness | corrugation of the base material protective layer surface is deep, the exterior material of the comparative examples 33-38 whose contour curve maximum height (Rz) of the base material protective layer surface exceeds 2000 nm reduces transfer to a recessed part, and is molded. The sliding property at the time of stretching was not sufficiently obtained.
Although the contour curve maximum height (Rz) on the surface of the base material protective layer is 500 nm to 2000 nm, the exterior materials of Comparative Examples 27, 29, and 31 in which the average length (Rsm) of the contour curve elements is less than 100 μm are base materials. The contact portion with the other material on the surface of the protective layer (protruding portion tip surface) increased, and blocking occurred on the outermost surface.
Further, the contour curve maximum height (Rz) of the surface of the base material protective layer is 500 nm to 2000 nm, but the exterior materials of Comparative Examples 28, 30, and 32 in which the average length (Rsm) of the contour curve elements exceeds 1500 μm are: While blocking occurred, the transfer unevenness of the lubricant occurred, the slipperiness of the outermost surface could not be obtained sufficiently, and the moldability deteriorated.

  As described above, the contour curve maximum height (Rz) on the surface of the sealant layer is 100 nm to 2000 nm, the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm, and the contour curve on the surface of the base material protective layer The exterior material having the maximum height (Rz) of 500 nm to 2000 nm and the average length (Rsm) of the contour curve element of 100 μm to 1500 μm is caused by excessive accumulation of lubricant at the contact portion with the molding die on the surface of the sealant layer. The occurrence of powder blowing is suppressed. Further, the lubricant is sufficiently transferred to the contact portion with the molding die in the outermost layer. As a result, the exterior material exhibited excellent blocking resistance and slipperiness, and excellent moldability was obtained.

1, 1A, 1B Secondary Battery Exterior Material 11 Base Material Layer 12 First Adhesive Layer 13 Metal Foil Layer 14 Corrosion Prevention Treatment Layer 15 Second Adhesive Layer 16 Sealant Layer 17 Base Material Protective Layer

Claims (5)

In an exterior material for a secondary battery in which at least a base material layer, a first adhesive layer, a metal foil layer, a corrosion prevention treatment layer, a second adhesive layer, and a sealant layer provided with a lubricant on the innermost surface are sequentially laminated from the outside. ,
The maximum height (Rz) of the contour curve of the innermost surface measured according to JIS B0601-1982 is 100 nm to 2000 nm, the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm, and the contour of the outermost surface. An exterior material for a secondary battery, wherein the maximum curve height (Rz) is 500 nm to 2000 nm, and the average length (Rsm) of the contour curve elements is 100 μm to 1500 μm.   The packaging material for a secondary battery according to claim 1, wherein the base material layer is a layer made of a polyamide film.   The exterior material for secondary batteries of Claim 1 or 2 with which the base material protective layer which protects the said base material layer is laminated | stacked on the outer side of the said base material layer.   The said base material protective layer contains the polyurethane resin formed from the polyester resin or 1 type or more chosen from the group which consists of a polyester polyol and an acrylic polyol, and an aliphatic isocyanate hardening | curing agent. The packaging material for secondary batteries as described in any one of Claims.   The secondary battery provided with the exterior material for secondary batteries as described in any one of Claims 1-4.

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