JP6525119B2 - Packaging material for battery, method for producing the same, and battery - Google Patents

Description

  The present invention relates to a battery packaging material, a method of manufacturing the same, and a battery.

  Conventionally, various types of batteries have been developed. In these batteries, battery elements composed of electrodes, electrolytes and the like need to be sealed with a packaging material and the like. Metal packaging materials are widely used as battery packaging materials.

  In recent years, with the advancement of performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., batteries having various shapes are required. Moreover, thickness reduction, weight reduction, etc. are also calculated | required by the battery. However, it is difficult to follow the diversification of battery shapes with metal packaging materials that are frequently used conventionally. Moreover, since it is metal, there is a limit to weight reduction of the packaging material.

  Therefore, a film-like laminate in which a base material layer / barrier layer / thermal adhesive resin layer is sequentially laminated is used as a battery packaging material that can be easily processed into various shapes and can achieve thinning and weight reduction. Proposed.

  In such a film-like battery packaging material, generally, a concave portion is formed by molding, and a battery element such as an electrode or an electrolytic solution is disposed in a space formed by the concave portion, and a thermally fusible resin layer By heat-sealing them together, a battery is obtained in which the battery element is housed inside the battery packaging material.

  In the process of manufacturing a battery packaging material formed of such a film-like laminate, or in the process of manufacturing a battery using the battery packaging material, the time of transportation is completed before the battery is completed. The surface characteristics on the side of the base material layer may be deteriorated, such as damage, heat deterioration at the time of heat fusion, adhesion of the electrolytic solution at the time of sealing the electrolytic solution, and the like. Since the surface on the substrate layer side is located on the outside of the battery, these characteristic deteriorations are required to be avoided as much as possible.

  For example, in Patent Document 1, a protective film is characterized in that the adhesive force is substantially eliminated in advance by heating, ultraviolet irradiation or the like with respect to a laminate film having a three-layer structure in which a protective layer and a heat fusion layer are laminated on metal foil. A method is proposed in which the battery is manufactured after pasting, and finally the protective film with reduced adhesion is peeled off by applying heat or ultraviolet light.

  However, in the method described in Patent Document 1, there is a problem that a layer or the like located under the protective film is deteriorated by heating or ultraviolet irradiation. In addition, it is necessary to set the heating temperature and the wavelength of ultraviolet light, and there is also a problem that the adhesion of the protective film is not constant due to the change of these setting values.

JP, 2009-43442, A

  The present invention is an invention made in view of such problems in the prior art. That is, the main object of the present invention is to provide a battery packaging material capable of effectively suppressing the characteristic deterioration of the outer surface of the battery packaging material in the process of producing the battery or the battery packaging material. Furthermore, another object of the present invention is to provide a method for producing the battery packaging material, a battery using the battery packaging material, and a method for producing the battery.

The present inventors diligently studied to solve the above-mentioned problems. As a result, it is composed of a laminate including at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order, the bonding layer includes a polyester resin, and the resin layer is The battery packaging material which can be peeled off from the laminate using an aqueous liquid does not require heating or ultraviolet irradiation which degrades the characteristics of the outer surface of the battery packaging material as disclosed in Patent Document 1, and for batteries or batteries It has been found that characteristic deterioration of the outer surface of the battery packaging material can be effectively suppressed in the process of producing the packaging material.
The present invention is an invention completed by repeating studies based on these findings.

That is, the present invention provides the inventions of the aspects listed below.
Item 1. A laminate comprising at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order,
The bonding layer contains a polyester resin,
The packaging material for batteries which the said resin layer is peelable from the said laminated body using aqueous liquid.
Item 2. The peeling strength in the case of peeling the resin layer from the laminate in a state where water is not attached to the bonding layer in an environment with a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure is 2.0 N / 15 mm or more ,And,
The peel strength in the case of peeling the resin layer from the laminate using the aqueous liquid in an environment at a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure is 1.0 N / 15 mm or less,
The packaging material for a battery according to Item 1, wherein the aqueous liquid is water.
Item 3. 3. The battery packaging material according to item 1 or 2, wherein a lubricant is present on the surface on the resin layer side of the laminate.
Item 4. The packaging material for a battery according to any one of Items 1 to 3, wherein a UV absorber is contained in at least one of the resin layer, the bonding layer, and the base material layer.
Item 5. 5. The battery packaging material according to item 4, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
Item 6. The packaging material for a battery according to any one of Items 1 to 5, wherein a light stabilizer is contained in at least one of the resin layer, the bonding layer, and the base material layer.
Item 7. Item 7. The battery packaging material according to item 6, wherein the light stabilizer is a hindered amine light stabilizer.
Item 8. At least a step of laminating the resin layer, the bonding layer, the base layer, the barrier layer, and the heat-fusible resin layer in this order to obtain a laminate.
The manufacturing method of the packaging material for batteries using the thing in which the said joining layer contains the polyester resin and the said resin layer can peel from the said laminated body using an aqueous liquid.
Item 9. Item 8. A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of Items 1 to 7.
Item 10. Use of a laminate comprising at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order for a battery packaging material,
The bonding layer contains a polyester resin,
Use of the laminate for a battery packaging material, wherein the resin layer is peelable from the laminate using an aqueous liquid.

  ADVANTAGE OF THE INVENTION According to this invention, the packaging material for batteries which can suppress effectively the characteristic degradation of the outer surface of the packaging material for batteries in the process of manufacturing the battery or battery packaging material can be provided. Further, according to the present invention, it is possible to provide a method for producing the battery packaging material, a battery using the battery packaging material, and a method for producing the battery.

It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram for demonstrating the measuring method of peeling strength.

  The battery packaging material of the present invention comprises at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order, and the bonding layer is made of polyester. A resin is included, and the resin layer is characterized by being peelable from the laminate using an aqueous liquid. Hereinafter, the battery packaging material of the present invention, the battery using the battery packaging material of the present invention, and the manufacturing method thereof will be described in detail with reference to FIGS. 1 to 3.

  In addition, in this specification, the numerical range shown by "-" means "or more" and "or less." For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.

1. Laminated structure and physical properties of battery packaging material The battery packaging material of the present invention is, for example, at least a resin layer 1a, a bonding layer 1b, a base material layer 2, a barrier layer 3, and heat as shown in FIGS. It is comprised from the laminated body which has the fusible resin layer 4 in this order. In the battery packaging material of the present invention, the resin layer 1a is the outermost layer, and the thermally fusible resin layer 4 is the innermost layer. That is, when assembling the battery, the battery element is sealed by sealing the battery element by thermally fusing the heat-fusible resin layers 4 located on the peripheral edge of the battery element.

  FIGS. 1 to 3 show an aspect in which the laminate of the resin layer 1 a and the bonding layer 1 b containing a polyester resin constitutes the protective layer 1. The bonding layer 1 b is provided to bond (more specifically, adhere) the resin layer 1 a to another layer. The bonding layer 1 b can be referred to as an adhesive layer.

  In the battery packaging material 10 of the present invention, as shown in FIG. 2 and FIG. 3, an adhesive layer is optionally added between the base layer 2 and the barrier layer 3 for the purpose of enhancing the adhesiveness thereof. 5 may be provided. In addition, as shown in FIG. 3, the battery packaging material 10 of the present invention is bonded between the barrier layer 3 and the heat fusible resin layer 4 as necessary for the purpose of enhancing the adhesiveness thereof. A layer 6 may be provided. Moreover, although illustration is abbreviate | omitted, between the joining layer 1b and the base material layer 2, the surface coating layer may be provided.

  As described later, the resin layer 1a can be peeled off from the laminate constituting the battery packaging material 10 using an aqueous liquid. This is because the bonding layer 1 b has adhesiveness by the polyester resin. In the battery packaging material of the present invention, the resin layer 1a can be easily peeled off from the laminate constituting the battery packaging material 10 using an aqueous liquid. In addition, peeling using an aqueous liquid has less influence on the base material layer 2 and the surface coating layer, and even if the base material layer 2 absorbs moisture, it may be dried. Can be suppressed.

  In the present invention, adhesion or tackiness means the property of bonding a plurality of objects together, is a concept included in adhesion in a broad sense, and is a sticky property (tackiness). The aqueous liquid is not particularly limited as long as it is a liquid containing water, but specific examples of the aqueous liquid include water, a water-containing polar organic solvent, and the like. Examples of the water-containing polar organic solvent include aqueous solutions of polar organic solvents such as alcohol, acetone, ethyl acetate and dimethyl ether. Examples of the aqueous solution of alcohol (hydrous alcohol) include aqueous solutions of lower alcohols such as methanol and ethanol. As a mass ratio (water: polar solvent) of water in a water-containing polar organic solvent, and a polar solvent, about 100: 1 to 100: 100 is mentioned. The aqueous liquid may be constituted by one kind of liquid or may be constituted by two or more kinds of liquids.

  Further, in the present invention, that the resin layer 1a is peelable from the laminate means that the resin layer 1a can be peeled off from the layer facing the bonding layer 1b. The bonding layer 1b may be peeled off from the surface on the base layer 2 side together with the resin layer 1a, and the component of the bonding layer 1b may remain on the surface on the base layer 2 side.

  The upper limit of the peel strength (A) of the resin layer 1a when water is attached to the bonding layer 1b in an environment with a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure (1 atm) is preferably about 1.0 N / 15 mm or less, more preferably about 0.5 N / 15 mm or less, the lower limit is not particularly, preferably about 0.0 N / 15 mm or more, more preferably about 0.01 N / 15 mm or more, more preferably about 0.1 N / 15 mm or more is mentioned. The range of the peel strength (A) is preferably about 0.0 to 1.0 N / 15 mm, about 0.0 to 0.5 N / 15 mm, about 0.01 to 1.0 N / 15 mm, or 0.01 About -0.5 N / 15 mm, about 0.1-1.0 N / 15 mm, about 0.1-0.5 N / 15 mm are mentioned. In the present invention, “removable from the laminate using an aqueous liquid” means, for example, that the resin layer 1a can be easily peeled off from the laminate using an aqueous liquid, and as a specific example, The strength (A) is to satisfy the above value.

  The lower limit of the peel strength (B) of the resin layer 1a when water is not attached to the bonding layer 1b in an environment with a temperature of 25 ° C., a relative humidity of 50% and an atmospheric pressure (1 atm) is preferably about 2. 0 N / 15 mm or more, more preferably about 2.2 N / 15 mm or more can be mentioned. There is no particular upper limit, but preferably about 30.0 N / 15 mm or less. The range of the peel strength (B) is preferably about 2.0 to 30.0 N / 15 mm, more preferably about 2.2 to 30.0 N / 15 mm.

  In the battery packaging material of the present invention, the peel strength (B) of the resin layer 1a when no water is attached to the bonding layer 1b is about 2.0 N / 15 mm or more, and water is attached to the bonding layer 1b. Preferably, the peel strength (A) of the resin layer 1a in the case of being made is about 1.0 N / 15 mm or less, the peel strength (B) is about 2.2 N / 15 mm or more, and the peel strength More preferably, (A) is about 0.5 N / 15 mm or less.

  In the battery packaging material of the present invention, the resin layer 1a has a high peel strength before water adheres to the bonding layer 1b, and the battery is used as the outermost layer of the laminate constituting the battery packaging material. The property deterioration of the packaging material is suitably suppressed, and the peel strength of the resin layer 1a is reduced by adhering the aqueous liquid to the bonding layer 1b at a desired timing. More specifically, when water adheres to the bonding layer 1b, moisture penetrates into at least one of the resin layer 1a, the bonding layer 1b, and the base material layer 2, and the adhesion of the bonding layer 1b decreases. The peel strength of the resin layer 1a is reduced. Thereby, resin layer 1a can be suitably exfoliated from a layered product. For example, printing may be performed on the outside of the battery from the viewpoint of the battery identification and the like. In the battery packaging material of the present invention, when the printing is performed, the characteristic deterioration of the surface of the battery packaging material on the side of the base material layer 2 is effectively suppressed, and the aqueous liquid is used when the printing is performed. By peeling the resin layer 1a from the laminate, the surface on the base material layer 2 side of the battery packaging material to be the printing surface can be easily exposed, and the ink is applied to the surface of the base material layer 2 and the surface coating layer. The present invention can also be suitably applied to applications in which printing according to In addition, the battery packaging material of the present invention including the resin layer 1a is subjected to molding using a mold, and then the resin layer 1a is separated from the laminate using an aqueous liquid. The effect of suppressing holes and the effect of suppressing damage to the surfaces of the base material layer 2 and the surface coating layer by a mold can be obtained, and the effect of improving formability can be suitably obtained. In addition, when the thermally fusible resin layer 4 is heat-sealed using the battery packaging material of the present invention provided with the resin layer 1a, the base layer 2 and the surface covering layer are deteriorated due to high temperature and high pressure. The protection by 1a can be effectively suppressed. Moreover, when using for the battery in which heat dissipation is calculated | required, and when using for the battery in which thinness is calculated | required, the resin layer 1a can be peeled and used. In addition, the timing and purpose which peel the resin layer 1a are not limited to these.

  Specifically, the method for measuring the peel strength of the resin layer 1a in an environment at a temperature of 25 ° C., a relative humidity of 50%, and an atmospheric pressure (1 atm) is as follows.

<Method of measuring peel strength with water attached>
The battery packaging material is cut into a rectangular shape of 100 mm (MD: Machine Direction) x 15 mm (TD: Transverse Direction) to obtain a test sample. In an environment with a temperature of 25 ° C., a relative humidity of 50% and an atmospheric pressure (1 atm), first, 35% hydrochloric acid is deposited on the ends of the resin layer 1a and the bonding layer 1b of the test sample, as shown in the schematic view of FIG. The resin layer 1a is peeled about 30 mm in the direction of the MD so as to be removed. Wipe off the hydrochloric acid adhering to the test sample and let it dry. Next, water (W) is attached to the portion (the bonding layer 1b between the resin layer 1a and the surface on the base layer 2 side) from which the resin layer 1a is peeled using a dropper. At this time, water (W) is attached over the entire direction of TD at the boundary between the resin layer 1 a and the surface on the base layer 2 side. Water is used in such a boundary portion that the water adheres sufficiently in the direction of TD. Next, using a tensile tester (for example, an autograph manufactured by Shimadzu Corporation), the resin layer 1a is measured from the surface of the base material layer 2 under the measurement conditions of a distance between chucks of 50 mm, a peeling speed of 50 mm / min and a peeling angle of 180 °. Peeling is performed, and the peeling strength when the distance between chucks reaches 57 mm is taken as the peeling strength (N / 15 mm) in a state where water is attached.

<Measurement of peeling strength in the state where water is not attached>
In the state where the above <water is attached except that water is not attached using a dropper to the part where the resin layer 1a is peeled off (the joint layer 1b between the resin layer 1a and the surface on the substrate layer 2 side) Method of Measuring Peeling Strength> The resin layer 1a is peeled from the surface of the base material layer 2 under the same measurement conditions as in the following, and the peeling strength when the distance between chucks reaches 57 mm is the peeling strength in the state where water is not attached. It shall be (N / 15 mm).

  The thickness of the laminate constituting the battery packaging material 10 of the present invention is not particularly limited, but the battery packaging material having excellent formability while reducing the thickness of the battery packaging material to increase the energy density of the battery From the viewpoint of making it, for example, 180 μm or less, preferably 150 μm or less, more preferably about 60 to 180 μm, further preferably about 60 to 150 μm.

2. Each Layer [Resin Layer 1a and Bonding Layer 1b] Forming Packaging Material for Battery
In the battery packaging material of the present invention, the resin layer 1a is located on the outermost layer of the battery packaging material, and can be peeled off from the laminate constituting the battery packaging material using an aqueous liquid at a desired timing. It is a layer.

  It is preferable that the resin layer 1a is laminated | stacked with the joining layer 1b of one layer, and the protective layer 1 of 2 layer structure is comprised, as the schematic diagram of FIGS. 1-3 shows.

  The bonding layer 1 b adheres to the base material layer 2 (the surface coating layer when a surface coating layer described later exists). Moreover, the resin layer 1a is located in the outermost layer side.

  As described above, until the battery is completed, the battery packaging material or damage during transportation of the battery, heat deterioration during heat fusion, adhesion of the electrolyte when encapsulating the electrolyte, etc. The surface properties of the packaging material on the side of the base material layer 2 may be degraded, and such degradation of properties is required to be avoided as much as possible.

  In the battery packaging material of the present invention, since the specific resin layer 1a and the bonding layer 1b which can be peeled off are provided, in the process of manufacturing the battery or the battery packaging material, the battery packaging as disclosed in Patent Document 1 It is not necessary to heat the substrate to deteriorate the characteristics of the outer surface of the material or to irradiate ultraviolet light, and the deterioration of the characteristics of the outer surface of the battery packaging material can be effectively suppressed.

  Bonding layer 1 b contains a polyester resin. The bonding layer 1 b is preferably a thermoplastic resin. The fact that the bonding layer 1b is a thermoplastic resin means, for example, in the measurement of the displacement of the probe using thermomechanical analysis, the probe is placed on the surface of the bonding layer 1b at the end of the battery packaging material (laminate) and then measured. The probe's position is lower than the initial value when the probe is heated from 40 ° C to 250 ° C under the condition of -4V and the heating rate of 5 ° C / min under the setting value of deflection of the probe at the start It can confirm by. About the detail of displacement amount measurement of the probe using a thermomechanical analysis, it is the same as that of the method demonstrated by the below-mentioned resin layer 1a. In addition, it can be confirmed by, for example, infrared spectroscopy that the bonding layer 1b contains a polyester resin.

  The polyester resin contained in the bonding layer 1 b is not particularly limited as long as the bonding layer 1 b can be peeled off and adheres to the layer adjacent to the bonding layer 1 b by the contact of the bonding layer 1 b with the aqueous liquid. Until the bonding layer 1b comes in contact with the aqueous liquid, it adheres firmly to the layer adjacent to the bonding layer 1b, and when the bonding layer 1b contacts the aqueous liquid, it easily peels off from the layer adjacent to the bonding layer 1b. From the viewpoint of making it possible, a polyester-based elastomer is mentioned as a preferable specific example of the polyester resin. The polyester-based elastomer is a polyester-based elastomer and thus has good heat resistance. Moreover, since polyester-based elastomers are polyester-based, they have high polarity and good wettability with aqueous liquids, and are easily peeled off using aqueous liquids. Further, the elastomer has many low molecular weight components and is easily peeled off. When the resin layer contains a polyester resin, the polyester elastomer has good adhesion to the polyester substrate, so when the resin layer is peeled off, the bonding layer is peeled off together with the resin layer, and on the substrate layer 2 side It is preferable from the point which the component of a joining layer does not remain easily. The polyester-based elastomer is not particularly limited, but is preferably a saturated polyester-based elastomer, and more preferably a saturated polyester-based elastomer containing a polyalkylene ether glycol segment. As a saturated polyester type elastomer containing a polyalkylene ether glycol segment, for example, a block copolymer composed of an aromatic polyester which is a hard segment and a polyalkylene ether glycol which is a soft segment and an aliphatic polyester is preferable. Furthermore, polyester polyether block copolymers having polyalkylene ether glycol as a soft segment are more preferred.

  As polyester polyether block copolymers, (i) aliphatic and / or alicyclic diols having 2 to 12 carbon atoms, (ii) aromatic dicarboxylic acids or alkyl esters thereof and / or aliphatic dicarboxylic acids or It is preferable to use the alkyl ester and (iii) a polyalkylene ether glycol as raw materials to polycondensate an oligomer obtained by an esterification reaction or a transesterification reaction. In addition, it can be confirmed by, for example, having tackiness (viscosity) at normal temperature that the bonding layer 1 b contains an elastomer.

  As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, for example, those generally used as a raw material of polyester, particularly a raw material of polyester-based elastomer can be used. Specifically, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. Among these, 1,4-butanediol or ethylene glycol is preferable, and 1,4-butanediol is particularly preferable. These diols may be used alone or in combination of two or more.

  As the aromatic dicarboxylic acid, raw materials of polyester, in particular, those generally used as raw materials of polyester elastomers can be used. Specifically, for example, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid and the like can be mentioned. Among these, terephthalic acid or 2,6-naphthalene dicarboxylic acid is preferable, and terephthalic acid is particularly preferable. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

  Examples of the alkyl ester of aromatic dicarboxylic acid include dimethyl ester and diethyl ester of aromatic dicarboxylic acid. Among these, dimethyl terephthalate and 2,6-dimethyl naphthalene dicarboxylate are preferable.

  As the aliphatic dicarboxylic acid, cyclohexane dicarboxylic acid is preferable, and as the alkyl ester thereof, dimethyl ester or diethyl ester is preferable. In addition to the above components, trifunctional alcohols and tricarboxylic acids or esters thereof may be copolymerized in small amounts, and further, aliphatic dicarboxylic acids such as adipic acid or dialkyl esters thereof may be used as copolymerization components.

  As the polyalkylene ether glycol, for example, polyethylene glycol, poly (1,2- and / or 1,3-propylene ether) glycol, poly (tetramethylene ether) glycol compound, poly (hexamethylene ether) glycol compound etc. Can be mentioned. Among these, poly (tetramethylene ether) glycol compounds are preferable. The poly (tetramethylene ether) glycol-based compound includes poly (tetramethylene ether) glycol and its analogous compounds. In addition, poly (hexamethylene ether) glycol-based compounds include poly (hexamethylene ether) glycol and its analogues.

  The preferred lower limit of the number average molecular weight of the polyalkylene ether glycol is about 400 or more, and the preferred upper limit is about 6000 or less. By setting the lower limit to about 400 or more, the block property of the copolymer becomes high, and by setting the upper limit to about 6000 or less, phase separation in the system hardly occurs, and polymer physical properties are easily expressed. A more preferable lower limit is about 500 or more, a more preferable upper limit is about 4000 or less, a still more preferable lower limit is about 600 or more, and a still more preferable upper limit is about 3000 or less.

  In addition, in this specification, a number average molecular weight means what was measured by gel permeation chromatography (GPC). In addition, the measurement of the number average molecular weight by GPC is a standard polymer (polystyrene) conversion molecular weight.

When a polyester polyether block copolymer consisting of polyester and polyalkylene ether glycol is used as the polyester elastomer, the lower limit of the content of the polyalkylene ether glycol component is preferably about 5% by mass or more, more preferably About 30% by weight or more, more preferably about 55% by weight or more, and the upper limit is preferably about 90% by weight or less, more preferably about 80% by weight or less. The content of the polyalkylene ether glycol component used nuclear magnetic resonance spectroscopy (H ¹ -NMR measurement) can be calculated based on the chemical shift and the integrated value of the hydrogen atom.

  The polyester-based elastomer is preferably a modified polyester-based elastomer modified with a modifier. The modification reaction for obtaining a modified polyester-based elastomer is performed, for example, by reacting the polyester-based elastomer with an α, β-ethylenically unsaturated carboxylic acid as a modifier. In the modification reaction, it is preferable to use a radical generator. In the modification reaction, a grafting reaction in which an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof is added to the polyester-based elastomer mainly occurs, but a decomposition reaction also occurs. As a result, the modified polyester-based elastomer may have a reduced molecular weight and a low melt viscosity. In addition, in the modification reaction, as another reaction, transesterification reaction and the like are generally considered to occur, and the resulting reaction product is generally a composition containing unreacted starting materials and the like. In such a case, the content of the modified polyester-based elastomer in the resulting reactant is about 10% by mass or more, more preferably about 30% by mass or more, and the content of the modified polyester-based elastomer is about 100% by mass More preferable.

  Examples of α, β-ethylenically unsaturated carboxylic acids used as modifiers include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, etc. Acid; 2-octene-1-yl succinic acid, 2-dodecen-1-yl succinic acid, 2-octadecen-1-yl succinic acid, maleic anhydride, 2,3-dimethylmaleic acid Anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1 2,3,6-Tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2.2 Unsaturated carboxylic acid anhydrides such as oct-5-ene-2,3-dicarboxylic acid anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride The thing is mentioned. Of these, acid anhydrides are preferred because of their high reactivity. The α, β-ethylenically unsaturated carboxylic acid can be appropriately selected according to the copolymer containing the polyalkylene ether glycol segment to be modified and modification conditions, and two or more types may be used in combination . In addition, (alpha), (beta)-ethylenic unsaturated carboxylic acid can also be melt | dissolved and used for the organic solvent etc.

  Examples of the radical generator include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene Organic and inorganic peroxides such as dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide and hydrogen peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxy) Chill) propionamide], azo compounds such as azodi -t- butane, and carbon radical generators such as dicumyl.

  The radical generator can be appropriately selected according to the type of polyester elastomer used for the modification reaction, the type of the α, β-ethylenically unsaturated carboxylic acid and the modification conditions, and two or more types may be used in combination It is also good. Furthermore, the radical generator can be used by dissolving it in an organic solvent or the like.

  The preferable lower limit of the compounding amount of the α, β-ethylenically unsaturated carboxylic acid is about 0.01 parts by mass or more, and the preferable upper limit is about 30.0 parts by mass or less with respect to 100 parts by mass of the polyester elastomer. When the amount is about 0.01 parts by mass or more, the modification reaction can be sufficiently performed, and when the amount is about 30.0 parts by mass or less, it is economically advantageous. A more preferable lower limit is about 0.05 parts by mass or more, a more preferable upper limit is about 5.0 parts by mass or less, a further preferable lower limit is about 0.10 parts by mass or more, and a further preferable upper limit is about 1.0 parts by mass or less.

  The preferable lower limit of the compounding amount of the radical generating agent is about 0.001 parts by mass or more, and the preferable upper limit is about 3.00 parts by mass or less with respect to 100 parts by mass of the polyester-based elastomer. By setting the amount to about 0.001 parts by mass or more, a modification reaction easily occurs, and by setting the amount to about 3.00 parts by mass or less, a decrease in material strength due to molecular weight reduction (reduction of viscosity) at the time of modification hardly occurs . A more preferable lower limit is about 0.005 parts by mass or more, a more preferable upper limit is about 0.50 parts by mass or less, a further preferable lower limit is about 0.010 parts by mass or more, and a further preferable upper limit is about 0.20 parts by mass or less The particularly preferred upper limit is about 0.10 parts by mass or less.

  Although a known reaction method such as a melt-kneading reaction method, a solution reaction method, or a suspension dispersion reaction can be used as a modification reaction for obtaining the above-mentioned modified polyester elastomer, the melt-kneading is usually carried out because it is inexpensive. The reaction method is preferred.

  In the method according to the melt-kneading reaction method, melt-kneading is performed after uniformly mixing the above-described components at a predetermined blending ratio. A Henschel mixer, a ribbon blender, a V-type blender etc. can be used for mixing of each component, A Banbury mixer, a kneader, a roll, multi-screw kneading extruders, such as a uniaxial or biaxial, etc. can be used for melt-kneading can do.

  The preferable lower limit of the kneading temperature in the case of melt-kneading is about 100 ° C. or more, and the preferable upper limit is about 300 ° C. or less. By setting it in the said range, the thermal deterioration of resin can be prevented. A more preferable lower limit is about 120 ° C. or more, a more preferable upper limit is about 280 ° C. or less, a still more preferable lower limit is about 150 ° C. or more, and a further preferable upper limit is about 250 ° C. or less.

  The preferable lower limit of the modification rate (grafting amount) of the modified polyester elastomer is about 0.01% by mass or more, and the preferable upper limit is about 10.0% by mass or less. When it is about 0.01% by mass or more, the affinity to the polyester is high, and when it is about 10.0% by mass or less, strength reduction due to molecular degradation at the time of modification can be reduced. A more preferable lower limit is about 0.03 mass% or more, a more preferable upper limit is about 7.0 mass% or less, a still more preferable lower limit is about 0.05 mass% or more, and a still more preferable upper limit is about 5.0 mass% or less is there.

The modification rate (grafting amount) of the modified polyester-based elastomer can be determined from the spectrum obtained by H ¹ -NMR measurement.

  The material constituting the resin layer 1a is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin, with preference given to a thermoplastic resin. The thermoplastic resin is not particularly limited, but preferably a polyester resin, a polyamide resin, an acrylic resin, a polyolefin resin, a polycarbonate resin from the viewpoint of suppressing deterioration of the surface characteristics of the base material 2 side of the battery packaging material. Among these, polyester resins are more preferable. In particular, from the viewpoint of enhancing the mechanical strength of the resin layer 1a and suitably peeling the resin layer 1a, the resin layer 1a is preferably made of a biaxially stretched polyester film. The biaxially stretched polyester film has enhanced orientation, and is excellent in moldability, tensile strength and puncture strength. In addition, only 1 type may be sufficient as resin which comprises the resin layer 1a, and 2 or more types may be sufficient as it.

  Preferred examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and copolyester. The polyester resin may be composed of only one type, or may be composed of two or more types. The polyester resin may be, for example, polyethylene terephthalate as a main component (content is, for example, 90% by mass or more, 95% by mass or more, 99% by mass or more), and polybutylene terephthalate may be contained as a subcomponent.

  Moreover, it is preferable that resin which is comprising the resin layer 1a has melting | fusing point higher than resin which is comprising the base material layer 2. As shown in FIG. Due to the high melting point of the resin forming the resin layer 1a, the resin layer 1a is deteriorated due to the high temperature and high pressure when the heat sealing resin layer 4 of the battery packaging material is heat sealed. Can be effectively suppressed. An embodiment in which the deterioration suppressing effect of the base material layer 2 by the resin layer 1a is particularly effectively exhibited is an embodiment in which the resin layer 1a is made of a polyester resin and the base material layer 2 is made of a polyamide.

  In the present invention, in the resin layer 1a, in the measurement of the displacement of the probe using thermomechanical analysis, the probe is placed on the surface of the resin layer 1a at the end of the battery packaging material (laminate) and the probe at the start of measurement When the probe is heated from 40 ° C to 220 ° C under the conditions of -4 V and a heating rate of 5 ° C / min, it is preferable that the position of the probe does not fall below the initial value. . Thereby, deterioration of the base material layer 2 due to high temperature and high pressure at the time of heat fusion bonding of the heat sealing resin layer 4 of the battery packaging material can be effectively suppressed by protection by the resin layer 1a.

  In the measurement of the displacement of the probe, first, the probe is placed on the surface of the resin layer 1a at the end of the battery packaging material (laminated body). The end portion at this time is a portion where the cross section of the resin layer 1 a is obtained by cutting in the thickness direction so as to pass through the central portion of the battery packaging material. The cutting can be performed using a commercially available rotary microtome or the like. In the case of measuring the amount of displacement of a battery packaging material used in a battery in which an electrolyte or the like is enclosed, the portion of the battery packaging material in which the thermally fusible resin layers are heat-sealed to each other Make a measurement. As an atomic force microscope to which a cantilever with a heating mechanism is attached, for example, an afm plus system manufactured by ANASIS INSTRUMENTS is used, and as a probe, a cantilever Therma Lever AN 2-200 (spring constant 0.5 to 3 N / m manufactured by ANASYS INSTRUMENTS) ) Can be used. The tip radius of the probe is 30 nm or less, the set value of the deflection of the probe is −4 V, and the temperature rising rate is 5 ° C./min. Next, when the probe is heated in this state, the surface of the resin layer 1a is expanded by the heat from the probe and the probe is pushed up, and the position of the probe is an initial value (the position when the temperature of the probe is 40 ° C.) It rises more than that. When the heating temperature further rises, the resin layer 1a is softened, the probe pierces the resin layer 1a, and the position of the probe is lowered. In the measurement of the displacement of the probe using an atomic force microscope equipped with a nanothermal microscope composed of a cantilever with a heating mechanism, the battery packaging material to be measured is at room temperature (25 ° C.) and 40 A probe heated to 0 ° C. is placed on the surface of the resin layer 1a to start measurement.

  In the battery packaging material of the present invention, from the viewpoint of further enhancing the insulation and durability, the setting value of the deflection of the probe at the start of the measurement is -4 V, and the condition that the temperature rise rate is 5 ° C / min. When the probe is heated from 40 ° C. to 220 ° C., the position of the probe placed on the surface of the resin layer 1 a does not fall below the initial value (the position when the temperature of the probe is 40 ° C.). When heated from 200 ° C. to 200 ° C., it is more preferable that the position of the probe placed on the surface of the resin layer 1 a does not decrease. The step of sealing the battery element by heat sealing the heat sealable resin layers of the battery packaging material is usually performed by heating to about 160 ° C. to 200 ° C. For this reason, when the probe is heated from 160 ° C. to 200 ° C., the battery packaging material in which the position of the probe placed on the surface of the resin layer 1a does not decrease can exhibit particularly high heat resistance. From the viewpoint of further improving the heat resistance, when the probe is heated from 40 ° C. to 250 ° C., the position of the probe placed on the surface of the resin layer 1 a does not lower than the initial value, and further heated to 160 ° C. to 200 ° C. It is further preferable that the position of the probe placed on the surface of the resin layer 1a does not decrease when the process is performed.

  The thickness of the resin layer 1a is not particularly limited, but it is preferably about 2 to 50 μm, more preferably about 2 to 20 μm, from the viewpoint of suppressing deterioration of the surface characteristics of the base material 2 side of the battery packaging material. More preferably, about 2 to 10 μm can be mentioned.

  From the same viewpoint, the thickness of the bonding layer 1 b is preferably about 0.2 to 10 μm, more preferably about 0.2 to 5 μm, and still more preferably about 0.2 to 3 μm. From the same viewpoint, the total thickness of the resin layer 1a and the bonding layer 1b is preferably about 2 to 50 μm, more preferably about 2 to 20 μm, and still more preferably about 2 to 10 μm.

A lubricant may be present on the surface of the resin layer 1a. The presence of the lubricant on the surface of the resin layer 1a can enhance the formability of the battery packaging material. It does not restrict | limit especially as a kind of lubricant, For example, the same thing as the lubricant illustrated by the below-mentioned heat-fusible resin layer is mentioned. Preferred lubricants are erucic acid amide, palmitic acid amide, stearic acid amide and oleic acid amide, and a more preferred lubricant is erucic acid amide. The amount of the lubricant present on the surface of the resin layer 1a is preferably about ² to ²⁰ g / m ² , more preferably about 3 to 17 g / m ² , and still more preferably about 3 to 8 g / m ² . The lubricant present on the surface of the resin layer 1a may be exuded from the inside of the resin layer 1a or may be coated on the surface of the resin layer 1a. The amount of lubricant present on the surface of the resin layer 1a can be confirmed by the following measurement method.

(Measurement of lubricant amount)
The battery packaging material is cut into A4 size (ISO 216) to prepare a sample. Next, the resin layer surface of each sample is washed with acetone, and the recovered acetone is volatilized and dried by nitrogen blow to obtain a solid. Next, 10 ml of chloroform is added to the solid, the solid is redissolved, and a gas chromatograph (GC, for example, GC-2010 manufactured by Shimadzu Corporation, column: UltraALLOY-1 (MS / HT), detector: FID, Quantitative method: The amount of lubricant on the surface of the resin layer is measured using an absolute calibration method.

[Base layer 2]
In the battery packaging material of the present invention, after peeling off the resin layer 1a, the base material layer 2 becomes a layer positioned on the outermost layer side. When no other layer (for example, a surface coating layer described later) is provided between the resin layer 1a and the base layer 2, the base layer 2 is a layer adjacent to the bonding layer 1b.

  The material for forming the base layer 2 is not particularly limited as long as it has insulating properties. Examples of materials for forming the base material layer 2 include resin films such as polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicone resin, phenol resin, and mixtures or copolymers thereof. It can be mentioned. Among these, a polyester resin and a polyamide resin are preferably mentioned, and a biaxially stretched polyester resin and a biaxially stretched polyamide resin are more preferably mentioned. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester, and polycarbonate. Specific examples of the polyamide resin include nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 6, 10, polymethaxylylene adipamide (MXD6) and the like. The polyamide resin may be composed of only one type, or may be composed of two or more types. The polyamide resin may include, for example, nylon 6 and polymetaxylylene adipamide (MXD6).

  The base material layer 2 may be formed of a resin film of one layer, but may be formed of a resin film of two or more layers in order to improve pinhole resistance and insulation. Specifically, a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, and a multilayer structure in which a plurality of polyester films are laminated are exemplified. When the substrate layer 2 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films laminated, and a laminate of a plurality of biaxially stretched polyester films laminated Body is preferred. For example, when forming the base material layer 2 from a resin film of two layers, it is made the composition which laminates polyester resin and polyester resin, the composition which laminates polyamide resin and polyamide resin, or the composition which laminates polyester resin and polyamide resin. It is more preferable to use a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated. In the case where the base material layer 2 has a multilayer structure, the thickness of each layer is preferably about 2 to 25 μm.

  When the base material layer 2 is formed of a multilayer resin film, two or more resin films may be laminated via an adhesive or an adhesive component such as adhesive resin, and the type and amount of adhesive component used, etc. Is similar to that of the adhesive layer 5 described later. In addition, it does not restrict | limit especially as a method to laminate the resin film of two or more layers, A well-known method can be adopted, for example, a dry laminating method, a sandwich laminating method, etc. are mentioned, Preferably a dry laminating method is mentioned. When laminating by the dry lamination method, it is preferable to use a urethane type adhesive as an adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 2 to 5 μm.

  The thickness of the base material layer 2 is not particularly limited as long as it exhibits the function as a base material layer, and for example, about 3 to 50 μm, preferably about 10 to 35 μm.

[Adhesive layer 5]
In the battery packaging material 10 of the present invention, the adhesive layer 5 is a layer provided between the substrate layer 2 and the barrier layer 3 as needed in order to firmly bond the substrate layer 2 and the barrier layer 3.

  The adhesive layer 5 is formed of an adhesive capable of adhering the base layer 2 and the barrier layer 3. The adhesive used to form the adhesive layer 5 may be a two-part curable adhesive or a one-part curable adhesive. Furthermore, the adhesion mechanism of the adhesive used to form the adhesive layer 5 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, and the like.

  Specific examples of the adhesive component that can be used to form the adhesive layer 5 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyesters; Polyether-based adhesives; Polyurethane-based adhesives; Epoxy-based resins; Phenolic resin-based resins; Polyamide-based resins such as nylon 6, nylon 66, nylon 12, copolymerized polyamides; Polyolefins, carboxylic acid-modified polyolefins, metal-modified polyolefins, etc. Polyolefin resins, polyvinyl acetate resins; cellulose adhesives; (meth) acrylic resins; polyimide resins; amino resins such as urea resins and melamine resins; chloroprene rubber, nitrile rubber , Styrene - rubber such as butadiene rubber; and silicone resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane adhesive is preferably mentioned.

  The thickness of the adhesive layer 5 is not particularly limited as long as it exhibits the function as an adhesive layer, and for example, about 1 to 10 μm, preferably about 2 to 5 μm.

  An ultraviolet absorber in a layer outside the barrier layer 3 of the battery packaging material of the present invention (preferably, at least one of the resin layer 1a, the bonding layer 1b, the base material layer 2, and the adhesive layer 5); It is preferable to contain at least one component of a light stabilizer and an antioxidant. By containing one of these components, delamination between layers is effectively suppressed on the outside of the barrier layer 3.

  In the present invention, the delamination of the layer outside the barrier layer 3 of the battery packaging material mainly means the peeling between these layers.

  The inclusion of these components in the layer outside the barrier layer 3 of the battery packaging material of the present invention can be analyzed, for example, using a gas chromatograph mass spectrometer (GC / MS). When the amount is small and not detected by GC / MS, it can be analyzed by, for example, liquid chromatography (HPLC). Pre-processing is performed as follows.

  The base layer (the resin layer and the bonding layer are laminated) and the barrier layer are physically separated without using a solvent. Next, in order to enhance the extraction efficiency of the additive component in each layer, the laminate of the resin layer, the bonding layer, and the base layer is wound and extracted together with a stainless steel mesh so that the adhesion between the layers is reduced. . Next, Soxhlet extraction is performed for 10 hours using chloroform as an extraction solvent to extract additive components. After distilling off the solvent, it is dissolved in a measuring solvent and subjected to analysis.

  UV absorber contained in a layer outside barrier layer 3 of the battery packaging material of the present invention (preferably, at least one of resin layer 1a, bonding layer 1b, base layer 2, and adhesive layer 5) The total content of these is preferably 10 to 500 ppm, more preferably about 30 to 100 ppm, and particularly preferably about 40 to 80 ppm, from the viewpoint of adhesion stability between layers. The total content of the light stabilizer is preferably 10 to 500 ppm, more preferably about 100 to 200 ppm, and particularly preferably 120 to 180 ppm, from the viewpoint of adhesion stability between layers. The total content of the antioxidant is preferably 10 to 1000 ppm, more preferably about 200 to 800 ppm, particularly preferably about 420 to 600 ppm, from the viewpoint of adhesion stability between layers.

  The type of UV absorber is not particularly limited, but preferably includes benzotriazole-based UV absorbers. Specific examples of UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone) And the like) 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5) -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary ester Ethyl 6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-) Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Liazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl)- , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5- 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-primary Tributyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl) Tributyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl) Benzoates such as 4--4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxy Substituted oxanilides such as zanilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Or metal chelates, particularly salts of nickel, chromium, or chelates. Commercially available UV absorbers include TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, TINUVIN326 and the like manufactured by BASF, and among these, TINUVIN 326 (2- [5-chloro (2H) -benzotriazole-, among these, is particularly preferred. 2-yl] -4-methyl-6- (tert-butyl) phenol) is effective.

  The UV absorbers may be used alone or in combination of two or more.

  The type of light stabilizer is not particularly limited, but preferably includes hindered amine light stabilizers. Specific examples of the light stabilizer include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,3, 6,6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 2,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,2,7 6,6-Tetramethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di (di) Tributyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate 1,6-bis (2 2,2,6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl) -4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N-) (2,2,6,6-tetra Tyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-) N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis {4- (1 -Octyloxy-2,2,6,6-tetramethyl) piperi Jyl} decantionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate and the like can be mentioned. Among these, a compound which is linked to the 1-position of piperidine is N-oxyalkyl or N-methyl is preferable. Commercially available light stabilizers include TINUVIN 765, TINUVIN 770, TINUVIN 780, TINUVIN 144 and TINUVIN 622LD manufactured by BASF, in particular TINUVIN 770 (bis (2,2,6,6-tetramethyl-4-piperidyl sebacate) ) Is valid.

  A light stabilizer may be used individually by 1 type, and may be used combining 2 or more types.

  Further, the type of the antioxidant is not particularly limited, but preferably a hindered phenolic antioxidant is mentioned. Specific examples of the antioxidant include Irganox 1330 (2,4,6-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) mesitylene), Irganox 1098 (N, N′-hexamethylene bis) [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], Irganox 1010 (tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propione Acid] pentaerythritol). When Irganox 1330 is contained as an antioxidant, it is a layer (preferably, the resin layer 1a, the bonding layer 1b, and the base material) outside the barrier layer 3 of the battery packaging material of the present invention from the viewpoint of adhesion stability between layers. The total content of Irganox 1330 contained in at least one layer of layer 2 and adhesive layer 5 is preferably about 10 to 500 ppm, more preferably about 90 to 200 ppm, and particularly preferably about 110 to 170 ppm. .

  The antioxidant may be used alone or in combination of two or more.

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function to prevent water vapor, oxygen, light and the like from invading the inside of the battery, in addition to the strength improvement of the battery packaging material. The barrier layer 3 is preferably a metal layer, that is, a layer formed of a metal. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium etc. are mentioned, Preferably aluminum is mentioned. The barrier layer 3 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is more preferable to form by aluminum alloy foil. From the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021 H-O, JIS H4160: It is more preferable to form by soft aluminum alloy foil, such as 1994 A8079 H-O, JIS H4000: 2014 A8021 P-O, JIS H 4000: 2014 A8079 P-O).

  The thickness of the barrier layer 3 is not particularly limited as long as it exhibits a function as a barrier layer such as water vapor, but from the viewpoint of reducing the thickness of the battery packaging material, it is preferably about 100 μm or less, more preferably about 10 to 100 μm. More preferably, about 10-80 micrometers is mentioned.

  In addition, it is preferable that at least one surface, preferably both surfaces, of the barrier layer 3 be subjected to chemical conversion treatment in order to stabilize adhesion, to prevent dissolution or corrosion, and the like. Here, the chemical conversion treatment means a treatment for forming an acid resistant film on the surface of the barrier layer. As the chemical conversion treatment, for example, chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium borate, chromium biphosphate, chromium acetate, acetyl acetate, chromium chloride, potassium chromium sulfate, etc .; Phosphoric acid treatment using phosphoric acid compounds such as sodium acid, potassium phosphate, ammonium phosphate, polyphosphoric acid and the like; using an aminated phenol polymer having repeating units represented by the following general formulas (1) to (4) And chromate treatment. In the aminated phenol polymer, repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. It is also good.

In the general formulas (1) to (4), X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. Further, R ¹ and R ² are the same or different and each represents a hydroxy group, an alkyl group or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Also, examples of the hydroxyalkyl group represented by X, R ¹ and R ² include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3- C1-C4 linear or branched with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group etc. An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and the hydroxyalkyl group represented by X, R ¹ and R ² may be identical to or different from each other. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and about 1 to 20,000. More preferable.

  In addition, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a coating in which fine particles of aluminum oxide, titanium oxide, cerium oxide, metal oxide such as tin oxide, or barium sulfate are dispersed in phosphoric acid is coated; A method of forming an acid resistant film on the surface of the barrier layer 3 can be mentioned by carrying out the baking treatment at 150 ° C. or higher. In addition, on the acid resistant film, a resin layer may be further formed by crosslinking the cationic polymer with a crosslinking agent. Here, as the cationic polymer, for example, polyethylene imine, an ionic polymer complex composed of polyethylene imine and a polymer having a carboxylic acid, primary amine graft acrylic resin obtained by graft polymerizing a primary amine on an acrylic main skeleton, polyallylamine Or derivatives thereof, aminophenol and the like. As these cationic polymers, only 1 type may be used and you may use combining 2 or more types. Moreover, as a crosslinking agent, the compound which has an at least 1 sort (s) of functional group chosen from the group which consists of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent etc. are mentioned, for example. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

  Moreover, as a method of specifically providing an acid resistant coating, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method as one example. Degreasing treatment by a known treatment method such as acid activation method, and then the degreasing surface is treated with metal phosphate such as chromium phosphate, titanium phosphate, zirconium phosphate, zinc phosphate and the like Treatment solution (aqueous solution) mainly composed of a mixture of metal salts, or treatment solution (aqueous solution) mainly composed of a mixture of nonmetal phosphate and nonmetal salts thereof, or acrylic resin with these Or applying a treatment solution (aqueous solution) composed of a mixture with a phenolic resin or an aqueous synthetic resin such as a urethane resin by a known coating method such as a roll coating method, a gravure printing method, or an immersion method. Ri, it is possible to form the acid-resistant coating. For example, when treated with a chromium phosphate salt treatment liquid, it becomes an acid-resistant film composed of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and is treated with a zinc phosphate salt treatment liquid In the case of an acid resistant coating, the coating is made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride and the like.

  Moreover, as another example of the specific method of providing an acid resistant film, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid resistant film can be formed by degreasing treatment by a known treatment method such as activation method and then applying known anodic oxidation treatment to the degreasing treatment surface.

  Moreover, phosphate-based and chromic acid-based films are mentioned as another example of the acid resistant film. Examples of phosphates include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate and chromium phosphate. Examples of chromic acid include chromium chromate.

  Moreover, as another example of the acid resistant coating, by forming an acid resistant coating such as phosphate, chromate, fluoride, triazine thiol compound, etc., between the aluminum and the substrate layer at the time of embossing and forming Anti-delamination, hydrogen fluoride generated by the reaction between electrolyte and water prevents dissolution and corrosion of the aluminum surface, especially dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface The properties (wettability) are improved, and the effect of preventing the delamination of the base layer and aluminum during heat sealing and the prevention of the delamination of the base layer and aluminum during press molding are shown in the embossed type. Among the substances forming the acid resistant film, an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the treatment of dry baking is good.

  The acid resistant film further comprises a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, wherein the phosphoric acid or phosphate is any of the above-mentioned. About 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.

  Furthermore, it is preferable that the said anionic polymer is a copolymer which has poly (meth) acrylic acid or its salt, or (meth) acrylic acid or its salt as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which consists of a compound which has a functional group in any one of an isocyanate group, glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

  Moreover, it is preferable that the said phosphoric acid or the said phosphate is condensed phosphoric acid or condensed phosphate.

  For the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatments may be performed in combination. Furthermore, these chemical conversion treatments may be performed using one type of compound alone, or may be performed using two or more types of compounds in combination. Among the chemical conversion treatments, a chromate chromate treatment, a chemical conversion treatment in which a chromium compound, a phosphoric acid compound, and an aminated phenol polymer are combined, and the like are preferable. Among the chromium compounds, chromic acid compounds are preferred.

  Specific examples of the acid resistant coating include those containing at least one of phosphate, chromate, fluoride, and triazine thiol. In addition, an acid resistant film containing a cerium compound is also preferable. As a cerium compound, cerium oxide is preferable.

  Moreover, as a specific example of an acid resistant film, a phosphate type film, a chromate type film, a fluoride type film, a triazine thiol compound film, etc. are mentioned. The acid resistant coating may be one of these or a combination of two or more. Furthermore, as an acid resistant coating, after degreasing the surface of the aluminum alloy foil on the chemical conversion treatment, a treatment liquid comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a nonmetallic phosphate and an aqueous synthetic resin It may be formed of a treatment liquid comprising

The analysis of the composition of the acid-resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry. Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry detects, for example, a peak derived from at least one of Ce ⁺ and Cr ⁺ .

  It is preferable that the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium. In addition, it is confirmed using X-ray photoelectron spectroscopy that at least one element selected from the group consisting of phosphorus, chromium and cerium is contained in the acid resistant coating on the surface of the aluminum alloy foil of the packaging material for batteries. can do. Specifically, first, in the battery packaging material, the heat fusible resin layer, the adhesive layer and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is placed in an electric furnace, and the organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Thereafter, X-ray photoelectron spectroscopy of the surface of the aluminum alloy foil is used to confirm that these elements are contained.

The amount of acid-resistant coatings to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, for example, in the case of performing the above-mentioned chromate treatment, the surface 1 m ² per barrier layer 3, the chromium compound is chromium About 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of conversion, about 0.5 to 50 mg, preferably about 1.0 to 40 mg, of the phosphorus compound in terms of phosphorus, and 1.0 of the aminated phenolic polymer It is desirable that it is contained at a rate of about 200 mg, preferably about 5.0 to 150 mg.

  The thickness of the acid-resistant coating is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably 1 to 100 nm, from the viewpoint of the cohesion of the coating and the adhesion to the aluminum alloy foil and the heat sealable resin layer. The degree is more preferably about 1 to 50 nm. The thickness of the acid resistant coating can be measured by a transmission electron microscope or a combination of an observation by a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.

  In the chemical conversion treatment, the temperature of the barrier layer is 70 after the solution containing the compound used for forming the acid resistant coating is applied to the surface of the barrier layer by the bar coating method, roll coating method, gravure coating method, immersion method or the like. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer, the barrier layer may be subjected in advance to a degreasing treatment by an alkaline immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like. By performing the degreasing treatment in this manner, the chemical conversion treatment on the surface of the barrier layer can be performed more efficiently.

[Heat-fusible resin layer 4]
In the battery packaging material of the present invention, the thermally fusible resin layer 4 corresponds to the innermost layer, and is a layer that thermally fuses the thermally fusible resin layers when the battery is assembled to seal the battery element.

The resin component used for the heat fusible resin layer 4 is not particularly limited as long as heat fusible is possible, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the heat-fusible resin layer 4 may contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The thermally fusible resin layer 4 may contain a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography mass spectrometry, etc., and there is no particular limitation on the analysis method. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (e.g., random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene and the like. . Moreover, as a cyclic monomer which is a constituent monomer of the cyclic polyolefin, for example, cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like can be mentioned. Among these polyolefins, preferred are cyclic alkenes, more preferably norbornene.

  The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as a carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof.

  The acid-modified cyclic polyolefin is prepared by copolymerizing part of the monomers constituting the cyclic polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof, or α, β- to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be carboxylic acid modified is the same as described above. Moreover, as a carboxylic acid used for modification | denaturation, it is the same as that of the acid component used for modification | denaturation of the said polyolefin.

  Among these resin components, preferred are polyolefins such as polypropylene, carboxylic acid-modified polyolefins, and more preferably polypropylene and acid-modified polypropylenes.

  The heat fusible resin layer 4 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types of resin components are combined. Furthermore, although the heat fusible resin layer 4 may be formed of only one layer, it may be formed of two or more layers of the same or different resin components.

  In the present invention, from the viewpoint of enhancing the moldability of the battery packaging material, it is preferable that a lubricant adheres to the surface of the heat-fusible resin layer. The lubricant is not particularly limited, but preferably includes amide lubricants. Specific examples of the amide lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl erucic acid amide. In addition, specific examples of methylolamide include methylol stearic acid amide and the like. Specific examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylene bisstearin An acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl sebacic acid amide etc. are mentioned. Specific examples of the unsaturated fatty acid bisamide include ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide Etc. Specific examples of fatty acid ester amides include stearoamidoethyl stearate and the like. Moreover, m-xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, N, N'-distearyl isophthalic acid amide etc. are mentioned as a specific example of aromatic-type bisamide. The lubricant may be used alone or in combination of two or more.

When a lubricant is present on the surface of the heat-fusible resin layer 4, the amount thereof is not particularly limited, but it is preferably about 3 mg / m ² or more, more preferably in an environment of 24 ° C. and 60% relative humidity. Is about 4 to 15 mg / m ² , and more preferably about 5 to 14 mg / m ² .

  The heat fusible resin layer 4 may contain a lubricant. Also, the lubricant present on the surface of the heat-fusible resin layer 4 may be one in which the lubricant contained in the resin constituting the heat-fusible resin layer 4 is exuded, or the heat-fusible resin layer The surface of 4 may be coated with a lubricant.

  The thickness of the heat fusible resin layer 4 can be set according to the presence or absence of the adhesive layer 5, the thickness of the adhesive layer 5, and the like, and in particular, if the function as the heat fusible resin layer is exhibited. The upper limit is, for example, about 100 μm or less, preferably about 85 μm or less, more preferably 60 μm or less, and the lower limit is, for example, about 15 μm or more, preferably 20 μm or more. About 15 to 100 μm, about 15 to 85 μm, about 15 to 60 μm, about 20 to 100 μm, about 20 to 85 μm, about 20 to 60 μm, and about 15 to 40 μm. In particular, for example, when the thickness of the adhesive layer 5 described later is 10 μm or more, the upper limit of the thickness of the heat-fusible resin layer 4 is preferably about 85 μm or less, more preferably about 60 μm or less The lower limit is, for example, about 15 μm or more, preferably 20 μm or more, and a preferable range is about 15 to 85 μm, about 15 to 60 μm, about 20 to 85 μm, or about 20 to 60 μm. Further, for example, when the thickness of the adhesive layer 5 described later is less than 10 μm, or when the adhesive layer 5 is not provided, the thickness of the heat-fusible resin layer 4 is preferably about 20 μm or more, more preferably There are about 35 to 85 μm.

[Adhesive layer 6]
In the battery packaging material of the present invention, the adhesive layer 6 is a layer which is optionally provided between the barrier layer 3 and the thermally fusible resin layer 4 in order to firmly bond the barrier layer 3 and the thermally fusible resin layer 4.

The adhesive layer 6 is formed of a resin capable of adhering the barrier layer 3 and the heat fusible resin layer 4. As the resin used to form the adhesive layer 6, the adhesive mechanism, the type of the adhesive component, etc. may be the same as the adhesive exemplified for the adhesive layer 5. Moreover, as resin used for formation of the contact bonding layer 6, polyolefin resin, such as polyolefin illustrated above-mentioned heat-fusion resin layer 4, cyclic polyolefin, carboxylic acid modified polyolefin, carboxylic acid modified cyclic polyolefin, can also be used . As the polyolefin, a carboxylic acid-modified polyolefin is preferable, and a carboxylic acid-modified polypropylene is particularly preferable, from the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4. That is, the adhesive layer 6 may contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The adhesive layer 6 may contain a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

  Furthermore, from the viewpoint of making the battery packaging material excellent in shape stability after molding while thinning the thickness of the battery packaging material, the adhesive layer 6 is a resin composition containing an acid-modified polyolefin and a curing agent. It may be a thing. As the acid-modified polyolefin, preferably, the same ones as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat fusible resin layer 4 can be exemplified.

  The curing agent is not particularly limited as long as it cures acid-modified polyolefin. Examples of the curing agent include epoxy-based curing agents, polyfunctional isocyanate-based curing agents, carbodiimide-based curing agents, oxazoline-based curing agents, and the like.

  The epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group. Examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like.

  The polyfunctional isocyanate-based curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or denating these, or the like Mixtures and copolymers with other polymers may be mentioned.

  The carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N = C = N-). As a carbodiimide type | system | group hardening | curing agent, the polycarbodiimide compound which has a carbodiimide group 2 or more at least is preferable.

  The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline curing agent include Epocross series manufactured by Nippon Shokubai Co., Ltd.

  From the viewpoint of, for example, enhancing the adhesion between the barrier layer 3 and the thermally fusible resin layer 4 by the adhesive layer 6, the curing agent may be composed of two or more types of compounds.

  The content of the curing agent in the resin composition forming the adhesive layer 6 is preferably in the range of about 0.1 to 50% by mass, and more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.

  The thickness of the adhesive layer 6 is not particularly limited as long as it exhibits the function as an adhesive layer, but if the adhesive exemplified in the adhesive layer 5 is used, it is preferably about 1 to 10 μm, more preferably 1 to There is about 5 μm. Further, in the case of using the resin exemplified for the heat fusible resin layer 4, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. In the case of a cured product of an acid-modified polyolefin and a curing agent, it is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. When the adhesive layer 6 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 6 can be formed by applying the resin composition and curing it by heating or the like.

[Surface coating layer]
In the battery packaging material of the present invention, a surface coating layer is provided on the outer side of the base material layer 2 (the side opposite to the barrier layer 3 of the base material layer 2), as necessary, for the purpose of improving design. You may provide. When the surface coating layer is provided, the surface coating layer is located between the bonding layer 1 b and the substrate layer 2.

  The surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin or the like. Among these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface covering layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, an additive may be blended in the surface coating layer.

  Examples of the additive include fine particles having a particle diameter of about 0.5 nm to 5 μm. The material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. Further, the shape of the additive is not particularly limited, and examples thereof include spheres, fibers, plates, indeterminate shapes, and balloons. As an additive, specifically, talc, silica, graphite, kaolin, montmorrroid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate and titanium oxide are preferably mentioned from the viewpoint of dispersion stability and cost. In addition, the surface may be subjected to various surface treatments such as insulation treatment, high dispersion treatment, and the like.

  The content of the additive in the surface coating layer is not particularly limited, but preferably about 0.05 to 1.0% by mass, more preferably about 0.1 to 0.5% by mass.

  Although it does not restrict | limit especially as a method to form a surface coating layer, For example, the method of apply | coating to the surface of the outer side of the base material layer 2 2 liquid curable resin which forms a surface coating layer is mentioned. In the case of blending the additive, the additive may be added to and mixed with the two-component curable resin and then applied.

  The thickness of the surface coating layer is not particularly limited as long as the above-described function as the surface coating layer is exhibited, and for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. Method for Producing Battery Packaging Material The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate obtained by laminating each layer of a predetermined composition is obtained, and at least resin layer 1a and bonding layer 1b, a base layer 2, a barrier layer 3, and a heat-fusible resin layer 4 are laminated in this order, the bonding layer 1b contains a polyester resin, and the resin layer 1a is an aqueous liquid The method of using what can peel from the base material layer 2 is mentioned.

  As an example of the manufacturing method of the packaging material for batteries of this invention, it is as follows. First, a laminate (hereinafter sometimes referred to as “laminate A”) in which the resin layer 1a, the bonding layer 1b, the base material layer 2, the adhesive layer 5, and the barrier layer 3 are sequentially stacked is formed. Specifically, in order to form the laminate A, first, the resin layer 1a, the bonding layer 1b, and the base material layer 2 are laminated by a method such as a co-extrusion lamination method. At this time, as described above, for example, the resin layer 1a and the base layer 2 are adhered to each other through the above-described bonding layer 1b, with the laminated structure of the resin layer 1a and the bonding layer 1b. A laminate of the bonding layer 1 b and the base material layer 2 can be formed. Alternatively, the adhesive surface side of the bonding layer 1b laminated on the film-like resin layer 1a and the film-like base layer 2 may be pressure-bonded to obtain a laminate.

  Next, the laminate of the resin layer 1 a, the bonding layer 1 b, and the base material layer 2 and the barrier layer 3 are laminated. In this lamination, for example, an adhesive used for forming the adhesive layer 5 is applied to the base material layer 2 or the barrier layer 3 whose surface has been subjected to a chemical conversion treatment as required, such as gravure coating or roll coating. It can carry out by the dry lamination method of laminating | stacking the said barrier layer 3 or the base material layer 2, and hardening the adhesive layer 5 after apply | coating and drying by a method. By the steps described above, a laminate A in which the resin layer 1a, the bonding layer 1b, the base material layer 2, the adhesive layer 5, and the barrier layer 3 are sequentially stacked is obtained.

  Next, the heat fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A. In the case where the heat fusible resin layer 4 is directly laminated on the barrier layer 3, the resin component constituting the heat fusible resin layer 4 is gravure-coated or roll-coated on the barrier layer 3 of the laminate A It may be applied by a method such as When the adhesive layer 6 is provided between the barrier layer 3 and the heat fusible resin layer 4, for example, (1) the adhesive layer 6 and the heat fusible resin layer on the barrier layer 3 of the laminate A Method of laminating 4 by coextrusion (co-extrusion laminating method), (2) Separately, a laminated body in which the adhesive layer 6 and the heat-fusible resin layer 4 are laminated is formed, and this is used as a barrier layer of the laminated body A (3) Method of laminating by thermal laminating method, (3) Method of extruding or solution coating an adhesive for forming the adhesive layer 6 on the barrier layer 3 of the laminate A, drying at a high temperature, and baking. Method of laminating the thermally adhesive resin layer 4 which is formed into a sheet (film) in advance on the adhesive layer 6 by the thermal laminating method, (4) the barrier layer 3 of the laminated body A, and the sheet beforehand Solution between the heat sealable resin layer 4 and the While pouring an adhesive layer 6 which is, and a method of bonding a laminate A and the heat-welding resin layer 4 through the adhesive layer 6 (sandwich lamination method).

  The order in which the resin layer 1a and the bonding layer 1b are stacked is not particularly limited. For example, after the base layer 2 and the barrier layer 3 are stacked, the bonding layer 1b and the resin are formed on the surface on the base layer 2 side. The layer 1a may be stacked. In addition, after laminating the heat sealable resin layer 4 and the like, finally, the bonding layer 1b and the resin layer 1a may be laminated on the base material layer 2 side to obtain a battery packaging material.

  In the case of providing the surface covering layer, for example, after laminating the surface covering layer on the surface of the base material layer 2 opposite to the barrier layer 3, the bonding layer 1b and the resin layer 1a are formed on the surface covering layer. Stack. The surface coating layer can be formed, for example, by applying the above-mentioned resin forming the surface coating layer to the surface of the base material layer 2. The order of the step of laminating the barrier layer 3 on the surface of the base layer 2 and the step of laminating the surface coating layer on the surface of the base layer 2 is not particularly limited. For example, after forming a surface coating layer on the surface of the base layer 2, the barrier layer 3 may be formed on the surface of the base layer 2 opposite to the surface coating layer.

  As described above, resin layer 1a / bonding layer 1b / surface coating layer provided as needed / base material layer 2 / adhesive layer 5 provided as needed / one or both surfaces as needed A laminate is formed of the chemical conversion-treated barrier layer 3 / the adhesive layer 6 / the heat-fusible resin layer 4 provided as needed. In order to strengthen the adhesion of the adhesive layer 5 and the adhesive layer 6 provided as needed, it may be further subjected to heat treatment such as hot roll contact, hot air, near infrared or far infrared . As conditions of such heat processing, 1 to 5 minutes are mentioned, for example at 150-250 degreeC.

  In the battery packaging material of the present invention, each layer constituting the laminate improves or stabilizes film forming ability, lamination processing, final product secondary processing (pouching, embossing) suitability, etc., as necessary. For this purpose, surface activation treatments such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed. For example, by subjecting at least one surface of the base material layer to corona treatment, film forming property, lamination processing, final product secondary processing suitability and the like can be improved or stabilized.

  Further, in the present invention, the resin layer is prepared by preparing the above-mentioned battery packaging material including the resin layer 1a and the bonding layer 1b, and using an aqueous liquid to separate the resin layer 1a from the laminate. The battery packaging material from which 1a was exfoliated can be manufactured. About the method of peeling the resin layer 1a from a laminated body, an aqueous liquid should just be made to adhere to the joining layer 1b as mentioned above.

  Furthermore, in the method for producing a packaging material for a battery according to the present invention, after the peeling step, a printing process is performed in which printing with ink is performed on the surface on the base layer 2 side of the laminate constituting the packaging material for a battery. You may provide further. Thereby, the packaging material for batteries by which printing was given to the surface by the side of substrate layer 2 can be manufactured suitably. That is, the battery packaging material of the present invention can be suitably used in applications where the resin layer 1a is peeled off using an aqueous liquid, and printing with ink is performed on the surface on the substrate layer 2 side.

  In addition, you may perform the peeling process of the resin layer 1a from the packaging material for batteries, and a printing process as mentioned later in the manufacturing process of the battery using the packaging material for batteries. By subjecting the packaging material for a battery of the present invention including the resin layer 1a and the bonding layer 1b to molding with a die, the moldability improving effect by the resin layer 1a and the bonding layer 1b can be obtained by performing the peeling step and the printing step. It can be enjoyed suitably. For example, printing may be performed on the outside of the battery from the viewpoint of the battery identification and the like. In the battery packaging material of the present invention, when the printing is performed, the characteristic deterioration of the surface of the battery packaging material on the side of the base material layer 2 is effectively suppressed, and the aqueous liquid is used when the printing is performed. By peeling the resin layer 1a from the laminate, the surface on the base material layer 2 side of the battery packaging material to be the printing surface can be easily exposed, and the ink is applied to the surface of the base material layer 2 and the surface coating layer. The present invention can also be suitably applied to applications in which printing according to In addition, the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b is subjected to molding using a mold, and then the resin layer 1a is a barrier by peeling the resin layer 1a from the laminate using an aqueous liquid. The effect of suppressing the pinholes in the layer 3 and the effect of suppressing damage to the surfaces of the base layer 2 and the surface coating layer by the mold can be obtained, and the effect of improving formability can be suitably obtained. Further, when the heat-fusible resin layer 4 is heat-fused using the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b, deterioration of the base layer 2 and the surface coating layer due to high temperature and high pressure Can be effectively suppressed by protection with the resin layer 1a. In addition, the timing and purpose which peel the resin layer 1a are not limited to these.

  The printing method using ink is not particularly limited, and, for example, pad printing, inkjet printing and the like are preferable. Pad printing is a printing method as follows. First, the ink is poured into the concave portion of the flat plate where the pattern to be printed is etched. Next, the silicon pad is pressed from above the recess to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to a print target to form a print on the print target. Such pad printing is easy to print on the surface of the formed battery packaging material because the ink is transferred to the printing object using an elastic silicon pad or the like, and the battery element is a battery packaging material. After sealing, it has the advantage of being able to print on the battery. Moreover, it has the same advantage also in inkjet printing.

4. Applications of Battery Packaging Material The battery packaging material of the present invention is used for a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the battery element provided with at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to make a battery.

  Specifically, a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is a battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward. The battery is covered by forming flanges (areas in which the heat fusible resin layers are in contact with each other) on the periphery of the element, and heat sealing the heat fusible resin layers of the flanges to seal them. A battery using a packaging material is provided. In addition, when accommodating a battery element using the battery packaging material of this invention, it is used so that the heat fusible resin part of the battery packaging material of this invention may become inside (surface which contacts a battery element). When the heat-fusible resin layer 4 is heat-sealed using the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b, the base layer 2 and the surface coating layer are deteriorated due to high temperature and high pressure. The protection by the resin layer 1a can be effectively suppressed. In the battery packaging material of the present invention, the resin layer 1a can be peeled off after the heat-fusible resin layer 4 is heat-fused.

  The package formed by the battery packaging material of the present invention can be formed by bending a sheet of battery packaging material and heat-sealing the edge of the heat fusible resin layer opposed thereto. It can also be formed by laminating two battery packaging materials so that the heat-sealable resin layers face each other and heat-sealing the edge. When two battery packaging materials are used, the battery packaging material of the present invention may be used on one side only, or the battery packaging material of the present invention may be used on both sides. Furthermore, depending on the desired timing to protect the surface on the base layer 2 side, the resin layer 1a may be peeled off first from one battery packaging material, or from the both battery packaging materials at the same timing. 1a may be peeled off.

  Furthermore, in the battery of the present invention, the resin layer 1a may be peeled off. Such a battery can be produced, for example, by the steps of containing a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the battery packaging material of the present invention; And peeling the layer 1a from the package. About the specific example of the method of peeling the resin layer 1a from a laminated body, it is the same as that of the above-mentioned method.

  Furthermore, in the method of manufacturing a battery of the present invention, after the peeling step, the method further includes a printing step of performing printing with ink on the surface on the substrate layer 2 side of the package constituting the battery packaging material It is also good. Thereby, the battery by which printing was given to the outer side of a battery can be manufactured suitably. In particular, by providing the printing step immediately after the peeling step in the battery manufacturing step, the outer surface (the resin layer 1a is peeled off by the resin layer 1a until just before the printing step in manufacturing the battery and the battery packaging material). It becomes possible to apply printing suitably to the battery by which characteristic degradation of the base layer 2 and the surface of a surface coating layer which becomes the outside surface of a battery is effectively suppressed.

  In the present invention, although the resin layer 1a is peelable, it may be used as it is as a battery in which the resin layer 1a is not peeled.

  When the resin layer 1a is peeled from the battery provided with the resin layer 1a and the bonding layer 1b, the resin layer 1a can be peeled at desired timing. Since the heat dissipation property is improved by peeling the resin layer 1a from the battery, when it is required to improve the heat dissipation property of the battery, the resin layer 1a is preferably peeled and used as a battery whose heat dissipation property is improved. Can. In addition, since the thickness of the battery can be reduced by peeling the resin layer 1a from the battery, when it is required to thin the battery, the battery is obtained by peeling the resin layer 1a to reduce the thickness. It can be used suitably. The timing and purpose of peeling the resin layer 1a from the battery are not limited to these. Moreover, about the method of peeling the resin layer 1a from a battery, an aqueous liquid should just be made to adhere to the joining layer 1b as mentioned above.

  The battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited. For example, lithium ion battery, lithium ion polymer battery, lead storage battery, nickel hydrogen storage battery, nickel cadmium storage battery, nickel Iron storage batteries, nickel-zinc storage batteries, silver oxide-zinc storage batteries, metal air batteries, multivalent cation batteries, capacitors, capacitors and the like can be mentioned. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are mentioned as a suitable application object of the packaging material for batteries of the present invention.

  Hereinafter, the present invention will be described in detail by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Manufacture of battery packaging materials>
Example 1
A polyethylene terephthalate film and a nylon film were laminated by coextrusion to prepare a biaxially stretched laminated film. In the laminated film, a junction formed of a polyester resin (poly (tetramethylene ether) glycol resin) is used between the biaxially stretched polyethylene terephthalate film (thickness 5 μm) and the biaxially stretched nylon film (thickness 20 μm) It is adhered by a layer (thickness 1 μm). The said laminated film is a laminated body on which the resin layer / joining layer / base material layer was laminated | stacked in order, and it is biaxially stretched after three-layer co-extrusion of resin layer / joining layer / base material layer. Further, in the laminated film, a UV absorber (TINUVIN 326), a light stabilizer (TINUVIN 770), and an antioxidant (Irganox 1330, Irganox 1098, Irganox 1010) are blended. Next, on the surface of the base material layer, an aluminum alloy foil (40 μm in thickness) as a barrier layer was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) is applied to one surface of an aluminum alloy foil having an acid resistant film formed on the surface, and the adhesive is applied to the surface of the aluminum alloy foil. A layer (3 μm thick) was formed. Next, the adhesive layer on the barrier layer and the base material layer are laminated by the dry lamination method, and then aging treatment is performed to sequentially laminate the resin layer / bonding layer / base material layer / adhesive layer / barrier layer. The resulting laminate was made. The aluminum foil used as the barrier layer is provided with an acid resistant film containing cerium oxide and a phosphate.

  Next, on the barrier layer of the obtained laminate (the surface of the acid resistant film), an adhesive (thickness after curing: 2 μm) consisting of a non-crystalline polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound Adhesive layer / heat fusible resin on the barrier layer by passing between the heat rolls and adhering the barrier layer side of the obtained laminate to the barrier layer side and the unstretched polypropylene film (80 μm in thickness). The layers were stacked. Next, by aging the obtained laminate, biaxially stretched polyethylene terephthalate film (5 μm) / bonding layer (1 μm) / biaxially stretched nylon film (20 μm) / adhesive layer (3 μm) / barrier layer (40 μm) ) / Adhesive layer (2 μm) / unstretched polypropylene film (80 μm) to obtain a battery packaging material laminated in this order. The layer configuration of the battery packaging material is shown in Table 1.

(Comparative example 1)
A two-component urethane adhesive (a polyethylene terephthalate film (12 μm in thickness) as a resin layer and a stretched nylon film (15 μm in thickness) as a substrate layer as a laminate of a resin layer, a bonding layer and a substrate layer What was adhere | attached by the polyol compound and the aromatic isocyanate type compound and 3 micrometers in thickness was prepared. Next, in the same manner as in Example 1, an aluminum alloy foil (40 μm in thickness) as a barrier layer is laminated on the surface of the base material layer by a dry lamination method, and resin layer / bonding layer / base material layer / adhesion A laminate in which the agent layer / barrier layer was laminated in order was produced. The acid resistant film formed on the surface of the aluminum alloy foil is roll coated with a treatment liquid comprising a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry mass). It is formed by applying and baking on both sides of the aluminum alloy foil by a method. Next, resin layer / junction layer / base material layer is formed by laminating acid-modified polypropylene (40 μm thick) as an adhesive layer and polypropylene (40 μm thick) as a heat fusible resin layer by a co-extrusion lamination method. A battery packaging material was obtained in which / adhesive layer / barrier layer / adhesive layer / heat sealable resin layer were sequentially laminated. The specific laminated constitution is shown in Table 1.

(Comparative example 2)
As a laminate of a resin layer, a bonding layer, and a substrate layer, a polyethylene terephthalate film (12 μm in thickness) as a resin layer and a stretched nylon film (15 μm in thickness) as a substrate layer have a two-component urethane adhesive What was adhered by (polyol compound and aromatic isocyanate compound, thickness 3 μm) was prepared. Next, in the same manner as in Example 1, an aluminum alloy foil (40 μm in thickness) as a barrier layer is laminated on the surface of the base material layer by a dry lamination method, and resin layer / bonding layer / base material layer / adhesion A laminate in which the agent layer / barrier layer was laminated in order was produced. The acid resistant film formed on the surface of the aluminum alloy foil is the same as in Comparative Example 1. Next, on the barrier layer of the obtained laminate (surface of the acid-resistant film), an adhesive (thickness after curing: 3 μm) consisting of non-crystalline polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound By applying and drying the barrier layer side of the obtained laminate and an unstretched random polypropylene film (80 μm in thickness) between the heat rolls and adhering, resin layer / bonding layer / base material layer / A battery packaging material was obtained in which the adhesive layer / barrier layer / adhesive layer / heat sealable resin layer were sequentially laminated. The specific laminated constitution is shown in Table 1.

(Comparative example 3)
An aluminum alloy foil (40 μm thick) as a barrier layer is laminated on the surface of a stretched nylon film (25 μm thick) as a base material layer by a dry lamination method, and base material layer / adhesive layer / barrier layer is in order A laminated laminate was produced. The acid resistant film formed on the surface of the aluminum alloy foil is the same as in Comparative Example 1. Next, in the same manner as Comparative Example 1, an acid-modified polypropylene (23 μm in thickness) as an adhesive layer and a polypropylene (23 μm in thickness) as a heat-fusible resin layer were laminated by a co-extrusion laminating method. Next, the bonding layer side of a resin layer formed by laminating a polyethylene terephthalate film (thickness 50 μm) as a resin layer and a bonding layer (thickness 1 μm) composed of a silicone resin (silicone elastomer), and the laminate prepared above The base material layer side of the body was laminated to obtain a battery packaging material in which a resin layer / bonding layer / base material layer / adhesive layer / barrier layer / adhesive layer / thermally fusible resin layer was sequentially laminated. The specific laminated constitution is shown in Table 1.

(Comparative example 4)
In Comparative Example 3, in the same manner as Comparative Example 3 except that the resin layer and the bonding layer were not laminated on the base material layer, the base material layer / adhesive layer / barrier layer / adhesive layer / thermally fusible resin The battery packaging material in which layers were laminated in order was obtained. The specific laminated constitution is shown in Table 1.

<Analysis of UV absorbers, light stabilizers and antioxidants>
Between the base material layer and the barrier layer of the packaging material for a battery of Example 1 was peeled about 10 g physically without using a solvent. Next, in order to enhance the extraction efficiency of the additive component in each layer, the laminate of the resin layer, the bonding layer, and the base layer is wound and extracted with a stainless steel mesh so that the adhesion between the layers is reduced. The Next, Soxhlet extraction is performed for 10 hours using chloroform as an extraction solvent to extract additive components. After the solvent was distilled off, it was dissolved in a measuring solvent and subjected to analysis. Irganox 1330, Irganox 1098, TINUVIN 326, TINUVIN 770 were detected by GC / MS. Irganox 1010 was detected by HPLC.

[Analysis by GC / MS (Gas Chromatograph Mass Spectrometry)]
(Device, measurement conditions)
Device: Gas chromatograph GC / MS-QP2010 Ultra manufactured by Shimadzu Corporation
Column: Frontier Lab UltraALLO ^{+ +} 1 (MS / HT), df = 0.15 μm, 0.25 mm I. D. × 15 m
Column temperature: 80 to 390 ° C 11 ° C / min hold
Carrier: He 1.1 mL / min
Injection method: Split method injection volume: 1 μL
Ionization method: EI method 70 eV
Sample preparation: Dissolve in 2 mL chloroform / methanol (1/1; v / v) mixed solvent

[Analysis by HPLC (liquid chromatograph)]
(Device, measurement conditions)
Device: HPLC Spec. PU-2085 manufactured by JASCO Corporation Column: Unison UK-C18 3 μm, 4.6 mm I. D. × 100 mm
Column temperature: 80 to 390 ° C 11 ° C / min hold
Carrier: He 1.1 mL / min
Injection method: split method 1:12
Injection volume: 1 μL
Determination method: Absolute calibration method Measurement sample: Dissolve in 2 mL chloroform / methanol (1/1; v / v) mixed solvent

<Measurement of Content of UV Absorbent, Light Stabilizer, and Antioxidant>
With respect to the battery packaging material of Example 1, the additive component is obtained from the laminate of the resin layer, the bonding layer, and the base material layer in the same manner as in the above-mentioned <Analysis of UV absorber, light stabilizer and antioxidant>. Were extracted, and a sample dissolved in the measurement solvent was prepared. The contents of the ultraviolet light absorber, the light stabilizer and the antioxidant were measured for the obtained sample by the following gas chromatograph (GC) and liquid chromatograph (HPLC). As a result, it was confirmed by HPLC that 370 ppm of Irganox 1098, 60 ppm of TINUVIN 326, 30 ppm of Irganox 1010, and 130 ppm of Irganox 1330 were contained. In addition, GC confirmed that 140 ppm of TINUVIN 770 was contained.

[Measurement of content by GC (gas chromatograph)]
(Device, measurement conditions)
Device: Gas chromatograph GC-2010 manufactured by Shimadzu Corporation
Column: MXT-1, manufactured by Shimadzu Corporation, df = 0.15 μm, 0.25 mm I. D. × 15 m
Column temperature: 80 to 390 ° C 11 ° C / min hold
Carrier: He 1.1 mL / min
Injection method: split method 1:12
Injection volume: 1 μL
Determination method: Absolute calibration method Measurement sample: Dissolve in 2 mL chloroform / methanol (1/1; v / v) mixed solvent

[Measurement of content by HPLC (liquid chromatograph)]
(Device, measurement conditions)
Device: HPLC Spec. PU-2085 manufactured by JASCO Corporation Column: Unison UK-C18 3 μm, 4.6 mm I. D. × 100 mm
Column temperature: 80 to 390 ° C 11 ° C / min hold
Carrier: He 1.1 mL / min
Injection method: split method 1:12
Injection volume: 1 μL
Determination method: Absolute calibration method Measurement sample: Dissolve in 2 mL chloroform / methanol (1/1; v / v) mixed solvent

<Measurement of Peeling Strength with Water Adhered>
About each battery packaging material obtained in Example 1 and Comparative Examples 1 to 3, the peel strength of the polyethylene terephthalate film in a state where water is attached to the surface of the polyethylene terephthalate film located on the outermost surface on the substrate layer side Was measured by the following measurement method. The battery packaging material was cut into a rectangular shape of 100 mm (MD) x 15 mm (TD) to prepare a test sample. First, 35% hydrochloric acid is attached to the end of the resin layer and the bonding layer of the test sample in an environment of temperature 25 ° C., relative humidity 50%, and atmospheric pressure (1 atm), as shown in the schematic view of FIG. The resin layer was peeled about 30 mm in the MD direction. The hydrochloric acid adhering to the test sample was wiped off and allowed to dry. Next, distilled water (W) was attached to the portion where the resin layer was peeled off (the bonding layer 1 b between the resin layer and the surface on the base material layer side) using a dropper. At this time, distilled water (W) was attached over the entire direction of TD at the boundary between the resin layer and the surface on the base layer side. Next, using a tensile tester (Autograph manufactured by Shimadzu Corporation), peel off the resin layer 1a from the surface of the base material layer under measurement conditions of 50 mm distance between chucks, 50 mm peeling speed, and 180 ° peeling angle. The peel strength when the distance between chucks reached 57 mm was taken as the peel strength (N / 15 mm) in the state where distilled water was attached. The results are shown in Table 1. The lower limit of the detection limit of the tensile tester used for measuring the peel strength is 0.3 N / 15 mm.

<Measurement of peeling strength in the state where water is not attached>
Peeling in a state where the above <water is attached except that distilled water is not attached using a dropper to the part where the resin layer is exfoliated (joining layer 1b between the resin layer and the surface on the substrate layer side) Measurement of Strength> The resin layer is peeled from the surface of the base material layer under the same measurement conditions as in the measurement> Peeling strength when the distance between chucks reaches 57 mm, peeling strength in the state where water is not attached (N / 15 mm) And The results are shown in Table 1.

<Evaluation of formability>
Each of the battery packaging materials obtained above was cut into strips of 150 mm (TD) x 100 mm (MD) to prepare test samples. The MD of the battery packaging material corresponds to the rolling direction of the aluminum alloy foil, and the TD of the battery packaging material corresponds to the TD of the aluminum alloy foil. The rolling direction of the aluminum alloy foil can be confirmed by the rolling marks of the aluminum alloy foil. The mold is a 30 mm (MD) × 50 mm (TD) rectangular male type (surface is specified in Table 2 of surface roughness standard piece for comparison in JIS B 0659-1: 2002 Annex 1 (reference) , Maximum height roughness (nominal value of Rz) is 1.6 μm), and female type with 0.5 mm clearance with this male type (surface is JIS B 0659-1: 2002 Annex 1 (reference) comparison A straight mold consisting of a maximum height roughness (nominal value of Rz) of 3.2 μm as defined in Table 2 of the surface roughness standard piece was used. The test sample was placed on the female mold so that the heat-fusible resin layer side was positioned on the male mold side. The test sample was pressed at a contact pressure of 0.1 MPa so as to have a molding depth of 5.0 mm, respectively, and was cold-formed (one-step drawing-in). The test samples of Example 1 and Comparative Examples 1 to 3 are molded in a state in which the resin layer and the bonding layer are laminated. With respect to the sample after cold forming, it was visually confirmed whether or not wrinkles were formed in the formed part. The results are shown in Table 1.

<Evaluation of printability on the surface of substrate layer>
A pattern was printed by pad printing on the surface of the base material layer of the test sample from which the resin layer was peeled off in the above <Determination of peel strength in the state where water is attached>. In addition, in the comparative example 4, since the resin layer and the joining layer were not provided, the pattern was printed by pad printing on the surface of the base material layer as it was. The pad printer used SPACE PAD 6GX made by Mishima Co., Ltd., and the ink used UV ink PJU-A black made by Navitas Co., Ltd. In addition, UV was irradiated for 30 seconds from a distance of 10 cm at an ultraviolet wavelength of 254 nm with a handy UV lamp SUV-4 manufactured by As One to cure the ink. The printability was evaluated according to the following criteria. The printability was measured at 24 ° C. in an environment of 50% relative humidity. The results are shown in Table 1.
A: The omission of printing is 2.5% or less B: The omission of printing is more than 2.5% and 5% or less C: The omission of printing is larger than 2.5%

<Evaluation of deterioration of base material layer at the time of heat fusion>
Each of the battery packaging materials obtained in Example 1 and Comparative Examples 1 to 4 is folded in two so that the heat fusible resin layers are opposed to each other, and heated using a seal bar (metal plate). The heat fusible resin layers were heat-sealed by sandwiching them from the side of the base material layer. The heat fusion conditions were such that the heating temperature of the seal bar was 220 ° C., the surface pressure was 1.0 MPa, and the time was 1 second. The base material layer was observed from above the resin layer of each battery packaging material after heat fusion, and the following criteria evaluated. The results are shown in Table 1.
A: No melting, deformation, discoloration, foaming or the like is observed in the substrate layer C: Melting, deformation, discoloration, or foaming is observed in the substrate layer

<Evaluation of peelability of resin layer after heat fusion>
Each packaging material for batteries after heat sealing obtained in <Evaluation of deterioration of base material layer at the time of heat sealing> is used as a test sample, and measurement of peel strength in the state where <water is attached Similarly, in the environment of temperature 25 ° C., relative humidity 50%, and atmospheric pressure (1 atm), first, 35% hydrochloric acid is deposited on the ends of the resin layer and the bonding layer of the test sample, and the MD direction is obtained. The resin layer was peeled about 30 mm. The hydrochloric acid adhering to the test sample was wiped off and allowed to dry. Next, distilled water (W) was attached to the portion where the resin layer was peeled off (the bonding layer 1 b between the resin layer and the surface on the base material layer side) using a dropper. At this time, distilled water (W) was attached over the entire direction of TD at the boundary between the resin layer and the surface on the base layer side. Next, it is shown in Table 1 whether or not the resin layer was peelable from the base material layer by pinching the resin layer with a finger for each test sample.

<Evaluation of peelability of resin layer before heat fusion>
Peeling of the resin layer before thermal fusion, in the same manner as in the above-mentioned <Evaluation of peelability of resin layer after thermal fusion>, except that each battery packaging material before thermal fusion is used as a test sample. The sex was evaluated. The results are shown in Table 1.

  In the laminate configuration shown in Table 1, PET is a polyethylene terephthalate layer, Ny is a nylon layer, AD is a bonding layer, DL is an adhesive layer formed by dry lamination, ALM is an aluminum alloy foil, PPa is an acid-modified polypropylene layer, CPP means an unstretched polypropylene layer, and PP means a polypropylene layer. Moreover, the numerical value described behind each layer of laminated constitution means thickness (μm), for example, “PET (12)” means “polyethylene terephthalate layer with thickness 12 μm”. Moreover, the result that the peel strength is 0.3 N / 15 mm or less means that the peel strength is equal to or less than the detection limit value.

  In Example 1 in which the bonding layer containing a polyester resin was provided on the resin layer, the peeling strength in the state in which water was not attached was high, and the peeling strength in the state in which water was attached was very low. Therefore, the resin layer could be easily peeled off in the state where water was attached. Moreover, even when it shape | molded in the state which laminated | stacked the resin layer and the joining layer, the wrinkles after shaping | molding did not exist and the external appearance was favorable. Furthermore, even if heat fusion is performed in a state in which the resin layer and the bonding layer are laminated, no deterioration is observed in the base material layer, and water is attached to the end faces of the resin layer and the bonding layer before and after heat fusion. The resin layer could be easily peeled off. From this result, if the peel strength in the case of peeling the resin layer from the laminate using an aqueous liquid is 1.0 N / 15 mm or less, the resin layer can be suitably peeled, and at 0.5 N / 15 mm or less If so, it can be said that the resin layer can be more suitably peeled off.

  On the other hand, in Comparative Examples 1 and 2 in which a urethane resin was used as the bonding layer, the peel strength in the state where water was not attached and the peel strength in the state where water was attached were also high. Therefore, it was difficult to peel off the resin layer even in the state where water was attached. In addition, although there is no wrinkle after molding even if molding is performed in a state where the resin layer and the bonding layer are laminated, and deterioration is not seen even if heat fusion is performed, the resin layer and the bonding layer Even when water was attached to the end face, the resin layer could not be peeled off. It is considered that the heat of heat fusion further increases the peel strength of the urethane resin, making it more difficult to peel off.

  In Comparative Example 3 in which a silicone resin was used as the bonding layer, the peel strength in the state in which water was not attached and the peel strength in the state in which water was attached were also low. Therefore, the resin layer can be easily peeled off even in a state where water is not attached, and when the protective layer is formed in a laminated state, it has wrinkles and the appearance is poor.

  In Comparative Example 4 in which the protective layer was not provided, the base layer was melted by heat fusion, and the nylon resin was attached to the seal bar used for the heat fusion.

DESCRIPTION OF SYMBOLS 1 ... Protective layer 1a ... Resin layer 1b ... Bonding layer 2 ... Base material layer 3 ... Barrier layer 4 ... Thermal adhesive resin layer 5 ... Adhesive layer 6 ... Adhesive layer 10 ... Packaging material W for batteries ... Water

Claims (8)

A laminate comprising at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat fusible resin layer in this order,
The bonding layer contains a polyester resin,
The peeling strength in the case of peeling the resin layer from the laminate in a state where water is not attached to the bonding layer in an environment with a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure is 2.0 N / 15 mm or more ,And,
The peeling strength in the case of peeling the resin layer from the laminate using an aqueous liquid in an environment of a temperature of 25 ° C., a relative humidity of 50% and an atmospheric pressure is 1.0 N / 15 mm or less,
The battery packaging material , wherein the aqueous liquid is water . The battery packaging material according to claim 1, wherein a lubricant is present on the surface on the resin layer side of the laminate. The packaging material for batteries of Claim 1 or 2 in which the ultraviolet absorber is contained in at least one layer of the said resin layer, a joining layer, and a base material layer. The packaging material for batteries of Claim 3 whose said ultraviolet absorber is a benzotriazole type ultraviolet absorber. The packaging material for batteries in any one of Claims 1-4 in which the light stabilizer is contained in at least one layer of the said resin layer, a joining layer, and a base material layer. The battery packaging material according to claim 5 , wherein the light stabilizer is a hindered amine light stabilizer. At least a step of laminating the resin layer, the bonding layer, the base layer, the barrier layer, and the heat-fusible resin layer in this order to obtain a laminate.
The bonding layer contains a polyester resin,
The peeling strength in the case of peeling the resin layer from the laminate in a state where water is not attached to the bonding layer in an environment with a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure is 2.0 N / 15 mm or more ,And,
The peeling strength in the case of peeling the resin layer from the laminate using an aqueous liquid in an environment of a temperature of 25 ° C., a relative humidity of 50% and an atmospheric pressure is 1.0 N / 15 mm or less,
The manufacturing method of the packaging material for batteries whose said aqueous liquid is water . A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package formed of the battery packaging material according to any one of claims 1 to 6 .