JP7041617B2 - Battery packaging materials, their manufacturing methods, and batteries - Google Patents

Description

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

Conventionally, various types of batteries have been developed, but in all batteries, a packaging material is an indispensable member for encapsulating a battery element such as an electrode or an electrolyte. Conventionally, metal packaging materials have been widely used for battery packaging, but in recent years, with the increasing performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., batteries are required to have various shapes. At the same time, there is a demand for thinner and lighter weight. However, the metal packaging material for batteries, which has been widely used in the past, has a drawback that it is difficult to keep up with the diversification of shapes and there is a limit to weight reduction.

Therefore, as a packaging material for batteries that can be easily processed into various shapes and can be made thinner and lighter, it is in the form of a film in which a base material layer / adhesive layer / barrier layer / heat-sealing resin layer is sequentially laminated. Laminates have been proposed (see, for example, Patent Document 1). Such a film-shaped packaging material for a battery is formed so that the battery element can be sealed by heat-welding the peripheral portions of the heat-sealing resin layers so as to face each other with a heat seal.

In the battery packaging material, when the battery element is enclosed, it is molded with a mold to form a space for accommodating the battery element. During this molding, the battery packaging material is stretched, so that there is a problem that cracks and pinholes are likely to occur in the barrier layer in the flange portion of the mold. In order to solve such problems, the surface of the heat-sealing resin layer of the battery packaging material is coated with an amide-based lubricant, or the resin forming the heat-sealing resin layer is mixed with an amide-based lubricant. A method of increasing the slipperiness of the heat-sealing resin layer by bleeding out to the surface is known. By adopting such a method, the battery packaging material is easily drawn into the mold during molding, and cracks and pinholes in the battery packaging material can be suppressed.

However, if the amount of the amide-based lubricant located on the surface of the heat-sealing resin layer is too large, there is a problem that the amide-based lubricant adheres to the mold and becomes a lump to contaminate the mold. When other packaging materials for batteries are molded while the mold is contaminated, a lump of lubricant adhering to the mold adheres to the surface of the packaging material for batteries and is used as it is for heat fusion of the heat-sealing resin layer. Will be done. Then, when the heat-sealing resin layer is heat-sealed, the melting method of the portion to which the lubricant adheres becomes non-uniform, so that a sealing failure occurs. In order to prevent this, it becomes necessary to increase the cleaning frequency for removing the lubricant adhering to the mold, and there is a problem that the continuous productivity of the battery is lowered.

On the other hand, if the amount of the amide-based lubricant located on the surface of the heat-sealing resin layer is too small, the slipperiness of the battery packaging material is lowered, so that there is a problem that the moldability of the battery packaging material is lowered.

Japanese Unexamined Patent Publication No. 2008-287971

In conventional packaging materials for batteries, an amide-based lubricant may be blended or coated on the heat-sealing resin layer as described above. However, despite the fact that the amide-based lubricant to be coated on the heat-sealing resin layer and the amide-based lubricant to be blended in the heat-sealing resin layer are set to a predetermined amount, the packaging material for a battery is formed at the time of molding. The amide-based lubricant may adhere to the mold to reduce continuous productivity, or cracks or pinholes may occur in the battery packaging material. For example, in both the case of blending an amide-based lubricant in the heat-bondable resin layer and the case of coating, the heat-melting depends on the storage environment from the manufacture of the battery packaging material to the time when it is subjected to molding. The amount of amide-based lubricant located on the surface of the adhesive resin layer changes.

Under such circumstances, the present invention is a packaging material for a battery provided with a heat-sealing resin layer containing an amide-based lubricant, has high moldability, and has continuous battery productivity. It is an object of the present invention to provide an excellent battery packaging material, a method for manufacturing the battery packaging material, and a battery using the battery packaging material.

The present inventors have made diligent studies to solve the above problems. As a result, it is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order, and the heat-sealing resin layer is an antioxidant, a light stabilizer, and a nucleation. It contains at least one selected from the group consisting of agents and an amide-based lubricant, and further absorbs obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays. From the spectrum, the absorption peak intensity A of the wave number 1650 cm-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant and the wave number derived from the -CH ₂ -variable vibration contained in the heat-sealing resin layer. The absorption spectrum intensity ratio X = A / B of the absorption peak intensity A to the absorption peak intensity B calculated by measuring the absorption peak intensity B of 1460 cm-1 is in the range of 0.05 or more and 0.80 or less. It has been found that the packaging material for batteries in the above has high moldability and excellent continuous productivity of batteries. The present invention has been completed by further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. It is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
The heat-sealing resin layer contains at least one selected from the group consisting of an antioxidant, a light stabilizer, and a nucleating agent, and an amide-based lubricant.
From the absorption spectrum obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays, the absorption of the wave number 1650 cm-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant. The said to the absorption peak intensity B calculated by measuring the peak intensity A and the absorption peak intensity B having a wave number of 1460 cm-1 derived from -CH ₂ -variable angle vibration contained in the heat-sealing resin layer. A packaging material for a battery, wherein the absorption spectrum intensity ratio X = A / B of the absorption peak intensity A is in the range of 0.05 or more and 0.80 or less.
Item 2. The antioxidant is at least one selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant.
Item 2. The battery packaging material according to Item 1, wherein the light stabilizer is at least one of an ultraviolet absorber and a hindered amine compound.
Item 3. Item 2. The battery packaging material according to Item 1 or 2, wherein the heat-sealing resin layer further contains a plasticizer.
Item 4. Item 2. The packaging material for a battery according to any one of Items 1 to 3, wherein the heat-sealing resin layer further contains a flame retardant.
Item 5. Item 2. The packaging material for a battery according to any one of Items 1 to 4, wherein the heat-sealing resin layer contains polyolefin.
Item 6. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the battery packaging material according to any one of Items 1 to 5.
Item 7. At least a substrate layer, a barrier layer, at least one selected from the group consisting of antioxidants, photostabilizers, and nucleating agents, and a heat-sealing resin layer containing an amide-based lubricant are laminated in this order. The process of preparing the packaging material for batteries, which consists of the laminated body,
From the absorption spectrum obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays, the absorption of the wave number 1650 cm-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant. The absorption with respect to the absorption peak intensity B, which is calculated by measuring the peak intensity A and the absorption peak intensity B of 1460 cm-1 derived from the -CH ₂ -variable angle vibration contained in the heat-sealing resin layer. A step of confirming that the absorption spectrum intensity ratio X = A / B of the peak intensity A is in the range of 0.05 or more and 0.80 or less, and
A method for manufacturing a packaging material for a battery.

According to the present invention, there is provided a battery packaging material having high moldability and excellent continuous battery productivity, a method for manufacturing the battery packaging material, and a battery using the battery packaging material. be able to. Further, according to the present invention, it is also possible to provide a method for manufacturing the packaging material for a battery and a battery using the packaging material for the battery.

It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention. It is a figure which shows an example of the cross-sectional structure of the packaging material for a battery of this invention.

The packaging material for a battery of the present invention is composed of a laminate having at least a base material layer, a barrier layer, and a heat-fusing resin layer in this order, and the heat-fusing resin layer is composed of an antioxidant and light. It contains at least one selected from the group consisting of stabilizers and nucleating agents, and amide-based lubricants, and by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays. From the obtained absorption spectrum, the absorption peak intensity A having a wave number of 1650 cm-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant and the -CH ₂ -variable vibration contained in the heat-sealing resin layer The absorption spectrum intensity ratio X = A / B of the absorption peak intensity A to the absorption peak intensity B calculated by measuring the absorption peak intensity B having a wave number of 1460 cm-1 is 0.05 or more and 0.80. It is characterized by being in the following range. Hereinafter, the battery packaging material of the present invention will be described in detail.

In addition, in this specification, the display of "-" indicating a numerical range indicates that it is equal to or more than the numerical value attached to the left side thereof and less than or equal to the numerical value attached to the right side thereof, for example, the numerical range "XY". "" Means that it is X or more and Y or less.

1. 1. Laminated Structure of Battery Packaging Material The battery packaging material 10 of the present invention is laminated with a base material layer 1, a barrier layer 3, and a heat-sealing resin layer 4 in this order, for example, as shown in FIGS. 1 to 4. It consists of a body. In the battery packaging material of the present invention, the base material layer 1 is on the outermost layer side, and the heat-sealing resin layer 4 is on the innermost layer. That is, at the time of assembling the battery, the heat-sealing resin layers 4 located on the peripheral edge of the battery element are heat-sealed to seal the battery element, whereby the battery element is sealed.

In the battery packaging material of the present invention, for example, as shown in FIGS. 2 to 4, the adhesive layer 2 is required between the base material layer 1 and the barrier layer 3 for the purpose of enhancing their adhesiveness. May have. Further, as shown in FIG. 3, an adhesive layer 5 may be provided between the barrier layer 3 and the heat-bondable resin layer 4 for the purpose of enhancing their adhesiveness, if necessary. Further, as shown in FIG. 4, a surface covering layer 6 or the like may be provided on the outside of the base material layer 1 (the side opposite to the heat-sealing resin layer 4), if necessary.

The total thickness of the laminate constituting the packaging material for a battery of the present invention is not particularly limited, but from the viewpoint of exhibiting high formability and high continuous productivity while making the total thickness of the laminate as thin as possible. Is preferably about 160 μm or less, more preferably about 35 to 155 μm, still more preferably about 45 to 120 μm. According to the present invention, excellent insulating properties can be exhibited even when the thickness of the laminate constituting the packaging material for a battery of the present invention is as thin as 160 μm or less, for example. Therefore, the battery packaging material of the present invention can contribute to the improvement of the energy density of the battery.

2. 2. Each layer forming the packaging material for batteries [base material layer 1]
In the packaging material for batteries of the present invention, the base material layer 1 is a layer located on the outermost layer side. The material forming the base material layer 1 is not particularly limited as long as it has an insulating property. Examples of the material forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluororesin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, polycarbonate, and a mixture or copolymer thereof. And so on.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and ethylene terephthalate as the main constituents of the copolymerized polyester and butylene terephthalate as the main constituents of the repeating unit. Examples thereof include the obtained copolymerized polyester. Further, as the copolymerized polyester having ethylene terephthalate as the main body of the repeating unit, specifically, a copolymer polyester having ethylene terephthalate as the main body of the repeating unit and polymerizing with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate)). (Abbreviated after), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) , Polyethylene (terephthalate / decandicarboxylate) and the like. The copolymerized polyester having butylene terephthalate as the main body of the repeating unit is specifically a copolymer polyester having butylene terephthalate as the main body of the repeating unit and polymerizing with butylene isophthalate (hereinafter, polybutylene (terephthalate / isophthalate)). (Abbreviated after), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decantycarboxylate), polybutylene naphthalate and the like. These polyesters may be used alone or in combination of two or more. Polyester has an advantage that it has excellent electrolytic solution resistance and is less likely to cause whitening or the like due to adhesion of the electrolytic solution, and is preferably used as a material for forming the base material layer 1.

Specific examples of the polyamide include an aliphatic polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid. Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I stands for isophthalic acid, T stands for terephthalic acid) and other hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamides, polymethoxylylenazi Aroma-containing polyamide such as pamide (MXD6); alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM6); further, a lactam component and an isocyanate component such as 4,4'-diphenylmethane-diisocyanate are copolymerized. Examples thereof include polyesteramide copolymers and polyetheresteramide copolymers, which are copolymers of the polyamides and copolymerized polyamides with polyesters and polyalkylene ether glycols; and copolymers thereof. These polyamides may be used alone or in combination of two or more. The stretched polyamide film has excellent stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.

In the base material layer 1, at least one of resin films and coatings of different materials can be laminated (multilayer structure) in order to improve pinhole resistance and insulation when used as a battery package. be. Specific examples thereof include 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. When the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate in which a plurality of biaxially stretched nylon films are laminated, and a laminate in which a plurality of biaxially stretched polyester films are laminated. The body is preferred. For example, when the base material layer 1 is formed of two layers of resin films, the polyester resin and the polyester resin are laminated, the polyamide resin and the polyamide resin are laminated, or the polyester resin and the polyamide resin are laminated. Is preferable, and a configuration in which polyethylene terephthalate and polyethylene terephthalate are laminated, a configuration in which nylon and nylon are laminated, or a configuration in which polyethylene terephthalate and nylon are laminated are more preferable. Further, since the biaxially stretched polyester is difficult to discolor when the electrolytic solution adheres to the surface, for example, the base material layer 1 is a multilayer structure of a biaxially stretched nylon film and a biaxially stretched polyester film. The base material layer 1 is preferably a laminate having biaxially stretched nylon and biaxially stretched polyester in this order from the barrier layer 3 side. When the base material layer 1 has a multilayer structure, the thickness of each layer is preferably 3 to 25 μm.

When the base material layer 1 has a multilayer structure, each resin film may be adhered via an adhesive, or may be directly laminated without an adhesive. In the case of adhering without using an adhesive, for example, a method of adhering in a heat-melted state such as a coextrusion laminating method, a sandwich laminating method, and a thermal laminating method can be mentioned. When adhering via an adhesive, the adhesive used may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a thermal pressure type, an electron beam curing type, an ultraviolet curing type and the like. Specific examples of the adhesive include the same adhesives as those exemplified in the adhesive layer 2. Further, the thickness of the adhesive can be the same as that of the adhesive layer 2.

In the present invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that the lubricant is adhered to the surface of the base material layer 1. The lubricant is not particularly limited, but preferably an amide-based lubricant exemplified in the heat-sealing resin layer described later.

When the lubricant is present on the surface of the base material layer 1, the abundance thereof is not particularly limited, but is preferably about 3 mg / m ² or more, more preferably 4 to 15 mg / m at a temperature of 24 ° C. and a humidity of 60%. About ² , more preferably about 5 to 14 mg / m ² .

The thickness of the base material layer 1 is preferably about 4 μm or more, more preferably about 10 to 75 μm, from the viewpoint of reducing the total thickness of the battery packaging material and making it a battery packaging material having excellent insulation. , More preferably about 10 to 50 μm.

[Adhesive layer 2]
In the packaging material for batteries of the present invention, the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as necessary in order to firmly bond them.

The adhesive layer 2 is formed by an adhesive capable of adhering the base material layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive mechanism used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatile type, a heat melting type, a thermal pressure type and the like.

Specific examples of the adhesive component that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolymerized polyester; polyether. Adhesives; Polyethylene adhesives; Epoxy resins; Phenolic resins; Polyethylene resins such as nylon 6, nylon 66, nylon 12, and copolymerized polyamides; Polyethylene resins such as polyolefins, carboxylic acid-modified polyolefins, and metal-modified polyolefins. , Polyvinyl acetate resin; Cellulous adhesive; (Meta) acrylic resin; Polyethylene resin; Polycarbonate; Amino resin such as urea resin and melamine resin; Rubber such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber; Silicone Examples include system resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane-based adhesive is preferable.

The thickness of the adhesive layer 2 is not particularly limited as long as it functions as an adhesive layer, and examples thereof include about 1 to 10 μm, preferably about 2 to 5 μm.

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function of improving the strength of the battery packaging material and preventing water vapor, oxygen, light and the like from entering the inside of the battery. The barrier layer 3 is preferably a metal layer, that is, a layer made of metal. Specific examples of the metal constituting the barrier layer 3 include aluminum, stainless steel, titanium, and the like, preferably aluminum. 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, and is formed of a metal foil. Is preferable, and it is more preferable to form it with an aluminum alloy foil. From the viewpoint of preventing the formation of wrinkles and pinholes in the barrier layer 3 during the manufacture of battery packaging materials, the barrier layer may be, for example, annealed aluminum (JIS H4160: 1994 A8021HO, JIS H4160: It is more preferably formed from a soft aluminum alloy foil such as 1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O).

The thickness of the barrier layer 3 is not particularly limited as long as it exhibits a barrier function 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, it is about 10 to 80 μm.

Further, it is preferable that at least one surface, preferably both sides, of the barrier layer 3 is subjected to chemical conversion treatment in order to stabilize adhesion, prevent dissolution and corrosion, and the like. Here, the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer. The chemical conversion treatment includes, for example, chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium bicarbonate, acetylacetate chromate, chromium chloride, potassium sulfate chromium; phosphorus. Phosphoric acid treatment with a phosphoric acid compound such as sodium acid, potassium phosphate, ammonium phosphate, polyphosphate; for an aminoated phenol polymer having repeating units represented by the following general formulas (1) to (4). Examples include the chromate treatment that was used. In the amination phenol polymer, the repeating unit represented by the following general formulas (1) to (4) may be contained alone or in any combination of two or more. May be good.

In the general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl 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, respectively, and represent a hydroxyl 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. Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group. Examples of the hydroxyalkyl groups represented by X, R ¹ and R ² include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group and 3-. A linear or branched chain having 1 to 4 carbon atoms in which one hydroxy group such as a hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, or a 4-hydroxybutyl group is substituted. An alkyl group can be 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 the same or different from each other. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. The number average molecular weight of the aminating phenol polymer having the repeating unit represented by the general formulas (1) to (4) is preferably, for example, about 5 to 1,000,000, and preferably about 1,000 to 20,000. More preferred.

Further, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a material in which metal oxides such as aluminum oxide, titanium oxide, cerium oxide and tin oxide and fine particles of 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 by performing a baking treatment at 150 ° C. or higher can be mentioned. Further, a resin layer obtained by cross-linking a cationic polymer with a cross-linking agent may be further formed on the acid-resistant film. Here, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of polyethyleneimine and a polymer having a carboxylic acid, a primary amine graft acrylic resin obtained by graft-polymerizing a primary amine on an acrylic main skeleton, and polyallylamine. Alternatively, a derivative thereof, aminophenol and the like can be mentioned. As these cationic polymers, only one kind may be used, or two or more kinds may be used in combination. Examples of the cross-linking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent, and the like. As these cross-linking agents, only one kind may be used, or two or more kinds may be used in combination.

As a method for specifically providing the acid-resistant film, for example, as an example, at least the inner layer side surface of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, or an electrolytic acid cleaning method. , The degreasing treatment is performed by a well-known treatment method such as an acid activation method, and then the degreased surface is subjected to a phosphoric acid metal salt such as a chromium phosphate salt, a titanium phosphate salt, a zirconium phosphate salt or a zinc phosphate salt, and these. A treatment solution (aqueous solution) containing a mixture of metal salts as a main component, or a treatment solution (aqueous solution) containing a mixture of a non-metal phosphate and these non-metal salts as a main component, or an acrylic resin with these. By applying a treatment liquid (aqueous solution) consisting of a mixture with a water-based synthetic resin such as a phenol-based resin or a urethane-based resin by a well-known coating method such as a roll coating method, a gravure printing method, or a dipping method, an acid-resistant film is formed. Can be formed. For example, when treated with a chromium phosphate-based treatment liquid, an acid-resistant film composed of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc. is formed and treated with a zinc phosphate-based treatment liquid. If so, the acid-resistant film is made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride and the like.

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

Further, as another example of the acid resistant film, a phosphate-based film or a chromic acid-based film can be mentioned. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, chromium phosphate and the like, and examples of the chromium acid system include chromium chromate and the like.

Further, as another example of the acid-resistant film, by forming an acid-resistant film such as a phosphate, a chromate, a fluoride, and a triazinethiol compound, the aluminum and the base material layer at the time of embossing are formed. Prevention of delamination, hydrogen fluoride generated by the reaction between the electrolyte and water prevents the aluminum surface from melting and corroding, especially the aluminum oxide present on the aluminum surface from melting and corroding, and adhering to the aluminum surface. It improves the property (wetting property) and shows the effect of preventing the delamination of the base material layer and aluminum during heat fusion, and in the embossed type, the effect of preventing the delamination of the base material layer and aluminum during press molding. Among the substances forming an 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 drying and baking treatment is good.

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

Further, it is preferable that the anionic polymer is a poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component. Further, it is preferable that the cross-linking agent is at least one selected from the group consisting of a compound having a functional group of any of an isocyanate group, a glycidyl group, a carboxyl group and an oxazoline group and a silane coupling agent.

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

As the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatment may be performed in combination. Further, these chemical conversion treatments may be carried out by using one kind of compound alone or by using two or more kinds of compounds in combination. Among the chemical conversion treatments, chromate treatment and chemical conversion treatment in which a chromium compound, a phosphoric acid compound, and an amination phenol polymer are combined are preferable. Among the chromium compounds, a chromic acid compound is preferable.

Specific examples of the acid-resistant film include those containing at least one of phosphate, chromate, fluoride, and triazinethiol. Further, an acid resistant film containing a cerium compound is also preferable. As the cerium compound, cerium oxide is preferable.

Specific examples of the acid-resistant film include a phosphate-based film, a chromate-based film, a fluoride-based film, and a triazinethiol compound film. The acid-resistant film may be one of these, or may be a combination of a plurality of types. Further, the acid-resistant film is a treatment liquid consisting of a mixture of a metal phosphate and an aqueous synthetic resin after degreasing the chemical conversion treatment surface of the aluminum alloy foil, or a mixture of a non-metal phosphate and an aqueous synthetic resin. It may be formed of a treatment liquid made of.

The composition of the acid-resistant film can be analyzed by using, for example, a time-of-flight secondary ion mass spectrometry method. Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry detects, for example, peaks 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. It was confirmed by X-ray photoelectron spectroscopy that the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contained at least one element selected from the group consisting of phosphorus, chromium and cerium. can do. Specifically, first, in the battery packaging material, the heat-sealing 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. Then, X-ray photoelectron spectroscopy on the surface of the aluminum alloy foil is used to confirm that these elements are contained.

The amount of the acid-resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, but for example, in the case of performing the above chromate treatment, the chromium compound is chromium per 1 m ² of the surface of the barrier layer 3. The conversion is about 0.5 to 50 mg, preferably about 1.0 to 40 mg, the phosphorus compound is about 0.5 to 50 mg, preferably about 1.0 to 40 mg, and the amination phenol polymer is 1.0. It is desirable that it is contained in a proportion of about 200 mg, preferably about 5.0 to 150 mg.

The thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably 1 to 10 μm from the viewpoint of the cohesive force of the film and the adhesion to the barrier layer 3 and the heat-sealed resin layer 4. About 100 nm, more preferably about 1 to 50 nm can be mentioned. The thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersion type X-ray spectroscopy or electron beam energy loss spectroscopy.

In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, or the like, and then the temperature of the barrier layer is 70. It is carried out by heating to about 200 ° C. Further, before the chemical conversion treatment is applied to the barrier layer, the barrier layer may be subjected to a degreasing treatment by an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like in advance. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the barrier layer.

[Heat-fused resin layer 4]
In the battery packaging material of the present invention, the heat-sealing resin layer 4 corresponds to the innermost layer, and is a layer in which the heat-sealing resin layers are heat-sealed to seal the battery element when the battery is assembled.

The resin component used in the heat-fusing resin layer 4 is not particularly limited as long as it can be heat-fused, and examples thereof include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins. Be done.

Specific examples of the polyolefin include polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; homopolypropylene, a block copolymer of polypropylene (for example, a block copolymer of propylene and ethylene), and polypropylene. Polypropylene such as random copolymers of polyethylene (eg, random copolymers of propylene and ethylene); polyethylene-butene-propylene tarpolymers and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

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, and isoprene. Be done. Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene and the like. Among these polyolefins, cyclic alkene is preferable, and norbornene is more preferable. Further, styrene can be used as a constituent monomer.

The carboxylic acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing the polyolefin with a carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

The carboxylic acid-modified cyclic polyolefin means that a part of the monomer constituting the cyclic polyolefin is copolymerized in place of α, β-unsaturated carboxylic acid or its anhydride, or α, β with respect to the cyclic polyolefin. -A polymer obtained by block-polymerizing or graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof. The same applies to the cyclic polyolefin that is modified with carboxylic acid. The carboxylic acid used for the modification is the same as that used for the modification of the polyolefin.

Among these resin components, carboxylic acid-modified polyolefin is preferable; and carboxylic acid-modified polypropylene is more preferable.

The heat-bondable resin layer 4 may be formed of one type of resin component alone, or may be formed of a blended polymer in which two or more types of resin components are combined. Further, the heat-sealing resin layer 4 may be formed of only one layer, or may be formed of two or more layers with the same or different resin components.

Further, the heat-sealing resin layer 4 contains an amide-based lubricant. Specific examples of the amide-based lubricant include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides. 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 unsaturated fatty acid amides include oleic acid amides and erucic acid amides. Specific examples of the substituted amide include N-oleyl palmitate amide, N-stearyl stearyl amide, N-stearyl oleate amide, N-oleyl stealic acid amide, N-stearyl erucate amide and the like. Further, specific examples of trimethylolamide include trimethylolstearic acid amide. Specific examples of saturated fatty acid bisamides include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, and hexamethylene bisstearate. Examples thereof include acid amides, hexamethylene bisbechenic acid amides, hexamethylene hydroxystearic acid amides, N, N'-distealyl adipic acid amides, N, N'-distearyl sebasic acid amides and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N'-diorail adipic acid amide, and N, N'-diorail sebacic acid amide. And so on. Specific examples of the fatty acid ester amide include stearoamide ethyl stearate and the like. Specific examples of the aromatic bisamide include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, N, N'-cystelyl isophthalic acid amide and the like. The lubricant may be used alone or in combination of two or more.

The content of the amide-based lubricant in the heat-sealing resin layer 4 is not particularly limited, but at least one selected from the group consisting of the antioxidant, the photostabilizer, and the nucleating agent described later together with the amide-based lubricant. By including the seeds in the heat-sealing resin layer 4, the amount of the amide-based lubricant located on the surface of the heat-sealing resin layer 4 becomes an amount suitable for moldability and continuous productivity (that is, absorption spectrum). From the viewpoint (where the intensity ratio X is in the above range), preferably about 500 to 2000 ppm, more preferably about 700 to 1800 ppm can be mentioned.

In the present invention, the heat-sealing resin layer 4 contains at least one selected from the group consisting of antioxidants, photostabilizers, and nucleating agents, in addition to the amide-based lubricant. Therefore, the amount of the amide-based lubricant located on the surface of the heat-sealing resin layer 4 is suitably set to the absorption spectrum intensity ratio X, which will be described later, which is suitable for moldability and continuous productivity. Although the details of this mechanism are not clear, functional groups that cause hydrogen bonds such as hydroxyl groups, carbonyl groups, and carboxyl groups contained in antioxidants, photostabilizers, and nucleating agents, and other intermolecular interactions. It is considered that the interaction between the substance causing the amide-based lubricant and the amide group of the amide-based lubricant effectively suppresses the bleed-out of the amide-based lubricant to the surface of the heat-sealing resin layer 4 in a large amount.

The content of at least one selected from the group consisting of antioxidants, photostabilizers, and nucleating agents in the heat-sealing resin layer 4 is not particularly limited, but is heat-fusing together with an amide-based lubricant. From the viewpoint of obtaining an absorption spectrum intensity ratio X suitable for moldability and continuous productivity by being contained in the resin layer 4, it is preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm. Even when two or more of the antioxidant, the light stabilizer, and the nucleating agent are contained in the heat-sealing resin layer 4, the total amount thereof is preferably within the above range.

The antioxidant is not particularly limited, but is preferably phenol from the viewpoint of suitably improving the moldability and continuous productivity of the packaging material for batteries by being contained in the heat-sealing resin layer 4 together with the amide-based lubricant. Examples thereof include based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. One type of antioxidant may be used alone, or two or more types may be used in combination.

Examples of the phenolic antioxidant include 2,6-di-tertiary butyl-4-ethylphenol, 2-third butyl-4,6-dimethylphenol, styrenated phenol, and 2,2'-methylenebis (4). -Ethyl-6-tertiary butylphenol), 2,2'-thiobis- (6-tertiary butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-third) Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3) , 5-Di-3rd butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-3th butyl-4-hydroxyphenyl) propionamide, 2,2'-Oxamide-bis [ethyl-3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3', 5'-di-tertiary butyl) -4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tertiary butylphenol), 3,5-bis (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tertiary amylhydroquinone, polymer of hindered phenol (trade name AO.OH998 manufactured by Adecapalmarol), 2,2'-methylenebis [6- (1-methyl) Cyclohexyl) -p-cresol], 2-third butyl-6- (3-third butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3) , 5-Di-Third Pentylphenyl) Ethyl] -4,6-di-Third Pentylphenyl acrylate, 6- [3- (3-Third Butyl-4-Hydroxy-5-Methyl) Propoxy] -2, 4,8,10-Tetra-tertiary butylbenz [d, f] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-third butyl-4-hydroxy) Phenol) propionate, bis [monoethyl (3,5-di-tertiary butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H)- Reaction product of benzofuranone and o-xylene, 2,6-di-tertiary butyl-4- (4,6-bis (octyl) Thio) -1,3,5-triazine-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3 -Bis- (4'-hydroxy-3'-third butyl-phenyl) butanoic acid] glycol ester, 2,6-di-tertiary butyl-p-cresol, 2,6-diphenyl-4-octadesiloxyphenol , Stearyl (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-third butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-third Butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-third butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-third butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tertiary butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-third butylphenol), bis [ 3,3-Bis (4-Hydroxy-3-3rd Butylphenyl) Butyric Acid] Glycolester, 4,4'-Butylidenebis (2,6-di-3rd Butylphenol), 4,4'-Butylidenebis (6) -3rd Butyl-3-Methylphenol), 2,2'-Etilidenebis (4,6-di-3rd Butylphenol), 1,1,3-Tris (2-Methyl-4-hydroxy-5-3) Butylphenyl) butane, bis [2-third butyl-4-methyl-6- (2-hydroxy-3-third butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6) -Dimethyl-3-hydroxy-4-third butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-third butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-Di-Triary Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-Tris [(3,5-Di-Triary Butyl-4-hydroxyphenyl) Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3', 5'-di-tertiary butyl-4'-hydroxyphenyl) propionate] methane, 2-third butyl-4-methyl-6- (2) -Acryloyloxy-3-3rd Butyl-5-Methylbenzyl) Phenol, 3,9-Bis [2- (3- (3-) Tertiary butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycolbis [β- (3-Triary Butyl-4-Hydroxy-5-Methylphenyl) Propionate], Stearyl-3- (3,5-Ditrithylbutyl-4-hydroxyphenyl) Propionic Acid Amid, Palmytyl-3- (3,5) -Di-tertiary butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-third) Examples thereof include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as butyl-4-hydroxyphenyl) propionic acid amide.

Examples of the phosphorus antioxidant include triphenylphosphite, diisooctylphosphite, heptaxitriphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, and diphenyltridecylphosphite. , Triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris (dipropylene glycol) phosphite, diisodecylpentaerythritol diphosphite, dioleylhydrogenphosphite, trilauryltrithiophosphite, bis (tridecyl) phos Fight, Tris (isodecyl) phosphite, Tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) phenylphosphite, tetraphenyldipropylglycoldiphosphite , Trisnonylphenyl Phenyl Phenyl, Tris (2,4-di-3rd Butylphenyl) Phenyl, Tris (2,4-Di-Triary Butyl-5-Methylphenyl) Phenyl, Tris [2-3rd Butyl] -4- (3-3 butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, distearyl Pentaerythritol diphosphite, distearyl pentaerythritol and calcium stearate salt, alkyl (C10) bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis ( 2,4-Di-Triary Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-third butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri- Tertiary Butylphenyl) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-third) Butyl-6-methylphenyl) ethylphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-third) Chill-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-third butylphenyl) butanetriphosphite, tetrakis (2,4-di-th) Tributylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanol-3-iriden) tris (2-1, 1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecylphosphite, 2,2'-methylenebis (4,6-tertiary butylphenyl) -2-ethylhexylphosphite, 2,2'- Methylenebis (4,6-di-tertiary butylphenyl) -octadecylphosphite, 2,2'-ethylidenebis (4,6-di-third butylphenyl) fluorophosphite, 4,4'-butylidenebis (3-butylidenebis) Methyl-6-tertiary butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tertiary butyldibenzo [d, f] [1,3,2] dioxaphosphe) Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphespiro [5,5] undecane, 2 , 4,6-Tri-Triary Butylphenyl-2-Butyl-2Ethyl-1,3-Propanediol Phosphite, Poly 4,4'-Isopropyridendiphenol C12-15 Alcohol Phosphite, 2-Ethyl-2 Examples thereof include phosphite of -butylpropylene glycol and 2,4,6-tri-3-butylphenol.

Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-third butylphenyl. ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropio Nate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-third butyl-m-cresol), 2,2'-thiobis (6-third butyl-p-cresol), distearyl-di Sulfide is mentioned.

When the heat-bondable resin layer 4 contains an antioxidant, the content thereof is not particularly limited, but by being contained in the heat-bondable resin layer 4 together with the amide-based lubricant, formability and continuous productivity are achieved. From the viewpoint of obtaining an absorption spectrum intensity ratio X suitable for the above, preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm can be mentioned.

Examples of the light stabilizer include an ultraviolet absorber and a hindered amine compound.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). 2- (2-Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-third octylphenyl) benzotriazole, 2- (2-hydroxy-3,5), etc. -Di-Triary Butylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3-3rd Butyl-5-Methylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3,5- Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-thioctyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-third butyl-5-carboxyphenyl) benzotriazole Polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-third Butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-3 octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl)- 5-Third Butylphenyl] -5-Chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-Hydroxy-3-third butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-third amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-third Butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- 2- (2-Hydroxyphenyl) such as (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole, etc. 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- [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) -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine, etc. 2- (2-Hydroxyphenyl) -4,6-diaryl-1,3,5-triazines; phenylsalicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl -4-Hydroxybenzoate, octyl (3,5-dithiary butyl-4-hydroxy) benzoate, dodecyl (3,5-dithiary butyl-4-hydroxy) benzoate, tetradecyl (3,5-dithird butyl) -4-Hydroxy) benzoate, hexadecyl (3,5-dithiary butyl-4-hydroxy) benzoate, octadecyl (3,5-dithird butyl-4-hydroxy) benzoate, behenyl (3,5-dithird) Phenylates such as butyl-4-hydroxy) benzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β -Cyano acrylates such as diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts or metal chelate, especially nickel, chromium salts or chelates, etc. Can be mentioned.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-. Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-Butan Tetracarboxylate, Tetrakiss (1,2,2,6,6-Pentamethyl-4-piperidyl) -1,2,3,4-Butane Tetracarboxylate, Bis (2,2,6,6- 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-ditertiary butyl-4-) Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (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-third octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2)) 6,6-Tetramethyl-4-piperidyl) amino) -s-triazine-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-triazine-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-triazine-6-yl] aminoundecane, 1, 6,11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] aminoundecane, bis {4- (1-octyloxy-2,2,6,6-tetramethyl) Piperidine} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidine) carbonate and the like can be mentioned. Among these, the compound linked to the 1-position position of piperidine is preferably a compound of N-oxyalkyl or N-methyl.

When the heat-bondable resin layer 4 contains a light stabilizer, the content thereof is not particularly limited, but the amide-based lubricant and the antioxidant are both contained in the heat-bondable resin layer 4, whereby molding is performed. From the viewpoint of obtaining the absorption spectrum intensity ratio X suitable for the property and continuous productivity, preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm can be mentioned.

Examples of the nucleating agent include carboxylic acid metals such as sodium benzoate, 4-terti-butyl benzoate aluminum salt, sodium adipate and disodium dicyclo [2.2.1] heptane-2,3-dicarboxylate. Salt, sodium bis (4-third butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-ditrith butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-dith) Phosphoric acid ester metal salts such as tributylphenyl) phosphate, polyvalent alcohol derivatives such as dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (p-ethylbenzylene) sorbitol, and bis (dimethylbenzylene) sorbitol, N, N ', N'-Tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide (RIKACLEAR PC1), N, N', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, N, Examples thereof include amide compounds such as N'-dicyclohexyl-naphthalenedicarboxamide and 1,3,5-tri (dimethylisopropoilamino) benzene.

When the heat-sealing resin layer 4 contains a nucleating agent, the content thereof is not particularly limited, but the amide-based lubricant and the antioxidant are both contained in the heat-sealing resin layer 4, whereby molding is performed. From the viewpoint of obtaining the absorption spectrum intensity ratio X suitable for the property and continuous productivity, preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm can be mentioned.

Further, from the viewpoint of suitably improving the moldability and continuous productivity of the battery packaging material, the heat-sealing resin layer 4 may contain at least one other additive such as a plasticizer and a flame retardant. .. Each of the other additives may be used alone or in combination of two or more. Although the details of this mechanism are not clear, amides are associated with functional groups that cause hydrogen bonds such as hydroxyl groups, carbonyl groups, and carboxyl groups contained in plasticizers and flame retardant agents, and other substances that cause intermolecular interactions. It is considered that the interaction of the amide-based lubricant with the amide group effectively suppresses the bleed-out of the amide-based lubricant to the surface of the heat-sealing resin layer 4 in a large amount.

Examples of the plasticizer include known commercially available plasticizers and softeners for rubber added to polyvinyl chloride, polyethylene, polyethylene, natural rubber and the like. Specifically, for example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, dicyclohexyl phthalate, or phthalic acid mixed group ester plasticizers, diisodecyl succinate, adipic acid. Aliper dibasic acid ester plasticizers such as dioctyl and dioctyl sevacinate, glycol ester plasticizers such as diethylene glycol dibenzoate and dipentaerythritol hexaester, fatty acid ester plasticizers such as butyl oleate and methyl acetyllithinolate, Phosphoric acid ester plasticizers such as tricresyl phosphate and trioctyl phosphate, epoxy plasticizers such as epoxidized soybean oil, butyl epoxidate stearate and octyl epoxystearate, and other plasticizers such as paraffin, chlorinated paraffin and polypropylene adipate. Examples thereof include agents and softening agents for rubber such as paraffin-based, naphthen-based, and aromatic mineral oils.

When the heat-bondable resin layer 4 contains a plasticizer, the content thereof is not particularly limited, but the amide-based lubricant and the antioxidant are both contained in the heat-bondable resin layer 4, so that the moldability is moldable. From the viewpoint of obtaining the absorption spectrum intensity ratio X suitable for continuous productivity, preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm can be mentioned.

Examples of the flame retardant include aromatic phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate). , Phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-Contains phosphinic acid esters such as oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, and phosphorus. Phosphonic flame retardant such as vinylbenzyl compound and red phosphorus, metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene. , Ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane , Brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A Examples thereof include type dimethacrylate, pentabromobenzyl acrylate, and bromine-based flame retardant such as brominated styrene.

When the heat-sealing resin layer 4 contains a flame retardant, the content thereof is not particularly limited, but the amide-based lubricant and the antioxidant are both contained in the heat-sealing resin layer 4, so that the moldability is moldable. From the viewpoint of obtaining the absorption spectrum intensity ratio X suitable for continuous productivity, preferably about 100 to 2000 ppm, more preferably about 300 to 1500 ppm can be mentioned.

In the packaging material for a battery of the present invention, C = O expansion / contraction of the amide group of the amide-based lubricant is obtained from the absorption spectrum obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer 4 is irradiated with infrared rays. Calculated by measuring the absorption peak intensity A with a wave number of 1650 cm-1 derived from vibration and the absorption peak intensity B with a wave number of 1460 cm-1 derived from -CH ₂ -variant angle vibration contained in the heat-sealing resin layer. The absorption spectral intensity ratio X = A / B of the absorption peak intensity A to the absorption peak intensity B is in the range of 0.05 to 0.80. More specifically, when the infrared absorption spectrum is acquired from the outermost surface side by the attenuation total reflection method of the Fourier transform infrared spectroscopic analysis method, the wave number 1650 cm-derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant. The absorption peak intensity A calculated by measuring the absorption peak intensity A of 1 and the absorption peak intensity B having a wave number of 1460 cm-1 derived from -CH ₂ -variable angle vibration contained in the heat-sealing resin layer. The absorption spectral intensity ratio X = A / B of the absorption peak intensity A to B is in the range of 0.05 to 0.80. The packaging material for a battery of the present invention has a high moldability and excellent continuous productivity of a battery by having an absorption spectrum intensity ratio X in such a specific range. In the present invention, the absorption spectrum intensity ratio X = A / B may be in the range of 0.05 to 0.80, but a more preferable absorption spectrum intensity ratio X = A / B is 0.10 to 0.80. Examples thereof include about 0.70, about 0.10 to 0.60, about 0.20 to 0.70, and about 0.20 to 0.60.

For the absorption spectrum intensity ratio X in the present invention, a sample is prepared by cutting the packaging material for a battery into 100 mm × 100 mm square, and the surface of the heat-sealing resin layer of this sample is surfaced by Thermo Fisher Scientific Co., Ltd. Manufactured by: Infrared absorption spectrum measurement by infrared spectroscopy in an environment of temperature 25 ° C. and relative humidity 50% using ATR mode of Nicolet iS10 FT-IR.

As described above, even in the conventional packaging materials for batteries, the heat-sealing resin layer has been blended with or coated with an amide-based lubricant. However, despite the fact that the amide-based lubricant coated on the heat-sealing resin layer and the amide-based lubricant blended in the heat-sealing resin layer are set to a predetermined amount, when the packaging material for a battery is molded, The amide-based lubricant may adhere to the mold to reduce continuous productivity, or cracks or pinholes may occur in the battery packaging material. And this is the storage environment and transportation from the manufacture of the packaging material for batteries to the time when it is used for molding, regardless of whether the amide-based lubricant is blended in the heat-sealing resin layer or when it is coated. This is due to the fact that the amount of amide-based lubricant located on the surface of the heat-sealing resin layer changes significantly due to the environment, especially the temperature change, during the period from the manufacture of the packaging material for batteries to the molding, such as the environment. .. Therefore, for example, although the same amount of amide-based lubricant was used when manufacturing the packaging material for batteries, the amount of amide-based lubricant located on the surface at the time of molding changes greatly depending on the storage environment and the like, and the mold is used. The amide-based lubricant may adhere to the amide-based lubricant to reduce the continuous productivity, or cracks or pinholes may occur in the packaging material for the battery. It should be noted that the storage environment from the manufacture of the battery packaging material to the time when it is subjected to molding, the transportation environment, and the environment between the manufacture of the battery packaging material and the time when it is subjected to molding, especially the temperature change, should be appropriately controlled. For example, although it is possible to suppress changes in the amount of amide-based lubricant between the manufacturing and molding of packaging materials for batteries, in reality, the storage environment and transportation environment may not be properly controlled, and battery manufacturing The problems of formability and continuous productivity may occur only after being subjected to molding.

On the other hand, the packaging material for a battery of the present invention contains at least one selected from the group consisting of an antioxidant, a light stabilizer, and a nucleating agent together with an amide-based lubricant. Since the amount of the amide-based lubricant located on the surface of the heat-bondable resin layer 4 has an absorption spectrum intensity ratio X suitable for moldability and continuous productivity, it is suitable for manufacturing a battery.

The thickness of the heat-sealing resin layer 4 is not particularly limited as long as it exhibits the function as the heat-sealing resin layer, but is preferably about 60 μm or less, more preferably about 15 to 40 μm.

[Adhesive layer 5]
In the packaging material for batteries of the present invention, the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-sealing resin layer 4 in order to firmly bond them.

The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the heat-sealing resin layer 4. As the resin used for forming the adhesive layer 5, the same adhesive as the adhesive exemplified in the adhesive layer 2 can be used in terms of the adhesive mechanism, the type of adhesive component, and the like. Further, as the resin used for forming the adhesive layer 5, polyolefin-based resins such as the polyolefins exemplified in the above-mentioned heat-sealing resin layer 4, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins can also be used. .. From the viewpoint of excellent adhesion between the barrier layer 3 and the heat-bondable resin layer 4, the polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene.

Further, from the viewpoint of making the battery packaging material excellent in shape stability after molding while reducing the thickness of the battery packaging material, the adhesive layer 5 is a curing of 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 examples as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat-sealing resin layer 4 can be exemplified.

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

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

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), and polymers or nurates thereof. Examples thereof include a mixture and a copolymer with another polymer.

The carbodiimide-based curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N = C = N-). As the carbodiimide-based curing agent, a polycarbodiimide compound having at least two or more carbodiimide groups 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-based curing agent include the Epocross series manufactured by Nippon Shokubai Co., Ltd.

The curing agent may be composed of two or more kinds of compounds from the viewpoint of enhancing the adhesion between the barrier layer 3 by the adhesive layer 5 and the heat-sealing resin layer 4.

The content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, more preferably in the range of about 0.1 to 30% by mass. It is more preferably in the range of about 0.1 to 10% by mass.

The thickness of the adhesive layer 5 is not particularly limited as long as it functions as an adhesive layer, but when the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 2 to 10 μm, more preferably 2 to 2. About 5 μm can be mentioned. Further, when the resin exemplified in the heat-sealing resin layer 4 is used, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. Further, in the case of a cured product of the acid-modified polyolefin and the curing agent, it is preferably about 30 μm or less, more preferably about 0.1 to 20 μm, and further preferably about 0.5 to 5 μm. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.

[Surface coating layer 6]
In the packaging material for a battery of the present invention, for the purpose of improving designability, electrolytic solution resistance, scratch resistance, moldability, etc., as necessary, above the base material layer 1 (barrier layer of the base material layer 1). A surface covering layer 6 may be provided on the side opposite to 3), if necessary. The surface coating layer 6 is a layer located on the outermost layer when the battery is assembled.

The surface coating layer 6 can be formed of, for example, polyvinylidene chloride, a polyester resin, a urethane resin, an acrylic resin, an epoxy resin, or the like. Among these, the surface coating layer 6 is preferably formed of a two-component curable resin. Examples of the two-component curable resin forming the surface coating layer 6 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 added to the surface coating layer 6.

Examples of the additive include fine particles having a particle size of 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. The shape of the additive is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape. As additives, specifically, talc, silica, graphite, kaolin, montmoriloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodium 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 Examples thereof include melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel. These additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. Further, the additive may be subjected to various surface treatments such as an insulation treatment and a high dispersibility treatment on the surface.

The method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer 6 on one surface of the base material layer 1. When the additive is blended, the additive may be added to the two-component curable resin, mixed, and then applied.

The thickness of the surface coating layer 6 is not particularly limited as long as it exhibits the above-mentioned functions as the surface coating layer 6, and examples thereof include about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. 3. Method for Manufacturing Battery Packaging Material The method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate in which each layer having a predetermined composition is laminated can be obtained. An example of the method for manufacturing the packaging material for a battery of the present invention is as follows. First, a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order (hereinafter, may be referred to as “laminate A”) is formed. Specifically, the laminated body A is formed by applying an adhesive used for forming the adhesive layer 2 on the base material layer 1 or, if necessary, on the barrier layer 3 having a chemical conversion treatment on the surface, by a gravure coating method. It can be carried out by a dry laminating method in which the barrier layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a roll coating method.

Next, the adhesive layer 5 and the heat-sealing resin layer 4 are laminated on the barrier layer 3 of the laminated body A in this order. For example, (1) a method of laminating the adhesive layer 5 and the heat-sealing resin layer 4 on the barrier layer 3 of the laminated body A by co-extruding (co-extruded laminating method), (2) separately, the adhesive layer 5 A method of forming a laminated body in which the heat-sealing resin layer 4 is laminated and laminating this on the barrier layer 3 of the laminated body A by a thermal laminating method. (3) Adhesive on the barrier layer 3 of the laminated body A. An adhesive for forming the layer 5 is laminated by an extrusion method, solution coating, drying at a high temperature, baking, or the like, and a heat-sealing resin layer 4 is previously formed into a sheet on the adhesive layer 5. A method of laminating by a thermal laminating method, (4) Adhesion while pouring a melted adhesive layer 5 between the barrier layer 3 of the laminated body A and the heat-bondable resin layer 4 formed in the form of a sheet in advance. Examples thereof include a method of laminating the laminate A and the heat-sealing resin layer 4 via the layer 5 (sandwich laminating method).

When the surface coating layer is provided, the surface coating layer is laminated on the surface of the base material layer 1 opposite to the barrier layer 3. The surface coating layer can be formed, for example, by applying the above resin forming the surface coating layer to the surface of the base material layer 1. The order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 is not particularly limited. For example, after forming the surface coating layer on the surface of the base material layer 1, the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.

As described above, the surface coating layer 6 provided as needed / the base material layer 1 / the adhesive layer 2 provided as needed / the barrier layer 3 / the adhesive layer 5 whose surface is chemically treated as needed. / A laminate composed of a heat-bondable resin layer 4 is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 or the adhesive layer 5, a hot roll contact type, a hot air type, near or far infrared rays are further formed. It may be subjected to the heat treatment of the formula or the like. Examples of the conditions for such heat treatment include 1 minute to 5 minutes at 150 ° C. to 250 ° C.

In the packaging material for batteries of the present invention, each layer constituting the laminated body improves or stabilizes film forming property, laminating process, suitability for secondary processing (pouching, embossing) of the final product, etc., as necessary. Therefore, surface activation treatments such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

In the method for producing a battery packaging material of the present invention, after preparing the battery packaging material laminated in this way, the above-mentioned intensity ratio X = A / B measurement method and calculation method by infrared absorption spectrum measurement are performed. The absorption spectrum intensity ratio X = A / B is in the range of 0.05 to 0.80 (more specifically, the attenuation of the Fourier-converted infrared spectroscopic analysis method from the outermost surface side of the heat-sealing resin layer. When the infrared absorption spectrum is acquired by the total reflection method, the absorption spectrum intensity ratio X = A / B is 0.05 to 0. By performing the step of confirming that it is in the range of 80), the packaging material for a battery of the present invention having high moldability and excellent continuous productivity of a battery can be produced.

4. Applications of Battery Packaging Materials The battery packaging materials of the present invention are used for packaging for sealing and accommodating battery elements such as positive electrodes, negative electrodes, and electrolytes. That is, a battery element having at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the packaging material for a battery of the present invention to form a battery.

Specifically, a battery element having at least a positive electrode, a negative electrode, and an electrolyte is used in the battery packaging material of the present invention, with metal terminals connected to each of the positive electrode and the negative electrode projecting outward. A battery is formed by covering the peripheral edge of an element so that a flange portion (a region where the heat-sealing resin layers come into contact with each other) can be formed, and heat-sealing and sealing the heat-sealing resin layers of the flange portion. Batteries using packaging materials are provided. When the battery element is housed in the package formed of the battery packaging material of the present invention, the heat-sealing resin portion of the battery packaging material of the present invention is on the inside (the surface in contact with the battery element). To form a package.

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 the secondary battery to which the packaging material for a battery of the present invention is applied is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, a lead livestock battery, a nickel / hydrogen livestock battery, and a nickel / cadmium livestock battery. , Nickel / iron livestock battery, nickel / zinc livestock battery, silver oxide / zinc livestock battery, metal air battery, polyvalent cation battery, condenser, capacitor and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the battery packaging material of the present invention.

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

Examples 1-10 and Comparative Example 1-9
<Manufacturing of packaging materials for batteries>
Aluminum foil (JIS H 4000: 2014 A8021P-O, thickness 40 μm) on which both sides were subjected to chemical conversion treatment on a substrate layer (thickness 25 μm for a single layer) formed of the resin shown in Table 1, respectively. ) Was laminated by the dry laminating method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil to form an adhesive layer (thickness 3 μm) on the barrier layer. Next, after laminating the adhesive layer and the base material layer on the barrier layer, an aging treatment was carried out to prepare a laminated body of the base material layer / adhesive layer / barrier layer. In the chemical conversion treatment of the aluminum foil used as the barrier layer, a treatment liquid consisting of a phenol resin, a chromium fluoride compound, and phosphoric acid was roll-coated so that the coating amount of chromium was 10 mg / m ² (dry mass). This was done by applying and baking on both sides of the aluminum foil by the method.

In Table 1, Ny is nylon, PET is polyethylene terephthalate, PBT is polybutylene terephthalate, AL is aluminum alloy, SUS is stainless steel, PPa is maleic anhydride-modified polypropylene, PP is random polypropylene, and PE is high-density polyethylene. means. The PET / Ny used as the base material layer is a laminate of a PET film (12 μm) and a Ny film (15 μm) (the PET film and the Ny film are bonded with a two-component urethane adhesive 3 μm). , PET is located on the outermost layer side.

Next, on the barrier layer of the laminated body, an adhesive layer made of the resin shown in Table 1 (thickness 23 μm, arranged on the barrier layer side), the following additives A to C, and a lubricant (1400 ppm of erucic acid amide). ) Was co-extruded from the heat-sealing resin layer (thickness 23 μm, innermost layer) made of the resin shown in Table 1 to laminate the adhesive layer / heat-sealing resin layer on the barrier layer. .. Next, the obtained laminate is aged and finally heated to obtain a battery packaging material in which a base material layer, an adhesive layer, a barrier layer, an adhesive layer, and a heat-sealing resin layer are laminated in this order. Obtained.

Details of antioxidants, light stabilizers, and nucleating agents are as follows.
Additive A: Phenolic antioxidant (ADEKA AO-20 manufactured by ADEKA)
Additive B: Hindered amine-based light stabilizer (ADEKA's ADEKA STAB LA-57)
Additive C: Nucleating agent (ADEKA STUB NA-11 manufactured by ADEKA)

(Measurement of infrared absorption spectrum by infrared spectroscopy)
Each battery packaging material obtained above was cut into 100 mm × 100 mm squares to prepare a sample. The surface of the sealant layer of this sample was measured by infrared absorption spectrum using the ATR mode of Thermo Fisher Scientific Co., Ltd .: Nicolet iS10 FT-IR at a temperature of 25 ° C. and a relative humidity of 50%. From the obtained absorption spectrum, the absorption peak intensity A having a wave number of 1650 cm-1 derived from the C = O expansion and contraction vibration of the amide group and the absorption peak intensity B having a wave number of 1460 cm-1 derived from the -CH ₂ -variable vibration were obtained. The measurement was performed, and the absorption spectrum intensity ratio X = A / B of the absorption peak intensity A to the absorption peak intensity B was calculated. The results are shown in Table 1.
(Measurement conditions of infrared absorption spectrum)
Method: Macro ATR method Detector: TGS
Wavenumber resolution: 4 cm-1
Number of integrations: 32 times Prism: Germanium Baseline: Average value of intensity in the range of wave number 1900 cm-1 to 2000 cm-1 Absorption peak intensity A: Base from the maximum value of absorption peak intensity in the range of wave number 1635 cm-1 to 1665 cm-1 Value obtained by subtracting the line value Absorption peak intensity B: Value obtained by subtracting the baseline value from the maximum value of the absorption peak intensity in the range of wave number 1435 cm-1 to 1475 cm-1.

(Evaluation of moldability)
Each battery packaging material obtained above was cut into 80 mm × 120 mm squares to prepare a sample. This sample is formed into a forming mold having a diameter of 30 × 50 mm (female mold, surface is JIS B 0659-1: 2002 Annex 1 (reference) Maximum height specified in Table 2 of the comparative surface roughness standard piece). Roughness (nominal value of Rz) is 3.2 μm) and the corresponding molding die (male mold, surface is JIS B 0659-1: 2002 Annex 1 (reference) Surface roughness standard for comparison) Using the maximum height roughness (nominal value of Rz) of 1.6 μm specified in Table 2 of the piece, molding is performed in 0.5 mm increments from a molding depth of 0.5 mm at a pressing pressure of 0.4 MPa. Cold forming was performed on each of the 10 samples at different depths. For the sample after cold forming, the deepest forming depth at which no wrinkles or pinholes or cracks were generated in all 10 samples was defined as the limit forming depth of the sample. From this limit molding depth, the moldability of the battery packaging material was evaluated according to the following criteria. The results are shown in Table 1.
5: Limit molding depth 6.0 mm or more 4: Limit molding depth 5.5 mm or more and less than 6.0 mm 3: Limit molding depth 5.0 mm or more and less than 5.5 mm 2: Limit molding depth 4.5 mm or more 5. Less than 0 mm 1: Limit molding depth 4.0 mm or more and less than 4.5 mm 0: Limit molding depth less than 3.5 mm

(Evaluation of continuous battery productivity)
The corners of the mold after the above moldability evaluation are visually observed, and the case where the lubricant is transferred to the mold and whitened is unsuitable for continuous moldability (evaluation C), and the case where the mold is not whitened. Was evaluated as having very high continuous moldability (evaluation A), and the case where the lubricant was transferred to the mold and slightly whitened was regarded as high continuous productivity (evaluation B). The results are shown in Table 1.

1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-sealing resin layer 5 Adhesive layer 6 Surface coating layer

Claims (6)

It is composed of a laminate having at least a base material layer, a barrier layer, and a heat-sealing resin layer in this order.
The heat-sealing resin layer contains a phenol-based antioxidant and an amide-based lubricant.
The content of the phenolic antioxidant contained in the heat-sealing resin layer is 300 ppm or more and 1500 ppm or less.
From the absorption spectrum obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays, the absorption of the wave number 1650 cm ^-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant. The said with respect to the absorption peak intensity B calculated by measuring the peak intensity A and the absorption peak intensity B having a wave number of 1460 cm ^-1 derived from −CH ₂ − variable angle vibration contained in the heat-sealing resin layer. A packaging material for a battery, wherein the absorption spectrum intensity ratio X = A / B of the absorption peak intensity A is in the range of 0.17 or more and 0.66 or less. The battery packaging material according to claim 1 , wherein the heat-sealing resin layer further contains a plasticizer. The packaging material for a battery according to claim 1 or 2 , wherein the heat-sealing resin layer further contains a flame retardant. The packaging material for a battery according to any one of claims 1 to 3 , wherein the heat-sealing resin layer contains polyolefin and the content of the amide-based lubricant is 500 ppm or more and 2000 ppm or less. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is housed in a package formed of the battery packaging material according to any one of claims 1 to 4 . At least, a step of preparing a battery packaging material composed of a laminate in which a base material layer, a barrier layer, and a heat-sealing resin layer containing a phenol-based antioxidant and an amide-based lubricant are laminated in this order.
From the absorption spectrum obtained by spectroscopically reflecting the reflected light when the surface of the heat-sealing resin layer is irradiated with infrared rays, the absorption of the wave number 1650 cm ^-1 derived from the C = O expansion and contraction vibration of the amide group of the amide-based lubricant. The said with respect to the absorption peak intensity B calculated by measuring the peak intensity A and the absorption peak intensity B having a wave number of 1460 cm ^-1 derived from −CH ₂ − variable angle vibration contained in the heat-sealing resin layer. A step of confirming that the absorption spectrum intensity ratio X = A / B of the absorption peak intensity A is in the range of 0.17 or more and 0.66 or less, and
Equipped with
A method for producing a packaging material for a battery, wherein the content of the phenolic antioxidant contained in the heat-sealing resin layer is 300 ppm or more and 1500 ppm or less.

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