CN111033787B

CN111033787B - Resist film, packaging material, and method for producing packaging material

Info

Publication number: CN111033787B
Application number: CN201880050499.3A
Authority: CN
Inventors: 望月洋一; 藤原亮; 瓜生敏史; 高萩敦子; 山下力也; 畑中秀仁
Original assignee: Dai Nippon Printing Co Ltd
Current assignee: Dai Nippon Printing Co Ltd
Priority date: 2017-08-03
Filing date: 2018-08-03
Publication date: 2023-09-05
Anticipated expiration: 2038-08-03
Also published as: JPWO2019027052A1; CN111033787A; WO2019027052A1; CN117039283A; JP6525121B1

Abstract

The packaging material for a battery of the first invention is composed of a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order, wherein the surface of the barrier layer on the adhesive layer side has a resist film in contact with the adhesive layer, and the resist film detects peak P of C1s from an o—c=o bond in the range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C‑C The peak P _OCO Divided by the height of peak P _C‑C The peak height ratio value P obtained by the height of (2) _COOH/C‑C Is in the range of 0.10 to 0.50 inclusive.

Description

Resist film, packaging material, and method for producing packaging material

Technical Field

The present invention relates to a resist film, a packaging material, a method for producing a packaging material, a metal material with a resist film and a metal material with a resin film, a packaging material for a battery, a method for producing a packaging material for a battery, and a battery.

Background

Currently, various types of batteries have been developed. In these batteries, it is necessary to encapsulate a battery element composed of an electrode, an electrolyte, and the like with a packaging material or the like. As a packaging material for a battery, a packaging material made of metal is widely used.

In recent years, with the increase in performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, cellular phones, and the like, batteries having various shapes have been demanded. In addition, the battery is required to be thin and lightweight. However, it is difficult to cope with the diversification of the battery shape by using a metal packaging material that is currently in widespread use. In addition, since the packaging material is made of metal, there is a limit to the weight reduction of the packaging material.

Therefore, as a packaging material for a battery which can be easily processed into various shapes and can be thinned and lightened, a film-like laminate in which a base material layer, a barrier layer, and a heat-fusible resin layer are laminated in this order has been proposed (for example, refer to patent document 1).

In such a film-shaped battery packaging material, a recess is generally formed by molding, and battery elements such as an electrode and an electrolyte are disposed in a space formed by the recess, and the heat-fusible resin layers are heat-fused to each other, whereby a battery in which the battery elements are housed in the battery packaging material can be obtained.

In addition, conventionally, as materials for packaging foods, medicines, cosmetics, cleaning agents, battery elements (electrolytic solutions, electrodes, etc.), etc., film-shaped packaging materials are known in which a base material layer is laminated on one surface of a barrier layer made of metal, etc., and a heat-fusible resin layer is laminated on the other surface. For example, patent document 2 discloses a heat sterilization packaging material in which a base film layer, a barrier layer, and a sealing layer are laminated in this order.

In such a packaging material comprising a film-like laminate, the heat-sealable resin layers are molded so as to face each other, and a space capable of accommodating the contents is provided, and the contents are accommodated in the space, whereby the heat-sealable resin layers are heat-sealed to each other.

For example, when such a film-shaped packaging material having a barrier layer is used as a packaging material for packaging foods and the like, the foods as the contents are sealed, whereby the contents can be protected from light, oxygen, moisture, bacteria and the like. The content is a pharmaceutical product, a cosmetic product, a cleaning agent, a battery element, or the like, and can be protected by sealing the content with a packaging material.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2008-287971

Patent document 2: japanese patent laid-open No. 2008-94401

Disclosure of Invention

Technical problem to be solved by the invention

(first invention)

When moisture intrudes into the battery, the moisture reacts with an electrolyte or the like to generate an acidic substance. For example, it is known that an electrolyte solution used in a lithium ion battery or the like contains a fluorine compound (LiPF ₆ 、LiBF ₄ Etc.), the fluorine compound reacts with water to generate hydrogen fluoride as an acid component.

The barrier layer of a battery packaging material formed of a film-like laminate is usually made of a metal foil or the like, and there is a problem that corrosion is likely to occur when an acid comes into contact with the barrier layer. As a technique for improving the acid resistance of such a battery packaging material, a technique of using a barrier layer formed with a resist film on the surface thereof by chemical surface treatment is known.

Conventionally, as chemical surface treatments for forming a resist film, various methods such as chromate treatment using a chromium compound such as chromium oxide and phosphoric acid treatment using a phosphoric acid compound have been known.

The corrosion of the barrier layer can be suppressed by forming a resist film on the surface of the barrier layer, but it is required to improve the adhesion between the resist film on the surface of the barrier layer and the layer in contact with the resist film. For example, in order to improve the adhesion between the barrier layer and the heat-fusible resin layer, an adhesive layer may be provided between the barrier layer and the heat-fusible resin layer.

In recent years, the use of batteries has been in various aspects, and in view of long-term use in severe environments, further improvement of adhesion between a barrier layer and a heat-fusible resin layer has been demanded.

Under such circumstances, a primary object of the first invention is to provide a packaging material for a battery, which is composed of a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order, and which is excellent in adhesion between a resist film provided on the surface of the barrier layer and the adhesive layer in contact with the resist film. Further, the first invention is also directed to a method for producing the battery packaging material and a battery using the battery packaging material.

(second invention)

Further, although corrosion of the barrier layer can be suppressed by forming a resist film on the surface of the barrier layer, it is also required to improve adhesion between the resist film on the surface of the barrier layer and the layer in contact therewith. For example, in order to improve the adhesion between the barrier layer and the base material layer, an adhesive layer may be provided between the barrier layer and the base material layer.

In recent years, the use of batteries has been in various aspects, and in view of long-term use in severe environments, further improvement of adhesion between a barrier layer and a base material layer has been demanded.

Under such circumstances, a main object of the second invention is to provide a packaging material for a battery, which is composed of a laminate comprising at least a base material layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order, and which is excellent in adhesion between a resist film provided on the surface of the barrier layer and the adhesive layer in contact with the resist film. Further, another object of the second invention is to provide a method for producing the battery packaging material and a battery using the battery packaging material.

(third invention)

The types of contents sealed with the film-like packaging material described above are various. For example, in the case of foods, there are cases where an acid component such as vinegar or an alcohol component that causes corrosion of the barrier layer is sealed. When used as a packaging material for retort sterilization, the packaging material is exposed to a high-temperature environment of 100 ℃ or higher in a state of containing contents. In addition, acidic or basic contents are also present in pharmaceuticals, cosmetics, cleaning agents, and the like.

In addition, battery elements such as an electrolyte and an electrode may be sealed in the packaging material to be used as a battery. For example, it is known that an electrolyte solution used in a lithium ion battery or the like contains a fluorine compound (LiPF ₆ 、LiBF ₄ Etc.), hydrogen fluoride is generated as an acid component upon reaction of the fluorine compound with water.

The barrier layer of a packaging material formed of a film-like laminate is generally formed of a metal foil or the like, and there is a problem that the acid component or the alkali component from the content is easily corroded when the acid component or the alkali component comes into contact with the barrier layer. As a technique for improving the corrosion resistance of such a packaging material, a technique of using a barrier layer formed with a corrosion-resistant coating film on the surface thereof by chemical surface treatment is known.

In recent years, various types of contents and applications of packaging materials have been used, and further improvement of adhesion between the barrier layer and the heat-fusible resin layer has been demanded.

In addition, metallic materials are used in a wide range of fields. Since the surface of a metal material is susceptible to corrosion by an acid or the like, a technique of providing a resist film as described above on the surface of a metal material is known.

Further, in the metal material, in order to improve the protective performance and the design, the surface may be covered with a resin film. Metal materials covered with resin films are widely used in the fields of automobile parts, home electric appliances, building materials, containers for beverages, and the like. Examples of the method for forming the resin coating layer on the metal material include coating, film lamination, and printing.

A resist coating film is also provided as a base treatment on the surface of such a metal material on which a resin film is laminated, and further improvement of adhesion between the resin film and the metal material is required.

Under such circumstances, a main object of the third invention is to provide a resist film capable of suppressing a decrease in adhesion between a metal material (e.g., a barrier layer of a packaging material or the like) and a resin layer (e.g., the adhesive layer or the resin film or the like) provided thereon in an atmosphere in which a component such as an electrolyte solution or the like causes corrosion of the metal material. Further, another object of the third invention is to provide a packaging material comprising a laminate comprising at least a base layer, a barrier layer and a heat-fusible resin layer in this order, wherein the deterioration of adhesion between a resist film provided on the surface of the barrier layer and a layer in contact with the resist film can be suppressed in an atmosphere in which a component such as an electrolyte solution causes corrosion of the barrier layer. Further, another object of the third invention is to provide a metal material with a resist film having a resist film on a surface of the metal material, and a metal material with a resin film having a resin film on the resist film.

Technical scheme for solving technical problems

(first invention)

The present inventors have made intensive studies to solve the above-described problems of the first invention. As a result, it was found that a packaging material for a battery, which comprises a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order, has a resist film in contact with the adhesive layer on the surface of the adhesive layer side of the barrier layer, and detects a peak P from an o—c=o bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy (XPS) _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C When the thickness is in the range of 0.10 to 0.50, the adhesion between the resist film provided on the surface of the barrier layer and the adhesive layer in contact therewith is excellent.

The first invention was completed based on further repeated studies based on these findings.

That is, the first invention provides the following aspects of the invention.

A packaging material for a battery, comprising a laminate having at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order,

The surface of the barrier layer on the adhesive layer side has a resist film in contact with the adhesive layer,

the resist film detects peak P of C1s from O-c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C ，

The peak P _OCO Divided by the height of the peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C Is in the range of 0.10 to 0.50 inclusive.

(second invention)

The inventors of the present invention have made intensive studies to solve the above-described problems of the second invention. As a result, it was found that a packaging material for a battery, which comprises a laminate having at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order, has a resist film in contact with the adhesive layer on the surface of the barrier layer on the adhesive layer side, and the resist film detects a peak P from an o—c=o bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy (XPS) _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C When the thickness is in the range of 0.10 to 0.50, the adhesion between the resist film provided on the surface of the barrier layer and the adhesive layer in contact therewith is excellent.

The second invention was completed based on further repeated studies based on these findings.

That is, the second invention provides the following embodiments.

A packaging material for a battery, comprising a laminate having at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order,

(third invention)

In order to solve the third problem as described above, the present inventors have also found thatThe technical problems are clear, and the intensive research is carried out. As a result, a resist film was found in which peak P of C1s derived from O-C=O bond was detected in the range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of the peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50, the resist film can suppress a decrease in adhesion between a metal material such as a barrier layer of a packaging material and a resin layer such as an adhesive layer or a resin film in an atmosphere in which a component that causes corrosion of the metal material such as an electrolyte is present.

The third invention was completed based on these findings and further repeated studies.

That is, the third invention provides the following embodiments.

A resist film in which a peak P of C1s derived from an O-C=O bond is detected in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C ，

Effects of the invention

(first invention)

With the first invention, it is possible to provide a packaging material for a battery which is composed of a laminate having at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, and which is excellent in adhesion between a resist film provided on the surface of the barrier layer and the adhesive layer in contact with the resist film. Further, according to the first invention, a method for producing the battery packaging material and a battery using the battery packaging material can be provided.

(second invention)

With the second aspect of the present invention, there can be provided a packaging material for a battery comprising a laminate comprising at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order, wherein the packaging material for a battery has excellent adhesion between a resist film provided on the surface of the barrier layer and the adhesive layer in contact with the resist film. Further, according to the second aspect of the present invention, there can be provided a method for producing the battery packaging material and a battery using the battery packaging material.

(third invention)

With the third invention, it is possible to provide a resist film capable of suppressing a decrease in adhesion between a metal material and a resin layer provided thereon in an atmosphere in which a component such as an electrolyte solution that causes corrosion of the metal material is present. Further, according to the third aspect of the present invention, there can be provided a packaging material comprising a laminate comprising at least a base layer, a barrier layer, and a heat-fusible resin layer in this order, wherein the deterioration of adhesion between a resist film provided on the surface of the barrier layer and a layer in contact with the resist film can be suppressed in an atmosphere in which a component such as an electrolyte solution causes corrosion of a metal material. Further, according to the third aspect of the present invention, there can be provided a metal material with a resist film having a resist film on a surface of the metal material, and a metal material with a resin film having a resin film on the resist film.

Drawings

Fig. 1 is a schematic view showing an example of a cross-sectional structure of a battery packaging material according to a first aspect of the present invention.

Fig. 2 is a schematic view showing an example of a cross-sectional structure of the battery packaging material according to the first invention.

Fig. 3 is a schematic view showing an example of a cross-sectional structure of the battery packaging material according to the first invention.

Fig. 4 is a schematic view showing an example of a cross-sectional structure of the battery packaging material according to the first invention.

Fig. 5 is a schematic view showing an example of a cross-sectional structure of a battery packaging material according to a second aspect of the present invention.

Fig. 6 is a schematic view showing an example of a cross-sectional structure of a battery packaging material according to a second aspect of the present invention.

Fig. 7 is a schematic view showing an example of a cross-sectional structure of a battery packaging material according to a second aspect of the present invention.

Fig. 8 is a schematic view showing an example of a cross-sectional structure of a battery packaging material according to a second aspect of the present invention.

Fig. 9 is a schematic view showing an example of a cross-sectional structure of a packaging material according to a third invention.

Fig. 10 is a schematic view showing an example of a cross-sectional structure of a packaging material according to a third invention.

Fig. 11 is a schematic view showing an example of a cross-sectional structure of a packaging material according to a third invention.

Fig. 12 is a schematic view showing an example of a cross-sectional structure of a packaging material according to a third invention.

Fig. 13 is a schematic view showing an example of a cross-sectional structure of a metal material with a resist film according to the third invention.

Fig. 14 is a schematic view showing an example of a cross-sectional structure of a metal material with a resin film according to a third aspect of the present invention.

Detailed Description

The present invention includes the following first, second and third inventions. Hereinafter, the first invention will be described in detail first, and then the second and third inventions will be described in detail sequentially. In the description of the second and third aspects of the present invention, the description of the contents overlapping with those of the first aspect of the present invention will be omitted as appropriate.

In the present specification, the numerical ranges indicated by "to" refer to "above" and "below". For example, the expression of 2 to 15mm means 2mm to 15 mm.

(first invention)

The packaging material for a battery of the first invention is characterized by comprising a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order, wherein the surface of the barrier layer on the adhesive layer side has a resist film in contact with the adhesive layer, and the resist film is detected in the range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy (hereinafter also referred to as XPS) To peak P from O-c=o bond _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C Is in the range of 0.10 to 0.50 inclusive. Hereinafter, a packaging material for a battery, a method for manufacturing the packaging material for a battery, and a battery using the packaging material for a battery according to a first aspect of the invention will be described in detail with reference to fig. 1 to 4.

1-1. Laminated structure of battery packaging material

The battery packaging material according to the first aspect of the present invention is composed of a laminate including at least a base material layer 1, a barrier layer 3, an adhesive layer 5, and a heat-fusible resin layer 4 in this order, as shown in fig. 1 to 4, for example. In the battery packaging material according to the first aspect of the invention, the base material layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. That is, when the battery is assembled, the heat-fusible resin layers 4 located at the peripheral edges of the battery element are heat-fused to each other to seal the battery element, whereby the battery element is packaged.

As shown in fig. 1 to 4, the battery packaging material according to the first invention has a resist film 3a in contact with the adhesive layer 5 on the surface of the barrier layer 3 on the adhesive layer 5 side. Fig. 1 is a schematic view showing that the resist film 3a is provided only on the surface of the barrier layer 3 on the adhesive layer 5 side. Fig. 2 and 4 are schematic views showing the case where the resist films 3a and 3b are provided on both sides of the barrier layer 3. As described below, in the battery packaging material according to the first aspect of the invention, the resist film 3a having peak characteristics detected by XPS analysis described below may be provided only on the surface of the barrier layer 3 on the adhesive layer 5 side, or the resist films 3a and 3b having peak characteristics detected by XPS analysis described below may be provided on both surfaces of the barrier layer 3.

As shown in fig. 2 to 4, the battery packaging material of the first invention may have an adhesive layer 2 between the base layer 1 and the barrier layer 3, if necessary, in order to improve the adhesion thereof. As shown in fig. 4, the battery packaging material of the first invention may further include a surface coating layer 6 on the side of the base material layer 1 opposite to the barrier layer 3 as needed in order to improve design properties, electrolyte resistance, scratch resistance, moldability, and the like.

The thickness of the laminate constituting the battery pack 10 of the first invention is not particularly limited, and from the viewpoint of reducing the thickness of the battery pack, improving the energy density of the battery, and forming a battery pack excellent in moldability, it is possible to cite, for example, 180 μm or less, preferably 150 μm or less, more preferably about 60 to 180 μm, and still more preferably about 60 to 150 μm.

1-2. Layers forming a battery packaging material

[ substrate layer 1]

In the battery packaging material according to the first aspect of the invention, the base material layer 1 is a layer located on the outermost layer side. The material for forming the base material layer 1 is not particularly limited as long as it has insulation properties. Examples of the material for forming the base layer 1 include resin films of polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicone resin, phenolic resin, polycarbonate resin, and mixtures and copolymers thereof. Among these, polyester resins and polyamide resins are preferable, and polyamide resins are more preferable. As the polyester resin, a biaxially stretched polyester resin is preferable, and as the polyamide resin, a biaxially stretched polyamide resin is preferable. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and copolyesters. Specific examples of the polyamide resin include nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 6,10, and poly (m-xylylene adipamide) (MXD 6).

The base material layer 1 may be formed of 1 resin film, but may be formed of 2 or more resin films in order to improve pinhole resistance and insulation. Specifically, a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like are cited. 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 obtained by laminating a plurality of biaxially stretched nylon films, or a laminate obtained by laminating a plurality of biaxially stretched polyester films is preferable. For example, when the base material layer 1 is formed of 2 resin films, it is preferable to form a laminate of a polyester resin and a polyester resin, a laminate of a polyamide resin and a polyamide resin, or a laminate of a polyester resin and a polyamide resin, and more preferable to form a laminate of polyethylene terephthalate and polyethylene terephthalate, a laminate of nylon and nylon, or a laminate of polyethylene terephthalate and nylon. Further, since the polyester resin is not likely to be discolored when the electrolyte is adhered to the surface, for example, in this laminated structure, the base material layer 1 is preferably laminated so that the polyester resin is located at the outermost layer. When the base material layer 1 is formed into a multilayer structure, the thickness of each layer is preferably about 2 to 25 μm.

When the base material layer 1 is formed of a plurality of resin films, 2 or more resin films may be laminated via a layer having an adhesive component such as an adhesive or an adhesive resin, and the kind and amount of the adhesive component used are the same as those of the adhesive layer 2 described later. Among them, the method of laminating 2 or more layers of resins is not particularly limited, and known methods may be used, and examples thereof include a dry lamination method, an interlayer lamination method, and a coextrusion lamination method, and a dry lamination method is preferable. When the lamination is performed by a dry lamination method, a polyurethane adhesive is preferably used as the adhesive layer. In this case, the thickness of the adhesive layer may be, for example, about 2 to 5. Mu.m.

In the first invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant is adhered to the surface of the base material layer 1. The lubricant is not particularly limited, and an amide-based lubricant is preferably used. Specific examples of the amide-based lubricant include the same lubricants as those exemplified for the heat-fusible resin layer 4 described later.

When a lubricant is present on the surface of the base material layer 1, the amount of the lubricant present is not particularly limited, and may be preferably about 3mg/m ² The above, more preferably 4 to 15mg/m ² Left and right, enterOne step preferably 5-14 mg/m ² Left and right.

The base material layer 1 may contain a lubricant. The lubricant present on the surface of the base material layer 1 may be a lubricant that is exuded from the resin constituting the base material layer 1, or may be a lubricant that is applied to the surface of the base material layer 1.

The thickness of the base material layer 1 is not particularly limited as long as the function as a base material layer can be exhibited, and examples thereof include about 3 to 50 μm, preferably about 10 to 35 μm.

[ adhesive layer 2]

In the battery packaging material 10 according to the first aspect of the invention, the adhesive layer 2 is a layer provided between the base layer 1 and the barrier layer 3 as needed to firmly adhere them. The adhesive layer 2 of the first invention may have the same structure as that shown in the adhesive layer 2 of the second invention described later.

The adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier layer 3. The adhesive used for forming the adhesive layer 2 may be a two-part curing adhesive or a one-part curing adhesive. The adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any type such as a chemical reaction type, a solvent evaporation type, a hot melt type, a hot press type, or 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 copolyesters; a polycarbonate resin; polyether resin; a polyurethane resin; an epoxy resin; phenolic resin; polyamide resins such as nylon 6, nylon 66, nylon 12 and copolyamide; polyolefin resins such as polyolefin, carboxylic acid-modified polyolefin and metal-modified polyolefin, and polyvinyl acetate resins; a cellulose-based adhesive; (meth) acrylic resins; polyimide resin; amino resins such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene-butadiene rubber, and other rubbers; silicone resins, and the like. These adhesive components may be used alone or in combination of at least 2 kinds. In addition, a suitable curing agent may be used in combination with the resin as the adhesive component to improve the adhesive strength. The curing agent is selected from a group consisting of polyisocyanate, polyfunctional epoxy resin, oxazoline group-containing polymer, polyamine resin, acid anhydride and the like, depending on the functional group of the adhesive component. As these adhesive components and curing agents, polyurethane adhesives composed of various polyols (those having hydroxyl groups in the adhesive components) and polyisocyanates are preferable. Further preferred examples of the two-part curable polyurethane adhesive include a two-part curable polyurethane adhesive comprising a main component of a polyol such as a polyester polyol, a polyether polyol and an acrylic polyol and a curing agent of an aromatic or aliphatic polyisocyanate.

The adhesive layer 2 may contain a colorant such as a pigment.

The thickness of the adhesive layer 2 is not particularly limited as long as the adhesive layer can function, 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 has a function of preventing intrusion of water vapor, oxygen, light, and the like into the battery in addition to a function of improving the strength of the battery packaging material. The barrier layer 3 is preferably a metal layer, i.e. a layer formed of metal. The metal constituting the barrier layer 3 may be specifically aluminum, stainless steel, titanium, or the like, and aluminum is preferable. The barrier layer 3 may be formed of, for example, a metal foil or a metal vapor deposition film, a film provided with these vapor deposition films, or the like, and is preferably formed of a metal foil, more preferably an aluminum foil.

When the barrier layer 3 is made of aluminum foil, the aluminum foil is formed of aluminum alloy. In the production of a packaging material for a battery, the barrier layer is more preferably formed of a soft aluminum foil such as annealed aluminum (JIS H4160:1994A8021H-O, JIS H4160:1994A 8079H-O, JIS H4000: 2014A 8021P-O, JIS H4000: 2014A 8079P-O) or the like, for example, from the viewpoint of preventing wrinkles or pinholes from occurring in the barrier layer 3.

Examples of the stainless steel foil include austenitic stainless steel foil and ferritic stainless steel foil. The stainless steel foil is preferably made of austenitic stainless steel.

Specific examples of austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, and SUS316L, and among these, SUS304 is particularly preferred.

The thickness of the barrier layer 3 is not particularly limited as long as it can function as a barrier layer for water vapor or the like, and from the viewpoint of reducing the thickness of the packaging material, the upper limit is preferably about 100 μm or less, more preferably about 80 μm or less, the lower limit is preferably about 10 μm or more, and the thickness range is preferably about 10 to 100 μm or so, and about 10 to 80 μm or so. This thickness is particularly suitable in the case where the barrier layer 3 is composed of an aluminium alloy foil. When the barrier layer 3 is made of a stainless steel foil, the thickness of the stainless steel foil is preferably about 85 μm or less, more preferably about 50 μm or less, still more preferably about 40 μm or less, still more preferably about 30 μm or less, and particularly preferably about 25 μm or less, and the lower limit thereof is about 10 μm or more, and the preferred thickness range is about 10 to 85 μm, about 10 to 50 μm, more preferably about 10 to 40 μm, more preferably about 10 to 30 μm, and still more preferably about 15 to 25 μm.

[ resist films 3a, 3b ]

In the battery packaging material according to the first aspect of the invention, the surface of the barrier layer 3 on the adhesive layer 5 side has a resist film 3a that contacts the adhesive layer 5.

The packaging material for a battery of the first invention is characterized in that the resist film 3a detects a peak P from an o—c=o bond in a range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy (XPS) _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50. By the value P of the peak height ratio _OCO/C-C Within such a specific range, the adhesion between the resist film 3a provided on the surface of the barrier layer 3 and the adhesive layer 5 in contact therewith is excellentDifferent from each other. The packaging material for a battery of the first invention has high adhesion between the resist film 3a and the adhesive layer 5, and can exhibit high peel strength even when subjected to a severe peel test as measured in examples, and can exhibit excellent adhesion over a long period of time.

The value P as the peak height ratio is a value from the viewpoint of further improving the adhesion between the resist film 3a and the adhesive layer 5 (and between the resist film 3b and the layer adjacent thereto, which will be described later) _OCO/C-C The lower limit may be preferably about 0.10, more preferably 0.15, and the upper limit may be preferably about 0.50. In addition, the value P is the peak height ratio _OCO/C-C The preferable range of (2) is about 0.10 to 0.50, more preferably about 0.15 to 0.50.

In the battery packaging material according to the first aspect of the present invention, from the viewpoint of further improving the adhesion between the resist film 3a and the adhesive layer 5 (and the resist film 3b described later and the layers adjacent thereto), the resist film 3a preferably detects the peak P of Cr2P3/2 from the chromium compound in the range of 576eV to 581eV by analysis using XPS _Cr . By detecting this peak, it was confirmed that the composition for forming the resist film 3a by the chemical surface treatment contained a chromium compound. Cr atoms having-COOH groups, -NH groups in the coating ₂ The core action of the coordination bond is that the group, -CN group and the like, and therefore, the core action forms a bridging structure with other functional groups having a structure capable of forming a ligand, such as polycarboxylic acid or an ammonium salt thereof, and durability such as corrosion resistance and chemical resistance is achieved.

In the battery packaging material according to the first aspect of the present invention, the resist film 3a preferably detects the peak P of P2P derived from the phosphoric acid compound in the range of 132eV to 135eV by analysis using X-ray photoelectron spectroscopy _P . By detecting the peak P _P It was confirmed that phosphoric acid or a salt thereof was contained in the composition for forming the resist film 3a by the chemical surface treatment. In chemical surface treatment, phosphoric acid etches a metal surface to form a high-durability coating such as a phosphate compound coating on the metal surface. In addition, it is considered that the coordination number is high as in CrThe metal atoms are also incorporated into the above-mentioned coordination bridge structure, and thus contribute to adhesion of the metal surface to the above-mentioned high-durability coating film.

In the battery packaging material of the first invention, the resist film 3a preferably detects the peak of F1s from the fluorine compound in the range of 685eV to 689eV by analysis with XPS from the same point of view. By detecting the peak P _F It was confirmed that the composition for forming the resist film 3a by the chemical surface treatment contained a fluorine compound. When the barrier layer is aluminum, fluorine atoms are bonded to aluminum to form an aluminum fluoride coating film having higher durability than an aluminum oxide coating film.

Further, from the same point of view, in the packaging material for a battery of the second invention, the resist film 3b is preferably formed at the peak P by analysis by X-ray photoelectron spectroscopy _Cr Peak P _P Peak P _F At least peak P is detected in _Cr More preferably, in addition to peak P _Cr Peak P is detected in addition to _P Peak sum P _F At least one of them, particularly preferably peak P _Cr Peak P _P Peak sum P _F All detected.

In the battery packaging material according to the first aspect of the present invention, the packaging material may have, on only the surface of the separator 3 on the adhesive layer 5 side, the above-mentioned various peaks (i.e., the value P of the above-mentioned peak-to-peak ratio) detected by XPS analysis _OCO/C-C And peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F At least 1) of the resist film 3a, the resist film 3b having the various peaks may be provided on the surface of the barrier layer 3 on the substrate layer 1 side. By providing the resist film 3b, adhesion between the resist film 3b on the surface of the barrier layer 3 and a layer (for example, the adhesive layer 2) in contact with the resist film can be improved, and, for example, delamination between the base material layer 1 and the barrier layer 3 can be prevented when the resist film is exposed to high temperature and high humidity conditions.

The method of analyzing the resist films 3a and 3b using XPS can be specifically performed under the following measurement conditions using an X-ray photoelectron spectroscopy analyzer. Among them, the measurement conditions of the X-ray photoelectron spectroscopy can be referred to JIS K0162:2010.

(measurement conditions)

Incident X-rays: mg kα (non-monochromic X-ray, hν= 1253.6 eV)

X-ray output: 10kV 20mA (200W)

Optoelectronic entry angle: 90 degree (input lens is arranged on the line of the sample method)

Measurement area:

peak offset correction: among the C1s peaks, correction was made so that the binding energy at which the peak intensity was maximum reached 285eV.

When analyzing peak positions (binding energy) of a resist film laminated on a battery packaging material using XPS, first, a layer laminated on a barrier layer (heat-fusible resin layer, adhesive layer, or the like) on the side to be analyzed is physically peeled off. At this time, it is not physically peeled off by water, an organic solvent, an aqueous solution of an acid or a base, or the like. When the adhesive layer remains on the surface of the barrier layer after the separation between the barrier layer and the adhesive layer, the remaining adhesive layer is removed by etching using Ar-GCIB. The surface of the barrier layer thus obtained was analyzed for a resist film using XPS. In addition, when the layer laminated on the barrier layer on the side to be analyzed is an adhesive layer, the layers are physically peeled off and etched away in the same manner, and analysis is performed.

The presence or absence of the various peaks can be easily confirmed as a detected peak displayed on a monitor screen of the X-ray photoelectron spectroscopy apparatus when the peaks are clear, but when the peaks are small and not clear, the presence or absence of the relevant peak of the atom is determined based on the area, the half width, and the presence or absence of the relevant peak. Specifically, the following operations are performed and judged. First, (1) when the content of the component is determined to be 0.1% or more based on the peak area after background subtraction and curve fitting by the Shirley method, the peak is determined to be present. Then, as a supplementary method, the following cases and the like are used as judgment references: (2) The half width of the peak that occurs by the fit has a half width that is greater than the energy resolution of the device; and (3) a peak of photoelectrons from an outer orbit than the main peak is also confirmed in addition to the main peak. Among them, an X-ray photoelectron spectroscopy device is usually attached with analysis software, and in the example, "Vision Processing" manufactured by the device manufacturer Kratos is used.

The resist films 3a and 3b can be formed by chemically surface-treating the surface of the barrier layer 3. From a value P suitable for forming a peak having the above peak height ratio _OCO/C-C Peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F In terms of the resist film of at least 1, the resist films 3a, 3b are preferably formed of a composition containing at least an acrylic resin having COOH groups, a chromium compound, and a phosphoric acid compound. More specifically, the surface of the barrier layer 3 is chemically surface-treated with a treatment liquid containing these components, whereby the resist films 3a, 3b can be formed appropriately. The chemical surface treatment may be performed by applying a treatment liquid to the surface of the barrier layer 3 and performing a sintering treatment. In addition, by properly adjusting the composition of the treatment liquid, the treatment method and the treatment conditions, the peak height ratio value P can be set _OCO/C-C Adjusting to the above range.

From the value P of the peak height ratio _OCO/C-C In view of the above-mentioned range and further improvement of the adhesion between the resist film 3a and the adhesive layer 5 (and between the resist film 3b and the adjacent layers), the acrylic resin is preferably polyacrylic acid, an acrylic methacrylate copolymer, an acrylic maleic acid copolymer, an acrylic styrene copolymer, or a derivative such as sodium salt, ammonium salt, or amine salt thereof. Particularly preferred are derivatives of polyacrylic acid such as ammonium salts, sodium salts, or amine salts of polyacrylic acid. In the first invention, polyacrylic acid refers to a polymer of acrylic acid. The acrylic resin is also preferably a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, and is also preferably an ammonium salt, sodium salt or amine salt of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride. The acrylic resin may be Only 1 kind of the above-mentioned components may be used, or 2 or more kinds may be mixed and used.

From the same viewpoint, the weight average molecular weight of the acrylic resin may be preferably about 1000 to 100 ten thousand, more preferably about 3000 to 80 ten thousand, and still more preferably about 1 to 80 ten thousand. The higher the molecular weight, the higher the durability, but the water solubility of the acrylic resin decreases, and the coating liquid becomes unstable, and the manufacturing stability is lacking. Conversely, the smaller the molecular weight, the lower the durability. In the first invention, the acrylic resin has a weight average molecular weight of 1000 or more, and has high durability and good production stability when it has a weight average molecular weight of 100 ten thousand or less. In the first invention, the weight average molecular weight of the acrylic resin is a value measured under the condition of using polystyrene as a standard sample and measured by Gel Permeation Chromatography (GPC).

In addition, the acid value of the acrylic resin is preferably large because it is preferable to have a good effect of contributing to the adhesion property when COOH is more abundant, but when a salt is formed as described above, the amount of o—c=o bonds may not be reflected by the acid value, and therefore, as in the first invention, analysis of o—c=o bonds by a spectrum of XPS may be considered, which can reflect the adhesion property.

From the same point of view, the chromium compound is preferably at least one of chromium (III) fluoride and chromium (III) nitrate. As described above, it is considered that a coordination bridge structure with Cr atoms as the center or a high durability coating structure due to aluminum fluoride can be formed.

In addition, as a method of forming a high-durability film by imparting a bridge structure to the resist films 3a and 3b described above, there is also a method of using a crosslinking agent that reacts with COOH groups. As the crosslinking agent, a compound having an isocyanate group, a compound having an oxazoline group, a compound having an amino group, a compound having an epoxy group, or the like is suitably used.

The composition for forming the resist films 3a and 3b preferably further contains phosphoric acid. Phosphoric acid has a cleaning effect on the surface of the barrier layer (specifically, an effect of removing a deteriorated oxide film and stains on the surface of the barrier layer), and an effect of forming a bridging structure by forming phosphate ions in the sintered film and coordinating with metal ions such as the surface of the barrier layer and chromium ions. In the first invention, phosphoric acid is not necessary in view of achieving the same effect with respect to carboxylate ions of the resist film, but phosphoric acid is preferably used from the viewpoint of improving the cleaning effect of the barrier layer and stabilizing the mass production of the battery packaging material.

From the viewpoint of further improving the adhesion of the resist film 3a to the adhesive layer 5 (and the resist film 3b and the layers adjacent thereto), particularly preferable compositions of the composition (treatment liquid) for forming the resist films 3a, 3b include a composition containing polyacrylic acid, chromium (III) fluoride and phosphoric acid, a composition containing polyacrylic acid and chromium (III) fluoride, a composition containing an acrylic methacrylate copolymer, chromium (III) fluoride and phosphoric acid, a composition containing an acrylic methacrylate copolymer, chromium (III) nitrate and phosphoric acid, a composition containing a sodium salt of an acrylic maleic acid copolymer, a composition containing chromium (III) fluoride and phosphoric acid, a composition containing a styrene acrylate copolymer, chromium (III) fluoride and phosphoric acid, various salts (sodium salt, ammonium salt, amine salt, etc.) of polyacrylic acid, a composition containing chromium (III) fluoride and phosphoric acid.

The concentration of the solid content of the treatment liquid for forming the resist film is not limited as long as the value P having the peak height ratio can be formed by applying and sintering the treatment liquid to the barrier layer _OCO/C-C Peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F The resist film of at least 1 of these is not particularly limited, and may be, for example, about 1 to 10 mass%.

The thickness of the resist films 3a and 3b is not particularly limited, and from the viewpoint of effectively improving the adhesion between the resist film 3a and the adhesive layer 5 (and between the resist film 3b and the layer adjacent thereto), it is preferably about 1nm to 10 μm, more preferably about 1 to 100nm, and even more preferably about 1 to 50 nm. The thickness of the resist film can be measured by observation with a transmission electron microscope or by a combination of observation with a transmission electron microscope and energy dispersive X-ray spectrometry or electron beam energy loss spectrometry.

From the same point of view, every 1m as the barrier layer 3 ² The amount of Cr in the surface resist films 3a and 3b is preferably about 0.5 to 30%, more preferably about 1 to 20%, and still more preferably about 3 to 10% by mass.

Examples of the method of applying the composition for forming the resist films 3a and 3b to the surface of the barrier layer 3 include bar coating, roll coating, gravure coating, dipping, and the like.

From the value P of the peak height ratio _OCO/C-C The heating temperature at the time of forming the resist film by sintering the treatment liquid is preferably about 120 to 210 ℃, more preferably about 140 to 190 ℃, in view of improving the adhesion between the resist film 3a and the adhesive layer 5 (and between the resist film 3b and the layer adjacent thereto) within the above-described predetermined range. From the same viewpoint, the sintering time is preferably about 1 to 30 seconds, more preferably about 5 to 10 seconds.

From the viewpoint of more effectively chemically surface-treating the surface of the barrier layer 3, it is preferable to perform degreasing treatment by a known treatment method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method before providing a resist film on the surface of the barrier layer 3.

[ adhesive layer 5]

In the battery packaging material according to the first aspect of the invention, the adhesive layer 5 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 in order to improve adhesion therebetween. More specifically, the adhesive layer 5 is provided so as to be in contact with the resist film 3a on the surface of the barrier layer 3.

In general, from the viewpoint of improving the adhesion between the barrier layer and the heat-fusible resin layer, it is preferable to have an adhesive layer between them, but when a resist film is provided on the heat-fusible resin layer side surface of the barrier layer, the adhesion between the resist film and the adhesive layer may be reduced. In contrast, in the battery packaging material according to the first aspect of the invention, the resist film 3a has the above-described value P of the specific peak height ratio _OCO/C-C Because ofThis can effectively improve the adhesion between the resist film 3a and the adhesive layer 5. That is, in the battery packaging material according to the first aspect of the present invention, the effect of excellent adhesion between the barrier layer having the resist film and the inner layer can be particularly effectively exhibited in the case where the resist film 3a on the surface of the barrier layer 3 and the inner heat-fusible resin layer 4 are laminated via the adhesive layer 5.

The adhesive layer 5 is formed of a resin capable of adhering the resist film 3a to the heat-fusible resin layer 4. As the resin for forming the adhesive layer 5, for example, the same adhesive as the adhesive exemplified for the adhesive layer 2 can be used, for example, the adhesive mechanism and the kind of the adhesive component. As the resin for forming the adhesive layer 5, a polyolefin resin such as polyolefin, cyclic polyolefin, acid-modified cyclic polyolefin, or the like may be used, and a resin component exemplified by the heat-fusible resin layer 4 described later may be used. The resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the adhesive layer 5 contains a polyolefin skeleton and can be analyzed by, for example, infrared spectrometry, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited. In addition, when the resin constituting the adhesive layer 5 is analyzed by infrared spectroscopy, a peak derived from maleic anhydride is preferably detected. For example, when measuring maleic anhydride-modified polyolefin by infrared spectrometry, the measurement is carried out at a wave number of 1760cm ^-1 Nearby sum wave number 1780cm ^-1 The vicinity detects a peak from maleic anhydride. However, when the degree of acid modification is low, the peak may be small and undetectable. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.

From the viewpoint of improving the adhesion between the resist film 3a and the adhesive layer 5 (and between the resist film 3b and the adjacent layer), the adhesive layer 5 preferably contains an acid-modified polyolefin. The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of a polyolefin with an acid component such as a carboxylic acid. Examples of the acid component for modifying the polyolefin include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride and itaconic anhydride, and anhydrides thereof. Further, examples of the modified polyolefin include: polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; polypropylene such as homopolypropylene, a block copolymer of polypropylene (e.g., a block copolymer of propylene and ethylene), and a random copolymer of polypropylene (e.g., a random copolymer of propylene and ethylene); ethylene-butene-propylene terpolymers, and the like. Among these polyolefins, polyethylene and polypropylene are preferably cited.

As described above, the peak P from the o—c=o bond is detected in the resist coating 3a _OCO . By including the acid-modified polyolefin modified with carboxylic acid or the like in the adhesive layer 5 in contact with the resist film 3a, the adhesion between the resist film 3a and the adhesive layer 5 can be more effectively improved in view of the high affinity of carboxylic acids to each other. For example, the carboxyl group or various salts such as ammonium salt, sodium salt and amine salt of the carboxyl group, ester bond and the like contain o—c=o bond. From the viewpoint of particularly effectively improving the adhesion between the resist film 3a and the adhesive layer 5, the combination of the resist film 3a and the adhesive layer 5 includes a combination of the resist film 3a and the adhesive layer 5 in which a peak P of C1s from an o—c=o bond is detected in a range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy, in which a peak P of C1s from an o—c=o bond is detected when analyzed by infrared spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285.0eV _C-C And peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C Is in the range of 0.10 to 0.50 inclusive.

Among the acid-modified polyolefins in the adhesive layer 5, maleic anhydride-modified polyolefin is particularly preferred, and maleic anhydride-modified polypropylene is further preferred.

The adhesive layer 5 is more preferably a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. The acid-modified polyolefin is preferably exemplified by the above-mentioned polymers.

The adhesive layer 5 is preferably a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group, and particularly preferably a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. The adhesive layer 5 preferably contains at least 1 selected from the group consisting of polyurethane resin, ester resin, and epoxy resin, and more preferably contains polyurethane resin and epoxy resin. As the ester resin, for example, an amide ester resin is preferable. Amide ester resins are typically formed by the reaction of carboxyl groups with oxazoline groups. The adhesive layer 5 is more preferably a cured product of a resin composition containing at least 1 of these resins and the acid-modified polyolefin described above. When unreacted materials of a curing agent such as an isocyanate group-containing compound, an oxazoline group-containing compound, or an epoxy resin remain in the adhesive layer 5, the presence of the unreacted materials can be confirmed by a method selected from infrared spectroscopy, raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like, for example.

In addition, from the viewpoint of further improving the adhesion between the resist coating film 3a and the adhesive layer 5, the adhesive layer 5 is preferably a cured product of a resin composition containing a curing agent having at least 1 selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a c—o—c bond. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like. Examples of the curing agent having a c=n bond include a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like. Examples of the curing agent having a C-O-C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and a urethane resin. The cured product of the resin composition containing the curing agent in the adhesive layer 5 can be confirmed by, for example, gas Chromatography Mass Spectrometry (GCMS), infrared spectrometry (IR), time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectrometry (XPS), or the like.

The compound having an isocyanate group is not particularly limited, and a polyfunctional isocyanate compound is preferable from the viewpoint of effectively improving the adhesion between the resist film 3a and the adhesive layer 5. The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups. Specific examples of the polyfunctional isocyanate curing agent include Pentane Diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a product obtained by polymerizing them or urethane (nurate), a mixture of these, and a copolymer of these and other polymers.

The content of the compound having an isocyanate group in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the resist film 3a and the adhesive layer 5.

The compound having an oxazoline group is not particularly limited as long as it has an oxazoline skeleton. Specific examples of the compound having an oxazoline group include a compound having a polystyrene main chain, a compound having an acrylic main chain, and the like. Examples of commercial products include eporos series produced by japan catalyst, inc.

The proportion of the oxazoline group-containing compound in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the resist film 3a and the adhesive layer 5.

Examples of the compound having an epoxy group include epoxy resins. The epoxy resin is not particularly limited as long as it can form a crosslinked structure using an epoxy group present in a molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and further preferably about 200 to 800. Wherein, in the first invention, the weight average molecular weight of the epoxy resin is a value measured under the condition of using polystyrene as a standard sample and measured by Gel Permeation Chromatography (GPC).

Specific examples of the epoxy resin include glycidyl ether derivatives of trimethylolpropane, bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether. The epoxy resin may be used alone or in combination of 1 kind or 2 or more kinds.

The proportion of the epoxy resin in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass%, in the resin composition constituting the adhesive layer 5. This effectively improves the adhesion between the resist film 3a and the adhesive layer 5.

The polyurethane resin is not particularly limited, and a known polyurethane resin can be used. The adhesive layer 5 may be, for example, a cured product of a two-part curable urethane resin.

The proportion of the urethane resin in the adhesive layer 5 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass%, in the resin composition constituting the adhesive layer 5. This can effectively improve the adhesion between the resist film 3a and the adhesive layer 5 in an atmosphere in which a component such as an electrolyte solution causes corrosion of the barrier layer.

In the first invention, when the adhesive layer 5 is a cured product of a resin composition containing at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin function as curing agents, respectively.

In view of particularly effectively improving the adhesion between the resist film 3a and the adhesive layer 5, it is preferable that the resist film 3a is formed of a treatment liquid containing an acrylic resin, a chromium compound and phosphoric acid, and the adhesive layer 5 is formed of a cured product of a resin composition containing an acid-modified polypropylene and an epoxy resin or a compound having an isocyanate group, as a combination of the resist film 3a and the adhesive layer 5. In this combination, the acrylic resin is preferably polyacrylic acid or a salt thereof, an acrylic methacrylate copolymer or an acrylic maleic acid copolymer, and particularly preferably polyacrylic acid. The weight average molecular weight of the polyacrylic acid or a salt thereof is preferably about 1 to 100 tens of thousands, more preferably about 50 to 100 tens of thousands. Although durability is improved at high molecular weight, it is not easily dissolved in water when preparing a treatment liquid. In addition, in this combination, maleic anhydride-modified polypropylene is particularly preferable as acid-modified polypropylene. The melting peak temperature of the maleic anhydride-modified polypropylene is preferably about 50 to 100 ℃. As the epoxy resin, glycidyl ether derivatives of trimethylolpropane and novolak type epoxy resins of bisphenol F are preferable. In addition, in this combination, as the compound having an isocyanate group, an urethane body of an aliphatic isocyanate is preferable, and particularly, an urethane body of PDI (pentamethylene diisocyanate) is preferable.

From the viewpoint of particularly effectively improving the adhesion between the resist film 3a and the adhesive layer 5, specific examples of particularly preferable combinations of the resist film 3a and the adhesive layer 5 include the following combinations: the resist film 3a is formed of a treatment liquid containing a polyacrylic acid having a molecular weight of about 50 to 100 tens of thousands and an acid value of about 500 to 1000, chromium (III) fluoride and phosphoric acid, and the adhesive layer 5 is formed of a cured product of a resin composition containing maleic anhydride-modified polypropylene having a melting peak temperature of 50 to 100 ℃ and an epoxy resin which is a glycidyl ether derivative of trimethylolpropane.

The upper limit of the thickness of the adhesive layer 5 is preferably about 40 μm or less, more preferably about 30 μm or less, further preferably about 20 μm or less, and the lower limit is preferably about 0.5 μm or more, more preferably about 1 μm or more, further preferably about 2 μm or more, from the viewpoint of effectively improving the adhesion between the resist coating 3a and the adhesive layer 5. The thickness of the adhesive layer 5 is preferably about 0.5 to 40. Mu.m, about 0.5 to 30. Mu.m, about 0.5 to 20. Mu.m, about 1 to 40. Mu.m, about 1 to 30. Mu.m, about 1 to 20. Mu.m, about 2 to 40. Mu.m, about 2 to 30. Mu.m, or about 2 to 20. Mu.m.

[ Heat-fusible resin layer 4]

In the battery packaging material according to the first aspect of the invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that seals the battery element by heat-fusing the heat-fusible resin layers together when the battery is assembled.

The resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-fused, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the resin constituting the heat-fusible resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the heat-fusible resin layer 4 contains a polyolefin skeleton and can be analyzed by, for example, infrared spectrometry, gas chromatography mass spectrometry, or the like, and the analysis method is not particularly limited. For example, when the maleic anhydride-modified polyolefin is measured by infrared spectrometry, the measurement is carried out at a wave number of 1760cm ^-1 Nearby sum wave number 1780cm ^-1 The vicinity detects a peak from maleic anhydride. However, when the degree of acid modification is low, the peak may be small and undetectable. In this case, the analysis can be performed by nuclear magnetic resonance spectroscopy.

Specific examples of the polyolefin include: polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; polypropylene such as homopolypropylene, a block copolymer of polypropylene (e.g., a block copolymer of propylene and ethylene), and a random copolymer of polypropylene (e.g., a random copolymer of propylene and ethylene); ethylene-butene-propylene terpolymers, and the like. Among these polyolefins, polyethylene and polypropylene are preferably cited.

The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene, and the like. Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic olefins such as norbornene; specific examples thereof include cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these polyolefins, cyclic olefins are preferable, and norbornene is more preferable. In addition, styrene may also be used as polyolefin.

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

The acid-modified cyclic polyolefin is a polymer obtained by copolymerizing an α, β -unsaturated carboxylic acid or an anhydride thereof instead of a part of a monomer constituting the cyclic polyolefin, or by block polymerizing or graft polymerizing an α, β -unsaturated carboxylic acid or an anhydride thereof with the cyclic polyolefin. The cyclic polyolefin modified with carboxylic acid is as above. The carboxylic acid to be modified with the cyclic polyolefin is the same as the carboxylic acid to be modified with the acid-modified polyolefin.

Among these resin components, polyolefin such as polypropylene and carboxylic acid-modified polyolefin are preferable; more preferably, polypropylene and acrylic modified polypropylene are exemplified.

From the viewpoint of excellent heat weldability, the heat weldable resin layer 4 preferably contains polypropylene, and more preferably is composed of polypropylene. When the adhesive layer 5 contains a modified polyolefin resin, the heat-fusible resin layer 4 preferably contains polypropylene.

The heat-fusible resin layer 4 may be formed of 1 resin component alone or a polymer blend in which 2 or more resin components are combined. The heat-fusible resin layer 4 may be formed of only 1 layer, or may be formed of 2 or more layers using the same or different resin components.

In the first invention, from the viewpoint of improving the moldability of the battery packaging material, it is preferable that a lubricant is adhered to the surface of the heat-fusible resin layer. The lubricant is not particularly limited, and an amide-based lubricant is preferably used. Specific examples of the amide-based lubricant include saturated fatty amides, unsaturated fatty amides, substituted amides, methylol amides, saturated fatty bisamides, and unsaturated fatty bisamides. Specific examples of the saturated fatty amide include lauramide, palmitoamide, stearamide, behenamide, and hydroxystearamide. Specific examples of the unsaturated fatty amide include oleamide and erucamide. Specific examples of the substituted amide include N-oleyl palmitoamide, N-stearyl stearamide, N-oleyl stearamide, and N-stearyl erucamide. Specific examples of the methylol amide include methylol stearamide and the like. Specific examples of the saturated fatty bisamide include methylene bis-stearamide, ethylene bis-decanoamide, ethylene bis-lauramide, ethylene bis-stearamide, ethylene bis-hydroxystearamide, ethylene bis-behenamide, hexamethylenebis-stearamide, hexamethylenebis-behenamide, hexamethylenehydroxystearamide, N '-distearyladipamide, and N, N' -distearylsebacamide. Specific examples of the unsaturated fatty bisamide include ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N '-dioleyladipamide, N' -dioleylsebacamide, and the like. Specific examples of the fatty acid ester amide include ethyl stearamide stearate. Specific examples of the aromatic bisamide include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N, N' -distearyl isophthalamide. The lubricant may be used alone or in combination of 2 or more.

When the lubricant is present on the surface of the heat-fusible resin layer 4, the amount of the lubricant present is not particularly limited, and may be preferably about 3mg/m ² The above, more preferably 4 to 15mg/m ² About, more preferably 5 to 14mg/m ² Left and right.

The heat-fusible resin layer 4 may contain a lubricant. The lubricant present on the surface of the heat-fusible resin layer 4 may be a lubricant that is oozed out from the resin constituting the heat-fusible resin layer 4, or may be formed by applying a lubricant to the surface of the heat-fusible resin layer 4.

The thickness of the heat-fusible resin layer 4 is not particularly limited as long as the function as a heat-fusible resin layer can be exhibited, and examples of the preferable lower limit include about 15 μm or more, examples of the preferable upper limit include about 60 μm or less, about 45 μm or less, about 40 μm or less, and about 35 μm or less, and examples of the preferable range include about 15 to 60 μm, about 15 to 45 μm, about 15 to 40 μm, and about 15 to 35 μm.

[ surface coating 6]

In the battery packaging material of the first invention, a surface coating layer 6 may be provided on the outer side of the base material layer 1 (on the side opposite to the barrier layer 3 of the base material layer 1) as necessary in order to improve design properties, electrolytic solution resistance, scratch resistance, moldability, and the like. When the surface coating layer 6 is provided, the surface coating layer 6 is a layer located on the outermost layer side of the battery packaging material.

The surface coating layer 6 may be formed of polyvinylidene chloride, polyester resin, polyurethane resin, acrylic resin, epoxy resin, or the like, for example. Of these, the surface coating layer 6 is preferably formed of a two-part curable resin. Examples of the two-part curable resin for forming the surface coating layer 6 include two-part curable urethane resins, two-part curable polyester resins, and two-part curable epoxy resins. In addition, additives may be blended into the surface coating layer.

Examples of the additive include fine particles having a particle diameter of about 0.5nm to 5. Mu.m. The material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, organic substances, and the like. The shape of the additive is not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and hollow sphere (balloon) shapes. Specific examples of the additives include talc, silica, graphite, kaolin, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high-melting nylon, acrylate resin, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. These additives may be used alone or in combination of 1 or more than 2. Among these additives, silica, barium sulfate, and titanium oxide are preferable from the viewpoints of dispersion stability, cost, and the like. The additive may be subjected to various surface treatments such as an insulating treatment and a high dispersibility treatment. In addition, additives such as lubricants, antiblocking agents, roughening agents, flame retardants, antioxidants, light stabilizers, adhesion imparting agents, antistatic agents, and elastomer resins may be contained in at least one of the surface and the inside of the surface covering layer 6, depending on the functionality and the like that the surface covering layer 6 or the surface thereof should have. Specific examples of the lubricant include the above-mentioned lubricants. The fine particles may function as a lubricant, an anti-blocking agent, and a roughening agent.

The content of the additive in the surface coating layer 6 is not particularly limited, but may be about 0.05 to 1.0 mass%, and more preferably about 0.1 to 0.5 mass%.

The method of 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 to the outer surface of the base material layer 1. When the additive is blended, the coating may be performed after the additive is added to the two-part curable resin and mixed.

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

1-3. Method for manufacturing packaging material for battery

The method for producing the battery packaging material of the first aspect of the present invention is not particularly limited as long as a laminate having laminated layers of a predetermined composition can be obtained, and the following methods can be used: comprises a step of laminating at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order to obtain a laminate,

when the barrier layer is laminated, a resist film is provided on the surface of the barrier layer on the adhesive layer side so as to be in contact with the adhesive layer, and the resist film 3a, The following coating was used: by analysis using XPS, the resist film 3a detected a peak P from an O-c=o bond in the range of 287eV to 290eV _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50.

As an example of the method for producing the battery packaging material of the first invention, the following is given. First, a laminate (hereinafter, also referred to as "laminate a") is formed by laminating a base layer 1, an adhesive layer 2, and a barrier layer 3 (having a resist film 3a, which will be omitted below) in this order. Specifically, the laminate a may be formed by a dry lamination method in which an adhesive for forming the adhesive layer 2 is applied to the base material layer 1 or the barrier layer 3 by a coating method such as a gravure coating method or a roll coating method, and after drying, the barrier layer 3 or the base material layer 1 is laminated to cure the adhesive layer 2. In this case, when the barrier layer 3 is laminated, a layer in which the above-described resist coating is formed in advance on at least one surface of the barrier layer 3 is used. The method of forming the resist films 3a and 3b is as described above.

Next, the adhesive layer 5 and the heat-fusible resin layer 4 are laminated on the barrier layer 3 of the laminate a. As a method of providing the adhesive layer 5 on the barrier layer 3, for example, a resin component constituting the adhesive layer 5 may be coated on the barrier layer 3 of the laminate a by a gravure coating method, a roll coating method, an extrusion lamination method, or the like. As a method for providing the adhesive layer 5 between the barrier layer 3 and the heat-fusible resin layer 4, for example, the following methods are mentioned: (1) A method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate a by coextrusion (coextrusion lamination method); (2) A method of forming a laminate of the adhesive layer 5 and the heat-fusible resin layer 4 and laminating the laminate on the barrier layer 3 of the laminate a by a heat lamination method; (3) A method in which an adhesive for forming the adhesive layer 5 is applied to the barrier layer 3 of the laminate a by an extrusion method or a solution, dried at a high temperature, and laminated by a sintering method or the like, and the heat-fusible resin layer 4 previously formed into a sheet shape is laminated on the adhesive layer 5 by a heat lamination method; (4) A method (sandwich lamination method) in which the laminate a and the heat-fusible resin layer 4 are bonded by the adhesive layer 5 while flowing into the molten adhesive layer 5 between the barrier layer 3 of the laminate a and the heat-fusible resin layer 4 which has been formed into a sheet in advance.

When the surface coating layer 6 is provided, the surface coating layer is laminated on the surface of the base material layer 1 opposite to the barrier layer 3. For example, the surface coating layer can be formed by applying the resin described above for 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.

By the above-described operation, a laminate comprising the surface coating layer, the base material layer 1, the adhesive layer 2, and the barrier layer 3, the adhesive layer 5, and the heat-fusible resin layer 4, each of which has a resist coating on at least one surface, is formed, and the adhesive layer 2 and the adhesive layer 5, each of which is provided as needed, may be subjected to heat treatment such as a hot roll contact type, a hot air type, a near infrared ray type, or a far infrared ray type, in order to secure adhesion between the adhesive layer 2 and the adhesive layer 5, each of which is provided as needed.

In the packaging material for a battery of the first aspect of the present invention, each layer constituting the laminate may be subjected to a surface activation treatment such as corona treatment, sand blast treatment, oxidation treatment, ozone treatment, or the like, as necessary, in order to improve or stabilize film forming property, lamination processing, suitability for 2 times of processing (bagging, embossing), or the like of the final product.

1-4. Use of packaging material for battery

The battery packaging material of the first aspect of the invention can be used in a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a battery element having at least a positive electrode, a negative electrode, and an electrolyte can be housed in a package formed of the battery packaging material of the first invention to form a battery.

Specifically, with the battery packaging material according to the first aspect of the present invention, a battery element having at least a positive electrode, a negative electrode, and an electrolyte is covered with a metal terminal connected to the positive electrode and the negative electrode so that a flange portion (a region where heat-fusible resin layers contact each other) can be formed at the peripheral edge of the battery element in a state in which the metal terminal protrudes outward, and the heat-fusible resin layers of the flange portion are heat-sealed with each other to seal the flange portion, whereby a battery using the battery packaging material can be provided. When the battery element is housed in the package formed of the battery packaging material of the first invention, the package is formed such that the heat-fusible resin portion of the battery packaging material of the first invention is inside (the surface in contact with the battery element).

The battery packaging material of the first invention can be used for both primary batteries and secondary batteries, and is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the first invention is applied is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel-hydrogen storage batteries, nickel-cadmium storage batteries, nickel-iron storage batteries, nickel-zinc storage batteries, silver-zinc oxide storage batteries, metal-air batteries, polyvalent cation batteries, capacitors (condensers), and the like. Among these secondary batteries, as preferable application objects of the battery packaging material of the first invention, lithium ion batteries and lithium ion polymer batteries are cited.

In the battery packaging material according to the first aspect of the invention, the barrier layer having the resist film can maintain high adhesion. Therefore, the battery packaging material of the first invention is particularly useful as a packaging material for small batteries used for mobile devices and the like, for example.

(second invention)

The packaging material for a battery of the second aspect of the invention is characterized by comprising a laminate having at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order, wherein the surface of the barrier layer on the adhesive layer side has a resist film in contact with the adhesive layer, and the resist film is formed at 28 by analysis by X-ray photoelectron spectroscopy (hereinafter sometimes referred to as XPS)Peak P from O-c=o bond was detected in the range of 7eV to 290eV _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C Is in the range of 0.10 to 0.50 inclusive. Hereinafter, a packaging material for a battery, a method for manufacturing the packaging material for a battery, and a battery using the packaging material for a battery according to a second aspect of the invention will be described in detail with reference to fig. 5 to 8.

2-1. Laminated structure of battery packaging material

For example, as shown in fig. 5 to 8, the battery packaging material of the second invention is composed of a laminate having at least a base material layer 1, an adhesive layer 2, a barrier layer 3, and a heat-fusible resin layer 4 in this order. In the battery packaging material according to the second aspect of the invention, the base material layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. That is, when the battery is assembled, the heat-fusible resin layers 4 located at the peripheral edges of the battery element are heat-fused to each other to seal the battery element, whereby the battery element is packaged.

As shown in fig. 5 to 8, in the battery packaging material of the second invention, the surface of the barrier layer 3 on the adhesive layer 2 side has a resist film 3b that contacts the adhesive layer 2. Fig. 5 is a schematic view showing that the resist film 3b is provided only on the adhesive layer 2 side surface of the barrier layer 3. Fig. 6 and 8 are schematic views of the barrier layer 3 having the resist films 3a and 3b on both sides thereof. As described below, the battery packaging material according to the second aspect of the invention may include a resist film 3b having peak characteristics detected by XPS analysis described below only on the adhesive layer 2 side surface of the barrier layer 3, or may include resist films 3a and 3b having peak characteristics detected by XPS analysis described below on both surfaces of the barrier layer 3.

As shown in fig. 6 to 8, the battery packaging material of the second invention may have an adhesive layer 5 between the barrier layer 3 and the heat-fusible resin layer 4, if necessary, in order to improve the adhesion thereof. As shown in fig. 8, the battery packaging material of the second invention may further include a surface coating layer 6 on the side of the base material layer 1 opposite to the barrier layer 3 as needed in order to improve design properties, electrolyte resistance, scratch resistance, moldability, and the like.

The thickness of the laminate constituting the battery pack 10 of the second invention is not particularly limited, and the same thickness as that exemplified in the first invention can be exemplified.

2-2. Layers forming a battery packaging material

[ substrate layer 1]

In the battery packaging material according to the second aspect of the present invention, the structure of the base material layer 1 is the same as that of the base material layer 1 according to the first aspect of the present invention, and therefore, the description thereof is omitted.

[ adhesive layer 2]

In the battery packaging material 10 according to the second aspect of the invention, the adhesive layer 2 is a layer provided between the base layer 1 and the barrier layer 3 so as to firmly adhere them. More specifically, the adhesive layer 2 is provided so as to be in contact with the resist film 3b on the surface of the barrier layer 3.

In general, from the viewpoint of improving the adhesion between the barrier layer and the substrate layer, it is preferable to have an adhesive layer between them, but when a resist film is provided on the surface of the barrier layer on the substrate layer side, the adhesion between the adhesive layer and the resist film may be reduced. In contrast, in the battery packaging material according to the second aspect of the present invention, the resist film 3b has a value P of a specific peak height ratio, which will be described later _OCO/C-C The adhesion between the adhesive layer 2 and the resist film 3b can be effectively improved. That is, in the battery packaging material according to the second aspect of the invention, the resist film 3b on the surface of the barrier layer 3 and the outer base material layer 1 are laminated with the adhesive layer 2 interposed therebetween, and the barrier layer having the resist film can particularly effectively exhibit an effect of excellent adhesion to the inner layer.

In addition, when the battery is placed in a high-temperature environment or a high-temperature and high-humidity environment, adhesion between the barrier layer and the substrate layer is likely to be reduced, and delamination may occur between the substrate layer and the barrier layer. When delamination occurs between the barrier layer and the base material layer, the puncture strength and pinhole resistance decrease, and the possibility of intrusion of water vapor into the battery increases. In contrast, in the battery packaging material according to the second aspect of the invention, by effectively improving the adhesion between the adhesive layer 2 and the resist film 3b, the decrease in adhesion can be suppressed even when the battery packaging material is placed in a high-temperature environment or a high-temperature and high-humidity environment, and delamination between the base material layer and the barrier layer can be suppressed even in a high-temperature and high-humidity environment.

The adhesive layer 2 is formed of an adhesive capable of adhering the base material layer 1 to the resist film 3 b. The adhesive used for forming the adhesive layer 2 may be a two-part curing adhesive or a one-part curing adhesive. The adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any type such as a chemical reaction type, a solvent evaporation type, a hot melt type, a hot press type, or the like.

The resin used for forming the adhesive layer 2 is preferably a resin having a polar group from the viewpoint of improving the adhesion between the base layer 1 and the barrier layer 3. The polar group may be any functional group containing at least 1 atom having an electronegativity larger than that of carbon. Examples of the atom having a greater electronegativity than carbon include nitrogen, oxygen, sulfur, and the like. Specific examples of the polar group include a nitrogen-containing binding group, an amino group, an isocyanate group, an oxazoline group, and an epoxy group. Wherein the nitrogen-containing bonding group means a divalent group having a nitrogen atom. Among these polar groups, a nitrogen-containing bonding group, an isocyanate group, an oxazoline group and an epoxy group are preferable from the viewpoint of further improving the adhesion of the adhesive layer 2 to the resist film 3 b. In addition, from the viewpoint of further improving the adhesion between the adhesive layer 2 and the resist film 3b and further improving the moldability of the battery packaging material, a nitrogen-containing bonding group is more preferable. Examples of the nitrogen-containing bonding group include a urethane bonding group, a thiourethane bonding group, a urea bonding group, a thiourea bonding group, an amide ester bonding group, and an amide bonding group, and from the viewpoint of further improving the adhesion between the adhesive layer 2 and the resist film 3b, the urethane bonding group and the amide ester bonding group are preferable, and the urethane bonding group is more preferable. Examples of the amino group include a primary amino group, a secondary amino group, and a tertiary amino group.

The polar group contained in the adhesive layer 2 can be analyzed by measuring infrared absorption spectrum by infrared spectrometry as described below.

< determination of infrared absorption Spectroscopy Using Infrared Spectroscopy >)

And cutting the packaging material for the battery to prepare a sample. The sample may be a square of 100mm×100mm in size, but even a smaller sample may be one of a size that can be measured by a measuring instrument. The substrate layer 1 of the obtained sample was peeled off, and the surface of the adhesive layer 2 was subjected to infrared absorption spectrometry using, for example, the ATR measurement mode of Nicolet iS10FT-IR manufactured by Thermo Fisher Scientific company, under an environment of a temperature of 25 ℃ and a relative humidity of 50%. Based on the obtained absorption spectrum, 3650cm of O-H stretching vibration from hydroxyl group was measured ^-1 -3580cm ^-1 And 3550cm ^-1 -3200cm ^-1 1300cm of the peak of (C) or of the O-H stretching vibration from the carboxyl group ^-1 -1000cm ^-1 1720cm from C=O stretching vibration ^-1 -1700cm ^-1 1000cm from O-H deformation vibration ^-1 -850cm ^-1 3500cm of N-H stretching vibration from amino group or peak of (C) ^-1 And 3400cm ^-1 Is confirmed by the peak of (2).

The method comprises the following steps: macro-ATR method

Wave number resolution: 8cm ^-1

Cumulative number of times: 32 times

A detector: DTGS detector

ATR prism: ge (gallium nitride)

Incidence angle: 45 degree

Baseline: wave number 800cm ^-1 To 3700cm ^-1 Average of intensities within a range of (2)

From the viewpoint of improving the adhesion between the adhesive layer 2 and the resist film 3b (and between the resist film 3b and the layer adjacent thereto), the adhesive layer 2 is preferably composed of a resin having a nitrogen-containing bonding group as a polar group, an isocyanate group, an oxazoline group, or an epoxy group, and more preferably composed of a resin having a nitrogen-containing bonding group.

As described below, the resist coating 3b detects the peak P from the o—c=o bond _OCO . The resin constituting the adhesive layer 2 in contact with the resist film 3b contains, as a polar group, a nitrogen-containing binding group, an isocyanate group, an oxazoline group or an epoxy group, and more preferably a nitrogen-containing binding group, whereby affinity with the polar group is improved, and adhesion between the adhesive layer 2 and the resist film 3b can be more effectively improved. For example, the o—c=o bond is contained in a carboxyl group or various salts such as ammonium salt, sodium salt, amine salt and the like, ester bond and the like. From the viewpoint of particularly effectively improving the adhesion between the adhesive layer 2 and the resist film 3b, the following combinations of the resist film 3b and the following adhesive layer 2 are given as examples of the combination of the adhesive layer 2 and the resist film 3 b: the resist film 3b detects a peak P of C1s from an o—c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285.0eV _C-C And peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50 inclusive; the adhesive layer 2 was found to be 3650cm by analysis by infrared spectroscopy ^-1 -3580cm ^-1 And 3550cm ^-1 -3200cm ^-1 Peak of O-H stretching vibration from hydroxyl group or 1300cm ^-1 -1000cm ^-1 Peak of O-H stretching vibration from carboxyl group, 1720cm ^-1 -1700cm ^-1 Peak from c=o stretching vibration, 1000cm ^-1 -850cm ^-1 From the peaks of O-H deformation vibrations.

Specific examples of the resin having a polar group that can be used to form the adhesive layer 2 include a cured product of a resin composition obtained by adding a curing agent to a resin as an adhesive component. Specific examples of the adhesive component include: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyesters; a polycarbonate resin; polyether resin; a polyurethane resin; an epoxy resin; phenolic resin; polyamide resins such as nylon 6, nylon 66, nylon 12 and copolyamide; polyolefin resins such as polyolefin, acid-modified polyolefin and metal-modified polyolefin, and polyvinyl acetate resins; a cellulose-based adhesive; (meth) acrylic resins; polyimide resin; amino resins such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene-butadiene rubber, and other rubbers; a silicone resin; and polyol compounds, etc. These adhesive components may be used alone or in combination of at least 2 kinds.

The curing agent may be, for example, a compound having the nitrogen-containing binding group as a polar group, a compound having the polar group, or the like, which is produced after curing, depending on the functional group of the adhesive component. The curing agent is preferably a curing agent having at least 1 kind selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a c—o—c bond, from the viewpoint of further improving the adhesion between the adhesive layer 2 and the resist film 3 b. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group, a curing agent having an epoxy group, and the like. Examples of the curing agent having a c=n bond include a curing agent having an oxazoline group, a curing agent having an isocyanate group, and the like. Examples of the curing agent having a C-O-C bond include a curing agent having an oxazoline group and a curing agent having an epoxy group.

Specific examples of the resin having a polar group by a combination of these adhesive components and a curing agent are preferably listed from the viewpoint of further improving the adhesion between the adhesive layer 2 and the resist film 3 b: a cured product (as a polar group, a urethane-binding group is formed) of a polyurethane resin composition containing a polyol compound (main agent) as an adhesive component and a compound having an isocyanate group as a curing agent; a cured product of a resin composition containing an adhesive component having a carboxyl group and a compound having an oxazoline group as a curing agent (as a polar group, an amide ester bond group is formed); a cured product of a resin composition containing, as an adhesive component, an acid-modified polyolefin and, as a curing agent, at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group (having, as a polar group, at least 1 selected from the group consisting of an isocyanate group, an oxazoline group and an epoxy group).

Among these resins having polar groups in the adhesive layer 2, a cured product of a polyurethane resin composition containing a polyol compound and a compound having an isocyanate group is more preferable from the viewpoint of further improving the adhesion between the adhesive layer 2 and the resist film 3b and further improving the moldability of the battery packaging material.

Examples of the polyol compound used in the urethane resin composition in the adhesive layer 2 include polyester polyol, polyester polyurethane polyol, polyether polyurethane polyol, and acrylic polyol. The hydroxyl equivalent weight and the weight average molecular weight of these polyol compounds are not particularly limited, and from the viewpoint of obtaining excellent moldability of the battery packaging material, for example, the hydroxyl equivalent weight (per mol) may be from 0.5 to 2.5, preferably from 0.7 to 1.9, and the weight average molecular weight may be from 500 to 120000, preferably from 1000 to 80000. Among these polyol compounds, polyester polyols, polyester polyurethane polyols, polyether polyurethane polyols are preferably cited, and polyester polyols are more preferably cited. These polyol compounds may be used alone or in combination of 1 or more than 2.

Examples of the isocyanate compound used in the polyurethane resin composition include polyisocyanates, adducts thereof, isocyanurate-modified products thereof, carbodiimide-modified products thereof, allophanate-modified products thereof, biuret-modified products thereof, and the like. Specific examples of the polyisocyanate include: aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), polyphenylmethane diisocyanate (polymeric MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), bis (4-isocyanatocyclohexyl) methane (H12 MDI), 1, 5-naphthalene diisocyanate (1, 5-NDI), 3 '-dimethyl-4, 4' -diphenylene diisocyanate (TODI), and Xylylene Diisocyanate (XDI); aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as 4,4' -methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate (IPDI). Specific examples of the above-mentioned adducts include adducts obtained by adding trimethylolpropane, ethylene glycol, etc. to the above-mentioned polyisocyanate. Among these isocyanate compounds, polyisocyanates and their adducts are preferable; more preferably, aromatic diisocyanates, adducts thereof, and isocyanurate modifications thereof are exemplified. These isocyanate compounds may be used alone or in combination of 1 or more than 2.

The polyurethane resin composition is preferably a polyurethane resin composition containing at least 1 polyol compound selected from the group consisting of polyester polyol, polyester polyurethane polyol, polyether polyol and polyether polyurethane polyol, and at least 1 isocyanate compound selected from the group consisting of aromatic diisocyanate, its adducts and isocyanurate modifications thereof, from the viewpoint of obtaining excellent moldability of the packaging material for a battery.

In the polyurethane resin composition, the ratio of the polyol compound (main agent) to the isocyanate compound (curing agent) is, for example, 1 to 30 moles, preferably 3 to 20 moles, per 1 mole of hydroxyl group of the polyol compound, from the viewpoint of obtaining excellent moldability of the battery packaging material.

In addition to the cured product of the polyurethane resin composition described above, examples of the resin having a polar group in the adhesive layer 2 include a cured product of a polyurethane resin composition obtained by combining a polyurethane compound having a hydroxyl group with a polyisocyanate compound, combining a polyurethane compound having an isocyanate group with a polyol compound, and the like, and a cured product obtained by using moisture such as air for the polyurethane compound having an isocyanate group.

In the adhesive layer 2, when the resin having a polar group is a cured product of a resin composition containing an acid-modified polyolefin as an adhesive component and at least 1 kind selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group as a curing agent, the acid-modified polyolefin is a polymer obtained by block polymerization or graft polymerization of a polyolefin with an acid component such as a carboxylic acid. Examples of the acid component used for the modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride and itaconic anhydride, and anhydrides thereof. Examples of the modified polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; polypropylene such as homopolypropylene, a block copolymer of polypropylene (e.g., a block copolymer of propylene and ethylene), and a random copolymer of polypropylene (e.g., a random copolymer of propylene and ethylene); ethylene-butene-propylene terpolymers, and the like. Among these polyolefins, polyethylene and polypropylene are preferably cited. Among the acid-modified polyolefins, maleic anhydride-modified polyolefin is particularly preferred, and maleic anhydride-modified polypropylene is further preferred.

The compound having an isocyanate group used together with the acid-modified polyolefin is not particularly limited, and a polyfunctional isocyanate compound is preferable from the viewpoint of effectively improving the adhesion between the adhesive layer 2 and the resist film 3 b. The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include Pentamethylene Diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a product obtained by polymerizing or urethanizing them, a mixture thereof, and a copolymer with other polymers.

The content of the compound having an isocyanate group used together with the acid-modified polyolefin in the adhesive layer 2 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 2. This effectively improves the adhesion between the adhesive layer 2 and the resist film 3 b.

The proportion of the oxazoline group-containing compound used together with the acid-modified polyolefin in the adhesive layer 2 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 2. This effectively improves the adhesion between the adhesive layer 2 and the resist film 3 b.

In the adhesive layer 2, the epoxy resin used together with the acid-modified polyolefin is not particularly limited as long as it can form a crosslinked structure using an epoxy group existing in a molecule, and a known epoxy resin can be used. The weight average molecular weight of the epoxy resin is preferably about 50 to 2000, more preferably about 100 to 1000, and further preferably about 200 to 800. In the second invention, the weight average molecular weight of the epoxy resin is a value measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample.

The proportion of the epoxy resin used together with the acid-modified polyolefin in the adhesive layer 2 is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 40 mass% in the resin composition constituting the adhesive layer 2. This effectively improves the adhesion between the adhesive layer 2 and the resist film 3 b.

From the viewpoint of particularly effectively improving the adhesion between the adhesive layer 2 and the resist film 3b, it is preferable that the adhesive layer 2 is composed of a resin having a urethane bonding group, an epoxy group or an isocyanate group as a polar group, and the resist film 3b is formed of a treatment liquid containing an acrylic resin, a chromium compound and phosphoric acid, as a combination of the adhesive layer 2 and the resist film 3 b. In this combination, the adhesive layer 2 is preferably composed of a cured product of a polyurethane resin composition containing a polyol compound and a compound having an isocyanate group, or a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group, and is particularly preferably composed of a cured product of a polyurethane resin composition containing a polyol compound and a compound having an isocyanate group, from the viewpoint of improving the moldability of the battery packaging material. The polyol compound is particularly preferably a polyester polyol, and the compound having an isocyanate group is particularly preferably an aromatic diisocyanate. As the acid-modified polypropylene, maleic anhydride-modified polypropylene is particularly preferred. The melting peak temperature of the maleic anhydride-modified polypropylene is preferably about 50 to 100 ℃. As the epoxy resin, glycidyl ether derivatives of trimethylolpropane and novolak type epoxy resins of bisphenol F are preferable. In addition, in this combination, as the compound having an isocyanate group, an urethane body of an aliphatic isocyanate is preferable, and particularly, an urethane body of PDI (pentamethylene diisocyanate) is preferable. In this combination, the acrylic resin is preferably polyacrylic acid or a salt thereof, an acrylic methacrylate copolymer or an acrylic maleic acid copolymer, and particularly preferably polyacrylic acid. The weight average molecular weight of the polyacrylic acid or a salt thereof is preferably about 1 to 100 tens of thousands, more preferably about 50 to 100 tens of thousands. Although durability is improved at high molecular weights, dissolution in water becomes difficult when preparing the treatment liquid.

From the viewpoint of particularly effectively improving the adhesion between the adhesive layer 2 and the resist film 3b and particularly effectively improving the moldability of the battery packaging material, specific examples of particularly preferred combinations of the adhesive layer 2 and the resist film 3b include the following combinations: the adhesive layer 2 is composed of a cured product of a polyurethane resin composition containing a polyester polyol having a molecular weight of 10000 to 40000 and an equivalent amount of hydroxyl groups of 0.7 to 1.9 per mol and an aromatic diisocyanate compound which is a Trimethylolpropane (TMP) adduct of Toluene Diisocyanate (TDI), and the resist coating 3b is composed of a treatment liquid containing a polyacrylic acid having a molecular weight of about 50 to 100 tens of thousands and an acid value of about 500 to 1000, chromium (III) fluoride and phosphoric acid.

The hardness of the adhesive layer 2 obtained by nanoindentation may be, for example, 20 to 400MPa. In addition, from the viewpoint of excellent moldability of the battery packaging material, the hardness of the adhesive layer 2 obtained by nanoindentation is preferably about 30 to 400MPa, more preferably about 40 to 375MPa, even more preferably about 50 to 350MPa, and particularly preferably about 50 to 70 MPa. The hardness can be determined by measuring the hardness in the following manner. Specifically, as the apparatus, a nanoindenter was used, and as the indenter of the nanoindenter, a Berkovich (Berkovich) type indenter having a triangular pyramid shape was used. First, the pressure head was pressed against the surface of the adhesive layer 2 of the battery packaging material in an environment having a relative humidity of 50% and a temperature of 23 ℃, the pressure head was pressed into the adhesive layer 2 from the surface until the load was 40 μn for 10 seconds, the pressure head was held for 5 seconds in this state, and then the load was removed for 10 seconds. Using maximum load P _max (mu N) and the contact projected area A (mu m) at the maximum depth ² ) By P _max The indentation hardness (MPa) was calculated. The position was changed and measured (n=5), and the average value of the obtained indentation hardness was used as the hardness of the adhesive layer 2 obtained by the nanoindentation method. The surface of the press-fit indenter is a portion where the cross section of the adhesive layer 2 is exposed, the portion being cut in the thickness direction so as to pass through the center portion of the battery packaging material. The cutting can be performed by using a commercially available rotary slicer or the like.

In the second invention, examples of the resin constituting the adhesive layer 2 having the above hardness include resins containing a nitrogen-containing bonding group as a polar group, preferably cured products of polyurethane resin compositions containing a polyol compound and a compound having an isocyanate group, more preferably cured products of polyurethane resin compositions having a hydroxyl equivalent (number/mol) of the polyol compound of 0.5 to 2.5, preferably 0.7 to 1.9, and a weight average molecular weight of 500 to 120000, preferably 1000 to 80000. Further, as a preferable resin constituting the adhesive layer 2 having the above hardness, a polyurethane resin composition containing at least 1 polyol compound selected from polyester polyol, polyester polyurethane polyol, polyether polyol and polyether polyurethane polyol, and at least 1 isocyanate compound selected from aromatic diisocyanate, its adduct and isocyanurate modified product thereof is specifically exemplified. Further, as a more preferable resin constituting the adhesive layer 2 having the above hardness, there is mentioned a polyurethane resin composition in which the ratio of the polyol compound to the isocyanate compound is 1 to 30 moles, preferably 3 to 20 moles, of the isocyanate group of the isocyanate compound to 1 mole of the hydroxyl group of the polyol compound.

The thickness of the adhesive layer 2 is not particularly limited as long as the function as an adhesive layer can be exhibited, and from the viewpoint of effectively improving the adhesion between the adhesive layer 2 and the resist film 3b and/or from the viewpoint of effectively improving the moldability of the battery packaging material, the upper limit is preferably about 10 μm or less, more preferably about 5 μm or less, further preferably about 4 μm or less, and the lower limit is preferably about 0.5 μm or more, more preferably about 1 μm or more, further preferably about 2 μm or more. The thickness of the adhesive layer 2 is preferably about 0.5 to 10. Mu.m, about 0.5 to 5. Mu.m, about 0.5 to 4. Mu.m, about 1 to 10. Mu.m, about 1 to 5. Mu.m, about 1 to 4. Mu.m, about 2 to 10. Mu.m, about 2 to 5. Mu.m, or about 2 to 4. Mu.m.

The adhesive layer 2 may contain a colorant, a thermoplastic elastomer, an adhesion-imparting agent, a filler, or the like as long as the adhesion is not impaired. The adhesive layer 2 contains a colorant, whereby the battery packaging material can be colored. As the colorant, known pigments, dyes, and the like can be used. In addition, 1 kind of colorant may be used alone, or 2 or more kinds may be mixed and used.

The type of pigment is not particularly limited insofar as the adhesiveness of the adhesive layer 2 is not impaired. Examples of the organic pigment include azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, viol pigments, perylene pigments, isoindolinone pigments, etc., examples of the inorganic pigment include carbon black pigments, titanium oxide pigments, cadmium pigments, lead pigments, chromium oxides, etc., and examples of the inorganic pigment include fine mica (mica) powder and fish scale foil.

Among the colorants, carbon black is preferable, for example, for making the appearance of the battery packaging material black.

The average particle diameter of the pigment is not particularly limited, and examples thereof include about 0.05 to 5. Mu.m, preferably about 0.08 to 2. Mu.m. The average particle diameter of the pigment is a median particle diameter measured by a laser diffraction/scattering type particle diameter distribution measuring device.

The content of the pigment in the adhesive layer 2 is not particularly limited as long as the battery packaging material can be colored, and examples thereof include about 5 to 60% by mass, preferably 10 to 40% by mass.

The adhesion between the base material layer 1 and the barrier layer 3 by the adhesive layer 2 can be evaluated by measuring, for example, initial peel strength, peel strength at 120 ℃. The initial peel strength and the peel strength at 120℃can be measured according to the following procedures.

< evaluation of adhesion-measurement of initial peel Strength >)

The battery packaging material was cut into a long strip having a width of 15mm×a length of 100mm, and used as a test piece. The barrier layer and the base material layer of the test piece were peeled off from each other by about several tens of mm in the longitudinal direction. Next, the barrier layer side and the base material layer side of the test piece were each mounted in a tensile tester so that the distance between the gauge lines was 50 mm. Wherein, in order that the chuck does not fall off during the test, the chuck section of the test piece may be reinforced with an adhesive tape. The tensile strength was measured at a speed of 50 mm/min in the 180℃direction, and the strength at which the distance between the reticles became 57mm was measured. The average of 3 measurements was taken as the initial peel strength (N/15 mm) between barrier layer and substrate layer. When the shape of the test piece cannot be prepared due to a small sample, the test piece is measured in a measurable size, converted to a width of 15mm, and then the peel strength is calculated.

< evaluation of adhesion-measurement of peel Strength at 120 ℃ >

According to JIS K7127:1999, the peel strength of the battery packaging material at each measured temperature in a 120 ℃ environment was measured as follows. Specifically, the battery packaging material was cut into a long strip of 15mm width x 100mm length in the width direction, and used as a test piece. The barrier layer and the base material layer of the cut sheet were separated from each other by about several tens of mm in the longitudinal direction. Next, the barrier layer side and the base material layer side of the test piece were each mounted in a tensile tester so that the distance between the gauge lines was 50 mm. Wherein, in order that the chuck does not fall off during the test, the chuck section of the test piece may be reinforced with an adhesive tape. After being left in a 120℃environment for 2 minutes in a state of being mounted in a tensile tester, the steel sheet was stretched in a 180℃direction at a speed of 50 mm/min in a 120℃environment, and the strength at which the distance between the reticles became 57mm was measured. The average of 3 measurements was taken as 120℃peel strength (N/15 mm) between barrier layer and substrate layer.

[ Barrier layer 3]

In the battery packaging material according to the second aspect of the invention, the structure of the barrier layer 3 is the same as that of the barrier layer 3 according to the first aspect of the invention, and therefore, the description thereof is omitted.

[ resist films 3a, 3b ]

In the battery packaging material according to the second aspect of the invention, the surface of the barrier layer 3 on the adhesive layer 2 side has a resist film 3b that contacts the adhesive layer 2.

The packaging material for a battery according to the second aspect of the invention is characterized in that the resist film 3b detects a peak P derived from an o—c=o bond in a range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy (XPS) _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50. By the value P of the peak height ratio _OCO/C-C Within such a specific range, the resist film 3b provided on the surface of the barrier layer 3 has excellent adhesion to the adhesive layer 2 in contact therewith. The battery packaging material of the second invention has high adhesion between the resist film 3b and the adhesive layer 2, and therefore exhibits high peel strength even when subjected to a severe peel test as measured in examples, and can exhibit excellent adhesion over a long period of time.

The value P as the peak height ratio is a value from the viewpoint of further improving the adhesion between the resist film 3b and the adhesive layer 2 (and between the resist film 3a and the layer adjacent thereto, which will be described later) _OCO/C-C The lower limit may be preferably about 0.10, more preferably 0.15, and the upper limit is preferably about 0.50. In addition, the value P is the peak height ratio _OCO/C-C The preferable range of (2) is about 0.10 to 0.50, more preferably about 0.15 to 0.50. Wherein P is _OCO/C-C When the amount is about 0.10 or more, as described above, better adhesion can be obtained, and a tendency to have good electrolyte resistance can also be obtained. On the other hand, P _OCO/C-C When the amount exceeds about 0.5, the introduction of an excessive amount of o—c=o bond may not only saturate the effect of improving the electrolyte resistance, but also cause a problem that the aggregation force of molecules constituting the treatment liquid for forming the resist film becomes too high, and the treatment liquid may lack stability. Specifically, P _OCO/C-C If the content exceeds about 0.5, the components constituting the treatment liquid are poorly water-soluble, and therefore, it becomes difficult to prepare the treatment liquid, and even if the treatment liquid can be prepared, problems such as gelation and precipitation occur due to aggregation of the components (for example, acrylic resin) with each other, and it becomes difficult to form a uniform and stable resist film. Further, when the treatment liquid is prepared and stored in advance as a treatment liquid stock solution having a higher concentration, there is a problem that storage stability of the treatment liquid stock solution, particularly storage stability in cold places, is lowered, and storage stability is easily lowered in winter, for example.

In the battery packaging material according to the second aspect of the invention, the battery packaging material further comprisesFrom the viewpoint of improving the adhesion between the resist film 3b and the adhesive layer 2 (and the resist film 3a and the layers adjacent thereto described later), the resist film 3b preferably detects the peak P of Cr2P3/2 from the chromium compound in the range of 576eV to 581eV by analysis using XPS _Cr . By detecting this peak, it was confirmed that the composition for forming the resist film 3b by the chemical surface treatment contained a chromium compound. Cr atoms having-COOH groups, -NH groups in the coating ₂ The core action of the coordination bond is that the group, -CN group and the like, and therefore, the core action forms a bridging structure with other functional groups having a structure capable of forming a ligand, such as polycarboxylic acid or an ammonium salt thereof, and durability such as corrosion resistance and chemical resistance is achieved.

In the battery packaging material according to the second aspect of the invention, the resist film 3b preferably detects the peak P of P2P derived from the phosphoric acid compound in the range of 132eV to 135eV by analysis by X-ray photoelectron spectroscopy _P . By detecting the peak P _P It was confirmed that phosphoric acid or a salt thereof was contained in the composition for forming the resist film 3b by the chemical surface treatment. In chemical surface treatment, phosphoric acid etches a metal surface to form a high-durability coating such as a phosphate compound coating on the metal surface. In addition, it is considered that the metal surface is brought into close contact with the high-durability coating film because the above coordination bridge structure is also introduced in the presence of a metal atom having a high coordination number such as Cr.

In the battery packaging material according to the second aspect of the invention, the peak of F1s from the fluorine compound is preferably detected in the range of 685eV to 689eV by analyzing the resist film 3b by XPS. By detecting the peak P _F It was confirmed that the composition for forming the resist film 3b by the chemical surface treatment contained a fluorine compound. When the barrier layer is aluminum, fluorine atoms are bonded to aluminum to form an aluminum fluoride coating film having higher durability than an aluminum oxide coating film.

Further, from the same point of view, in the packaging material for a battery of the second invention, the following is advantageousThe resist film 3b is preferably formed on the peak P by analysis by X-ray photoelectron spectroscopy _Cr Peak P _P Peak P _F At least peak P is detected in _Cr More preferably, in addition to peak P _Cr Peak P is detected in addition to _P Peak sum P _F At least one of them, particularly preferably peak P _Cr Peak P _P Peak sum P _F All detected.

In the battery packaging material according to the second aspect of the invention, the packaging material may have, on only the surface of the separator 3 on the adhesive layer 2 side, the above-described various peaks (i.e., the value P of the above-described peak-to-peak ratio) detected by XPS analysis _OCO/C-C Peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F At least 1) of the resist film 3b, the resist film 3a having the various peaks may be provided on the surface of the barrier layer 3 on the adhesive layer 5 side. By providing the resist film 3a, adhesion between the resist film 3a on the surface of the barrier layer 3 and a layer (for example, the adhesive layer 5) in contact with the resist film can be improved.

The method of analyzing the resist films 3a and 3b of the second invention using XPS is the same as that described in the first invention.

In the second invention, when analyzing peak positions (binding energy) of a resist film laminated on a battery packaging material using XPS, first, a layer (adhesive layer) laminated on a barrier layer on the side to be analyzed is physically peeled off. At this time, it is not physically peeled off by water, an organic solvent, an aqueous solution of an acid or a base, or the like. When the adhesive layer remains on the surface of the barrier layer after the separation between the barrier layer and the adhesive layer, the remaining adhesive layer is removed by etching with Ar-GCIB. The surface of the barrier layer thus obtained was analyzed for a resist film by XPS. The layers laminated on the barrier layer on the side to be analyzed are heat-fusible resin layers, adhesive layers, and the like, and the layers are physically peeled off and etched away in the same manner, and analyzed.

In addition, as in the first invention, the presence or absence of each of the above peaks can be easily confirmed as a detected peak displayed on the monitor screen of the X-ray photoelectron spectroscopy apparatus when the peak is clear, but when the peak is small and not clear, the presence or absence of the relevant peak of the atom is determined based on the area, the half width, and the presence or absence of the relevant peak.

The resist films 3a and 3b can be formed by chemically surface-treating the surface of the barrier layer 3 in the same manner as in the first invention. From a value P suitable for forming a peak having the above peak height ratio _OCO/C-C Peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F In terms of the resist film of at least 1, the resist films 3a, 3b are preferably formed of a composition containing at least an acrylic resin having COOH groups, a chromium compound, and a phosphoric acid compound. More specifically, the surface of the barrier layer 3 is chemically surface-treated with a treatment liquid containing these components, whereby the resist films 3a, 3b can be formed appropriately. The chemical surface treatment may be performed by applying a treatment liquid to the surface of the barrier layer 3 and performing a sintering treatment. Wherein the peak height ratio value P can be obtained by appropriately adjusting the composition of the treatment liquid, the treatment method and the treatment conditions _OCO/C-C Adjusting to the above range.

From the value P of the peak height ratio _OCO/C-C In view of the above-mentioned range and further improvement of the adhesion between the adhesive layer 2 and the resist film 3b (and between the resist film 3a and the layer adjacent thereto), the acrylic resin may be exemplified by the same resin as exemplified in the first invention. The weight average molecular weight and acid value of the acrylic resin are the same as those of the first invention.

From the same point of view, the chromium compound is the same as the first invention.

The method and the crosslinking agent for forming a high-durability coating film by imparting a crosslinked structure to the resist coating films 3a and 3b as described above are similar to those of the first invention.

Further, the composition for forming the resist films 3a and 3b preferably further contains phosphoric acid. The phosphoric acid is the same as the first invention.

From the viewpoint of further improving the adhesion of the adhesive layer 2 to the resist film 3b (and the resist film 3a and the layers adjacent thereto), particularly preferable compositions of the composition (treatment liquid) for forming the resist films 3a, 3b include a composition containing polyacrylic acid, chromium (III) fluoride and phosphoric acid, a composition containing polyacrylic acid and chromium (III) fluoride, a composition containing an acrylic methacrylate copolymer, chromium (III) fluoride and phosphoric acid, a composition containing an acrylic methacrylate copolymer, chromium (III) nitrate and phosphoric acid, a composition containing a sodium salt of an acrylic maleic acid copolymer, a composition containing chromium (III) fluoride and phosphoric acid, a composition containing a styrene acrylate copolymer, chromium (III) fluoride and phosphoric acid, various salts (sodium salt, ammonium salt, amine salt, etc.) of polyacrylic acid, a composition containing chromium (III) fluoride and phosphoric acid.

The solid content concentration of the processing liquid for forming the resist coating film is the same as that of the example in the first invention.

The thickness of the resist films 3a and 3b is not particularly limited, and from the viewpoint of effectively improving the adhesion between the adhesive layer 2 and the resist film 3b (and between the resist film 3a and the layer adjacent thereto), it is preferably about 1nm to 10 μm, more preferably about 1 to 100nm, and even more preferably about 1 to 50 nm. The thickness of the resist film can be measured by observation with a transmission electron microscope or by a combination of observation with a transmission electron microscope and energy dispersive X-ray spectrometry or electron beam energy loss spectrometry.

From the same point of view, every 1m as the barrier layer 3 ² The amount of Cr in the surface resist coatings 3a, 3b is the same as in the example of the first invention.

The method of applying the composition for forming the resist coatings 3a, 3b to the surface of the barrier layer 3 is also the same as the first invention.

From the value P of the peak height ratio _OCO/C-C The adhesive layer 2 and the resist film 3b (and the resist film 3a and the layer adjacent thereto) are set to the above-described predetermined range, and are made from the viewpoint of improving the adhesion thereof The heating temperature for forming a resist film by sintering the treatment solution is preferably about 120 to 210 ℃, more preferably about 140 to 190 ℃. From the same viewpoint, the sintering time is preferably about 1 to 30 seconds, more preferably about 5 to 10 seconds.

In the second invention, from the viewpoint of more effectively chemically surface-treating the surface of the barrier layer 3, it is also preferable to perform degreasing treatment by a known treatment method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method before providing the surface of the barrier layer 3 with a resist film.

[ adhesive layer 5]

In the battery packaging material according to the second aspect of the invention, the adhesive layer 5 is a layer that is provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed to improve adhesion between them. More specifically, the adhesive layer 5 is provided so as to be in contact with the resist film 3a on the surface of the barrier layer 3. The adhesive layer 5 of the second invention may have the same structure as that shown in the adhesive layer 5 of the first invention.

In general, from the viewpoint of improving the adhesion between the barrier layer and the heat-fusible resin layer, it is preferable to have an adhesive layer between them, but when a resist film is provided on the heat-fusible resin layer side surface of the barrier layer, the adhesion between the resist film and the adhesive layer may be reduced. In contrast, in the battery packaging material according to the second aspect of the invention, the resist film 3a has the above-described value P of the specific peak height ratio _OCO/C-C By providing the adhesive layer 5, adhesion between the resist film 3a and the adhesive layer 5 is effectively improved.

The adhesive layer 5 is formed of a resin capable of adhering the resist film 3a to the heat-fusible resin layer 4. As the resin for forming the adhesive layer 5, for example, the same adhesive as the adhesive exemplified for the adhesive layer 2 can be used, for example, the adhesive mechanism and the kind of the adhesive component. In the adhesive exemplified by the adhesive layer 2, from the viewpoint of further improving the adhesion between the resist film 3a and the adhesive layer 5, the resin used for forming the adhesive layer 5 is preferably a cured product of a resin composition containing a compound containing an isocyanate group, an oxazoline group or an epoxy group as a curing agent in the adhesive component, more preferably a cured product of a resin composition containing an acid-modified polyolefin as an adhesive component and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group and a compound having an epoxy group as a curing agent.

[ Heat-fusible resin layer 4]

In the battery packaging material according to the second aspect of the invention, the heat-fusible resin layer 4 has the same structure as the heat-fusible resin layer 4 according to the first aspect of the invention, and therefore, the description thereof will be omitted.

[ surface coating 6]

In the battery packaging material according to the second aspect of the invention, the surface coating layer 6 has the same structure as the surface coating layer 6 according to the first aspect of the invention, and therefore, the description thereof will be omitted.

2-3. Method for manufacturing packaging material for battery

The method for producing the battery packaging material of the second aspect of the present invention is not particularly limited as long as a laminate having laminated layers of a predetermined composition can be obtained, and the following methods can be used: comprises a step of laminating at least a base material layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,

when the barrier layer is laminated, a resist film is provided on the surface of the barrier layer on the adhesive layer side so as to contact the adhesive layer, and the resist film is used as a resistThe following films were used as the sexual film 3 b: by using XPS analysis, the resist film 3b detected the peak P from the O-c=o bond in the range of 287eV to 290eV _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50.

As an example of the method for producing the battery packaging material of the second invention, the following is given. First, a laminate (hereinafter, also referred to as "laminate a") is formed by laminating a base layer 1, an adhesive layer 2, and a barrier layer 3 (having a resist film 3b, which will be omitted below) in this order. Specifically, the laminate a can be formed by the following dry lamination method: the adhesive for forming the adhesive layer 2 is applied to the base material layer 1 or the barrier layer 3 by a coating method such as gravure coating or roll coating, and after drying, the adhesive layer 2 is cured by laminating the barrier layer 3 or the base material layer 1. In this case, when the barrier layer 3 is laminated, a layer in which the above-described resist coating is formed in advance on at least one surface of the barrier layer 3 is used. The method of forming the resist films 3a and 3b is as described above.

Next, the adhesive layer 5 and the heat-fusible resin layer 4 are laminated on the barrier layer 3 of the laminate a. As a method of providing the adhesive layer 5 on the barrier layer 3, for example, a resin component constituting the adhesive layer 5 may be coated on the barrier layer 3 of the laminate a by a gravure coating method, a roll coating method, an extrusion lamination method, or the like. As a method of providing the adhesive layer 5 between the barrier layer 3 and the heat-fusible resin layer 4, for example, the following methods may be mentioned: (1) A method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate a by coextrusion (coextrusion lamination method); (2) A method of forming a laminate of the adhesive layer 5 and the heat-fusible resin layer 4 and laminating the laminate on the barrier layer 3 of the laminate a by a heat lamination method; (3) A method in which an adhesive for forming the adhesive layer 5 is applied to the barrier layer 3 of the laminate a by an extrusion method or a solution, dried at a high temperature, and laminated by a sintering method or the like, and the heat-fusible resin layer 4 previously formed into a sheet shape is laminated on the adhesive layer 5 by a heat lamination method; (4) A method (sandwich lamination method) in which the laminate a and the heat-fusible resin layer 4 are bonded by the adhesive layer 5 while flowing into the molten adhesive layer 5 between the barrier layer 3 of the laminate a and the heat-fusible resin layer 4 which has been formed into a sheet in advance.

By the above-described operation, a laminate composed of the surface coating layer, the base material layer 1, the adhesive layer 2, the barrier layer 3 having a resist coating on at least one surface, the adhesive layer 5, and the heat-fusible resin layer 4 is formed, and the adhesive layer 2 and the adhesive layer 5, if necessary, are firmly bonded to each other, and further subjected to heat treatment such as a hot roll contact type, a hot air type, a near infrared ray type, a far infrared ray type, or the like.

In the battery packaging material of the second aspect of the present invention, each layer constituting the laminate may be subjected to a surface activation treatment such as corona treatment, sand blast treatment, oxidation treatment, or ozone treatment as necessary in order to improve or stabilize film forming property, lamination treatment, suitability for 2 times of processing (bagging and embossing) of the final product, and the like.

2-4. Use of packaging material for battery

The description of the use of the battery pack according to the second aspect of the invention is the same as that of the battery pack according to the first aspect of the invention, and therefore, the description thereof is omitted.

(third invention)

The resist film of the third aspect of the invention is characterized by using X-ray photoelectron spectroscopyAnalysis by the method detected peak P of C1s from O-c=o bond in the range 287eV to 290eV _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C And peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C Is in the range of 0.10 to 0.50 inclusive.

The packaging material according to the third aspect of the present invention is a packaging material comprising a laminate comprising at least a base layer, a barrier layer, and a heat-fusible resin layer in this order, wherein the barrier layer has a resist film according to the third aspect of the present invention on one surface. In addition, in the case of a packaging material according to the third aspect of the present invention, when the packaging material is composed of a laminate including at least a base layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, the surface of the barrier layer on the adhesive layer side has the resist film according to the third aspect of the present invention so as to be in contact with the adhesive layer.

Further, the metal material with a resist film according to the third aspect of the present invention is characterized by comprising a metal material and the resist film according to the third aspect of the present invention formed on the surface of the metal material. The metal material with a resin film according to the third aspect of the present invention is characterized by comprising a metal material, a resist film according to the third aspect of the present invention provided on the surface of the metal material, and a resin film provided on the surface of the resist film.

The resist film, the packaging material, the method of manufacturing the same, the metal material with the resist film, and the metal material with the resin film according to the third invention will be described in detail below with reference to fig. 9 to 14. Fig. 9 to 12 show a manner in which the third resist film 3a of the present invention is provided on the surface of the packaging material 13 on the adhesive layer 5 side of the barrier layer 3 so as to be in contact with the adhesive layer 5. Fig. 11 and 12 show a manner in which a resist film 3b is provided on the surface of the packaging material 13 on the side of the base material layer 1 of the barrier layer 3 so as to be in contact with the adhesive layer 2. Fig. 13 shows a method in which the resist film 3a of the third invention is provided on the surface of the metal material 7 of the metal material 11 having the resist film. Fig. 14 shows a method in which the resist film 3a of the third invention is provided on the surface of the metal material 7 of the metal material 12 with a resin film.

In the third invention, the corrosion resistance means acid resistance, alkali resistance, and the like. Further, as a component that causes corrosion of the metal material or the barrier layer, there are an acid component (including an electrolytic solution), an alkali component, and the like. As described above, it is known that an electrolyte solution used in a lithium ion battery or the like contains a fluorine compound (LiPF ₆ 、LiBF ₄ Etc.) and then generates hydrogen fluoride as an acid component when the fluorine compound reacts with water, and in general, the electrolyte reacts with moisture in the environment to be acidic.

3-1. Corrosion-resistant coating film

Regarding the resist film 3a of the third invention, by analysis by X-ray photoelectron spectroscopy, the resist film detects the peak P of C1s from o—c=o bond in the range of 287eV to 290eV _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C And peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50. That is, the resist film 3a of the third invention is the same as the resist film 3a of the first invention. By making the peak height ratio value P _OCO/C-C Within such a specific range, the resist film 3a of the third invention can suppress the decrease in adhesion between the metal material (for example, a barrier layer of the packaging material of the third invention, a metal material of the metal material with a resin film of the third invention, and the like described later) and the resin layer (for example, an adhesive layer of the packaging material of the third invention, a resin film of the metal material with a resin film of the third invention, and the like described later) provided thereon in an atmosphere in which a component that causes corrosion of the metal material, such as an electrolyte solution, is present.

The peak height ratio value P of the resist film 3a is a value from the viewpoint of more effectively suppressing the decrease in adhesion between the metal material (hereinafter, for example, the barrier layer 3 or the metal material 7) and the resin layer (hereinafter, for example, the adhesive layer 5 or the resin film 8) _OCO/C-C The lower limit is preferably about 0.15, and the upper limit is preferably about 0.45, more preferably 0.30. In addition, as peak heightValue of ratio P _OCO/C-C Preferable ranges of (2) include about 0.10 to 0.45, about 0.10 to 0.30, about 0.15 to 0.50, about 0.15 to 0.45, and about 0.15 to 0.30.

From the viewpoint of more effectively suppressing the decrease in the adhesion of the acid-resistant coating film 3a to the resin layer in the presence of the component that causes corrosion of the metal material such as the electrolyte, the peak P of Cr2P3/2 from the chromium compound is preferably detected in the range of 576eV to 581eV by analysis using XPS for the acid-resistant coating film 3a _Cr . By detecting this peak, it was confirmed that the chromium compound was contained in the treatment liquid for forming the resist film 3a by the chemical surface treatment. Cr atoms having-COOH groups, -NH groups in the coating film ₂ The core action of coordination bonding is performed by the group, -CN group, etc., and therefore, a bridging structure is formed with other functional groups having a structure capable of forming a ligand, such as polycarboxylic acid or an ammonium salt thereof, and durability of corrosion resistance is achieved.

In addition, from the same point of view, the resist film 3a preferably detects the peak P of P2P from the phosphoric acid compound in the range of 132eV to 135eV by analysis using X-ray photoelectron spectroscopy _P . By detecting the peak P _P It was confirmed that phosphoric acid or a salt thereof was contained in the treatment liquid for forming the resist film 3a by the chemical surface treatment. In chemical surface treatment, phosphoric acid etches a metal surface to form a high-durability coating such as a phosphate compound coating on the metal surface. In addition, it is considered that the metal surface is brought into close contact with the high-durability coating film because the above coordination bridge structure is also introduced in the presence of a metal atom having a high coordination number such as Cr.

In addition, from the same point of view, by analysis using XPS, the resist film 3a preferably detects the peak P of F1s from a fluorine compound in the range of 685eV to 689eV _F . By detecting the peak P _F It was confirmed that the fluorine compound was contained in the treatment liquid for forming the resist film 3a by the chemical surface treatment. When the metal material is aluminum, fluorine atoms are bonded to aluminum to form an aluminum fluoride coating film having higher durability than an aluminum oxide coating film.

The method of analyzing the resist film 3a by XPS is the same as that described in the first invention.

In analyzing a resist film laminated on the packaging material 13 described later by XPS, first, a layer (adhesive layer, heat-fusible resin layer, adhesive layer, or the like) laminated on the barrier layer is physically peeled off. At this time, it is not physically peeled off by water, an organic solvent, an aqueous solution of an acid or a base, or the like. When a layer (e.g., an adhesive layer or the like) laminated on the barrier layer remains on the surface of the barrier layer after the barrier layer and the layer (e.g., adhesive layer or the like) laminated on the barrier layer are peeled off, the remaining layer is removed by etching with ar—gcib. The surface of the barrier layer thus obtained was analyzed for a resist film by XPS. In the case of analyzing a resist film of a metal material 12 provided with a resin film described later by XPS, the resin film laminated on the metal material was also physically peeled off, and the surface of the metal material was analyzed by XPS.

In the same manner as in the first invention, the presence or absence of each of the above peaks can be easily confirmed as a detected peak displayed on the monitor screen of the X-ray photoelectron spectroscopy apparatus when the peak is clear, but when the peak is small and not clear, the presence or absence of the relevant peak of the atom is determined based on the area, the half width, and the presence or absence of the relevant peak.

The resist film 3a may be formed by chemically surface-treating the surface of the metal material. From a value P suitable for forming a peak having the above peak height ratio _OCO/C-C Peak P from chromium compound _Cr Peak P from phosphate compound _P And peak P from fluorine compound _F In terms of the resist film of at least 1, the resist film is preferably formed from a composition containing at least an acrylic resin having COOH groups, a chromium compound, and a phosphoric acid compound. More specifically, the surface of the metal material is chemically surface-treated with a treatment liquid containing these components, whereby the resist film 3a can be formed appropriately. The chemical surface treatment can be carried out by applying a treatment liquidAnd sintering the surface of the metal material.

From the value P of the peak height ratio _OCO/C-C In view of the above-described range and more effectively suppressing the decrease in adhesion between the resist film 3a and the layer adjacent thereto (for example, the adhesive layer 5 and the like) (and between the resist film 3b and the layer adjacent thereto), the acrylic resin may be the same resin as exemplified in the first invention. The weight average molecular weight and acid value of the acrylic resin are the same as those of the first invention.

The method and the crosslinking agent for imparting a crosslinked structure to the resist film 3a to form a film with high durability are similar to those of the first invention.

The phosphoric acid compound has a cleaning effect on the surface of the metal material (specifically, an effect of removing a deteriorated oxide film or stain on the surface of the barrier layer) and an effect of forming a phosphate ion in the sintered film to coordinate with a metal ion such as the surface of the barrier layer or chromium ion to form a bridged structure. In the third invention, it is considered that the carboxylate ions of the resist film achieve the same effect, and therefore, from the viewpoint of improving the cleaning effect of the metal material and stably forming the resist film, it is preferable to use a phosphoric acid compound.

From the viewpoint of further improving the adhesion of the acid-resistant coating film 3a to the resin layer in an atmosphere in which a component that causes corrosion of a metal material such as an electrolyte solution exists, particularly preferred compositions of the composition (treatment solution) for forming the resist coating film 3a include a composition containing polyacrylic acid, chromium (III) fluoride and phosphoric acid, a composition containing polyacrylic acid and chromium (III) fluoride, a composition containing acrylic methacrylate copolymer, chromium (III) fluoride and phosphoric acid, a composition containing acrylic methacrylate copolymer, chromium (III) nitrate and phosphoric acid, a composition containing sodium salt of acrylic maleic acid copolymer, chromium (III) fluoride and phosphoric acid, a composition containing acrylic styrene copolymer, chromium (III) fluoride and phosphoric acid, various salts (sodium salt, ammonium salt, amine salt, etc.) of polyacrylic acid, and a composition containing chromium (III) fluoride and phosphoric acid.

The solid content concentration of the treatment liquid for forming the resist film 3a is the same as that of the first embodiment.

The thickness of the resist film 3a is not particularly limited, and from the viewpoint of further improving the adhesion between the acid-resistant film 3a and the resin layer in an atmosphere in which a component such as an electrolyte solution causes corrosion of the metal material, it is preferably about 1nm to 10 μm, more preferably about 1 to 100nm, and still more preferably about 1 to 50 nm. The thickness of the resist film can be measured by observation with a transmission electron microscope or by a combination of observation with a transmission electron microscope and energy dispersive X-ray spectrometry or electron beam energy loss spectrometry.

From the same point of view, every 1m as a metal material ² The amount of Cr in the resist film 3a on the surface is the same as that in the example of the first invention.

The method of applying the treatment liquid for forming the resist film 3a to the surface of the metal material is also similar to the first invention.

From the value P of adjusting the composition of the treatment liquid to make the peak height ratio _OCO/C-C In view of the above-mentioned predetermined range and further improvement of the adhesion between the acid-resistant coating 3a and the resin layer in the atmosphere in which the component causing corrosion of the metal material such as the electrolyte is present, the heating temperature at the time of sintering the treatment liquid to form the resist coating is preferably about 120 to 210 ℃, more preferably about 140 to 190 ℃. From the same viewpoint, the sintering time is preferably about 1 to 30 seconds, more preferably about 5 to 10 seconds.

In view of more effectively performing a chemical surface treatment on the surface of the metal material, it is preferable to perform degreasing treatment by a known treatment method such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or an acid activation method before providing a resist film on the surface of the metal material.

3－2. Packaging material

Laminated structure of packaging material

For example, as shown in fig. 9 to 12, the packaging material of the third invention is composed of a laminate having at least a base material layer 1, a barrier layer 3, and a heat-fusible resin layer 4 in this order. In the packaging material according to the third aspect of the present invention, the base material layer 1 is the outermost layer, and the heat-fusible resin layer 4 is the innermost layer. That is, when the content is contained in the package body formed of the packaging material, the heat-fusible resin layers 4 located at the peripheral edges of the content are heat-fused to each other to seal the content, whereby the content is sealed.

As shown in fig. 9 to 12, in the packaging material of the third invention, a resist film 3a is provided on one surface of the barrier layer 3. When the packaging material of the third invention has the adhesive layer 5, the surface of the barrier layer 3 on the adhesive layer 5 side has the resist film 3a in contact with the adhesive layer 5. Fig. 9 and 10 are schematic views showing the resist film 3a provided only on the surface of the barrier layer 3 on the adhesive layer 5 side. Fig. 11 and 12 are schematic views showing the case where the resist films 3a and 3b are provided on both sides of the barrier layer 3. As described below, the packaging material according to the third aspect of the present invention may include the resist film 3a having the peak characteristics detected by XPS analysis only on one surface side (the adhesive layer 5 side when the adhesive layer 5 is provided) of the barrier layer 3, or may include the resist films 3a and 3b having the peak characteristics detected by XPS analysis on both surfaces of the barrier layer 3.

As shown in fig. 10 to 12, the packaging material of the third invention may have an adhesive layer 2 between the base material layer 1 and the barrier layer 3, if necessary, in order to improve the adhesiveness thereof. As shown in fig. 12, the packaging material of the third invention may have a surface coating layer 6 on the side of the base material layer 1 opposite to the barrier layer 3, if necessary, in order to improve design properties, solvent resistance, scratch resistance, moldability, and the like.

The thickness of the laminate constituting the packaging material 13 of the third invention is not particularly limited, and from the viewpoint of reducing the thickness of the packaging material and forming a packaging material excellent in moldability, for example, about 180 μm or less, preferably about 150 μm or less, more preferably about 60 to 180 μm, and still more preferably about 60 to 150 μm may be mentioned.

Forming layers of packaging material

[ substrate layer 1]

In the packaging material of the third invention, the base material layer 1 is a layer located on the outermost layer side. In the third invention, the structure of the base material layer 1 is the same as that of the base material layer 1 of the first invention, and therefore, the description thereof is omitted.

[ adhesive layer 2]

The adhesive layer 2 is formed of an adhesive capable of adhering the base material layer 1 to the barrier layer 3. In the third invention, the structure of the adhesive layer 2 is the same as that of the adhesive layer 2 of the first invention, and therefore, the description thereof is omitted.

[ Barrier layer 3]

In the packaging material 13, the barrier layer 3 has a function of preventing intrusion of water vapor, oxygen, light, and the like into the content in addition to a function of improving the strength of the packaging material. In the third invention, the structure of the barrier layer 3 is the same as that of the barrier layer 3 of the first invention, and therefore, the description thereof is omitted.

[ resist films 3a, 3b ]

In the packaging material of the third invention, the resist film 3a of the third invention is provided on the surface of one surface side (preferably the heat-fusible resin layer 4 side) of the barrier layer 3. When the packaging material of the third invention has the adhesive layer 5, the adhesive layer 5 and the resist film 3a of the third invention described above are provided on the surface of the barrier layer 3 on the adhesive layer 5 side. The details of the resist film 3a of the third invention are as described in the above description of "3-1. Resist film". In addition, the packaging material 13 may have a resist film 3b on the base material layer 1 side of the barrier layer 3. The resist film 3b preferably has the peak characteristics described above, which are detected by XPS analysis.

In the packaging material 13 of the third invention, the resist film 3a detects the peak P from the o—c=o bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy (XPS) _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50. By making the peak height ratio value P _OCO/C-C Within such a specific range, the resist film 3a provided on the surface of the barrier layer 3 and a layer (for example, the adhesive layer 5 provided as needed) in contact with the resist film have excellent adhesion in an atmosphere in which a component such as an electrolyte solution causes corrosion of the barrier layer. The packaging material of the third invention has high adhesion between the resist film 3a and the layer in contact with the resist film, and therefore exhibits high peel strength even when subjected to a severe peel test as measured in examples, and can exhibit excellent adhesion over a long period of time.

[ adhesive layer 5]

In the packaging material 13 according to the third aspect of the present invention, the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4 as needed to improve adhesion therebetween. More specifically, the adhesive layer 5 is provided in contact with the resist film 3a on the surface of the barrier layer 3. In the third invention, the structure of the adhesive layer 5 is the same as that of the adhesive layer 5 of the first invention, and therefore, the description thereof is omitted.

[ Heat-fusible resin layer 4]

In the packaging material 13 according to the third aspect of the present invention, the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that seals the contents by heat-fusing the heat-fusible resin layers to each other when the contents are stored in the packaging material. In the third invention, the configuration of the heat-fusible resin layer 4 is the same as that of the heat-fusible resin layer 4 of the first invention, and therefore, the description thereof is omitted.

[ surface coating 6]

In the packaging material 13 of the third invention, the surface coating layer 6 may be provided on the outer side of the base material layer 1 (on the side opposite to the barrier layer 3 of the base material layer 1) as needed in order to improve design properties, solvent resistance, scratch resistance, moldability, and the like. When the surface coating layer 6 is provided, the surface coating layer 6 becomes the outermost layer of the packaging material 13. In the third invention, the structure of the surface coating layer 6 is the same as that of the surface coating layer 6 of the first invention, and therefore, the explanation is omitted.

Method for producing packaging material

The method for producing the packaging material of the third aspect of the present invention is not particularly limited as long as a laminate of laminated layers having a predetermined composition can be obtained, and the following methods can be mentioned: the method comprises a step of laminating at least a base layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate, wherein a resist film is provided on one surface of the barrier layer when the barrier layer is laminated, and the resist film 3a of the third invention is used as the resist film. In the packaging material according to the third aspect of the invention, when the barrier layer is laminated including the step of laminating the adhesive layer between the barrier layer and the heat-fusible resin layer, the resist film is provided on the surface of the barrier layer on the adhesive layer side in contact with the adhesive layer. The resist film 3a of the third invention is as described in "3-1. Resist film".

As an example of the method for producing the packaging material of the third invention, the following is given. First, a laminate (hereinafter, also referred to as "laminate a") is formed by laminating the base layer 1, the adhesive layer 2 and the barrier layer 3, which are provided as needed, in this order. Specifically, the laminate a can be formed by the following dry lamination method: the adhesive for forming the adhesive layer 2 is applied to the base material layer 1 or the barrier layer 3 (the resist film 3a in the case of having the resist film 3a, which will be omitted below) by a coating method such as a gravure coating method or a roll coating method, and after drying, the barrier layer 3 or the base material layer 1 is laminated, and the adhesive layer 2 is cured. In this case, when the barrier layer 3 is laminated, a layer in which the above-described resist coating is formed in advance on at least one surface of the barrier layer 3 is used. The method of forming the resist films 3a and 3b is as described above.

Next, a heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate a. When the heat-fusible resin layer 4 is directly laminated on the barrier layer 3, the resin component constituting the heat-fusible resin layer 4 may be coated on the barrier layer 3 of the laminate a by a gravure coating method, a roll coating method, an extrusion lamination method, or the like. In addition, when the adhesive layer 5 is provided between the barrier layer 3 and the heat-fusible resin layer 4, for example, the following methods may be used: (1) A method of laminating the adhesive layer 5 and the heat-fusible resin layer 4 on the barrier layer 3 of the laminate a by coextrusion (coextrusion lamination method); (2) A method of forming a laminate of the adhesive layer 5 and the heat-fusible resin layer 4 and laminating the laminate on the barrier layer 3 of the laminate a by a heat lamination method; (3) A method in which an adhesive for forming the adhesive layer 5 is applied to the barrier layer 3 of the laminate a by an extrusion method or a solution, dried at a high temperature, and then laminated by a sintering method or the like, and the heat-fusible resin layer 4 previously formed into a sheet shape is laminated on the adhesive layer 5 by a heat lamination method; (4) A method (sandwich lamination method) in which the laminate a and the heat-fusible resin layer 4 are bonded by the adhesive layer 5 while flowing into the molten adhesive layer 5 between the barrier layer 3 of the laminate a and the heat-fusible resin layer 4 which has been formed into a sheet in advance.

By the above-described operation, a laminate composed of the surface coating layer, the base material layer 1, the adhesive layer 2, and the barrier layer 3, which are provided as needed, and the adhesive layer 5, which are provided as needed, and the heat-fusible resin layer 4, which are provided as needed, and the adhesive layer 2, the adhesive layer 5, and the barrier layer 2, which are provided as needed, and the adhesive layer 2, the adhesive layer 5, which are provided as needed, are formed, and the laminate may be subjected to heat treatment such as a hot-roll contact type, a hot-air type, a near infrared type, a far-infrared type, and the like.

In the packaging material of the third aspect of the present invention, each layer constituting the laminate may be subjected to a surface activation treatment such as corona treatment, sandblasting treatment, oxidation treatment, or ozone treatment as needed in order to improve or stabilize film forming property, lamination treatment, suitability for 2 times of processing (bagging and embossing) of the final product, and the like.

Use of packaging material

The packaging material of the third aspect of the present invention can be used for packaging bodies for sealing and storing foods, pharmaceuticals, cosmetics, cleaning agents, battery elements (electrolyte, electrodes, etc.), and the like. The package formed of the packaging material according to the third aspect of the present invention can store and circulate the contents.

Specifically, the contents can be sealed by accommodating the contents in a space of a package formed by molding the packaging material and heat-sealing the heat-fusible resin layers to each other. As a method of forming the packaging material into a space, for example, a mold may be used to form a recess from the heat-fusible resin layer side of the film-shaped packaging material to the base material layer side, and the recess may be formed into a space.

Further, a method of molding a film-like packaging material into a bag may be mentioned. Examples of such a bag-like packaging material include square bags, upright bags, pillow corner bags, four-column pillow corner bags, deformed four-column pillow corner bags, corner bottom bags, half-folded bottom corner bags, and half-folded bags.

The packaging material of the third aspect of the present invention comprises at least a base layer, a barrier layer, and a heat-fusible resin layer in this order, and the adhesion between the resist film provided on the surface of the barrier layer and the layer in contact with the resist film is excellent in the presence of a component such as an electrolyte solution that causes corrosion of the barrier layer. Therefore, the packaging material of the third invention is suitable for use as, for example, packaging materials for foods, pharmaceuticals, cosmetics, cleaning agents, and the like.

3-3. Metal material with corrosion-resistant coating

As shown in fig. 13, the metal material with resist coating 11 of the third invention has a metal material 7 and a resist coating 3a of the third invention. The resist film 3a of the third invention is provided on the surface of the metal material 7. The resist film 3a of the third invention is as described in "3-1. Resist film". As the resist film 3a, the resist film 3a of the barrier layer 3 may be used.

As a method for forming the resist film 3a on the surface of the metal material 7, a method described in "3-1. Resist film" may be used.

The metal material 7 is not particularly limited as long as it is a material made of metal. Examples of the metal include aluminum, stainless steel, nickel, copper, zinc, and steel, and an alloy containing at least 1 of these metals.

The shape of the metal material 7 is not particularly limited, and examples thereof include a plate shape and a foil shape.

The thickness of the metal material 7 is not particularly limited, and examples thereof include about 0.005 to 5 mm.

The metal material with a resist film 11 of the third invention is suitable for use as, for example, automobile parts, household electrical appliance parts, construction parts, container parts, battery parts, and the like, since it has the resist film 3a on its surface that protects the surface of the metal material 7 from acid corrosion. For example, a specific example of the battery member may be a metal terminal or a current collector, which is required to have resistance to an electrolyte (to be acidic by reacting with moisture in the environment) and which is formed of the metal material 11 with a resist film according to the third invention.

3-4. Metal material with resin film

As shown in fig. 14, the metal material 12 with a resin film of the third invention has a metal material 7, a resist film 3a of the third invention, and a resin film 8. The resist film 3a of the third invention is provided on the surface of the metal material 7. The resist film 3a of the third invention is as described in "3-1. Resist film". As the resist film 3a, the resist film 3a of the barrier layer 3 may be used.

The metal material 7 is not particularly limited as long as it is a material composed of a metal, and the same materials as those exemplified in the above-mentioned "3-3. Metal material with resist coating" are cited. The shape and thickness of the metal material 7 are also the same as those of the metal material with a resist film.

The metal material with resin film 12 of the third invention has the resist film 3a and the resin film 8 on the surface thereof for protecting the surface of the metal material 7 from acid corrosion, and further the adhesion between the metal material 7 and the resin film 8 in the atmosphere in which the component causing corrosion of the barrier layer such as the electrolytic solution is present can be suitably improved by the resist film 3a. Therefore, the metal material 12 with a resin film is suitable for use as, for example, automobile parts, household electrical appliance parts, building parts, container parts, and the like.

The resin film 8 may be arbitrarily selected according to the application and is not particularly limited. Examples of the resin constituting the resin film 8 include polyester resins, polyethylene resins, polypropylene resins, polycarbonate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyamide resins, polyvinyl acetate resins, epoxy resins, polyimide resins, and the like.

The thickness of the resin film 8 may be arbitrarily selected according to the application and is not particularly limited. The thickness of the resin film 8 may be, for example, about 0.005 to 0.25 mm.

The method of laminating the resin film 8 on the resist film 3a formed on the metal material 7 is not particularly limited, and examples thereof include a method of laminating with an adhesive, a method of laminating with thermal compression bonding, and the like.

Examples

(first invention)

Hereinafter, the first invention will be described in detail with reference to examples and comparative examples. However, the first invention is not limited to the embodiment.

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Examples 1A to 18A and comparative examples 1A to 2A

As the base material layer, a biaxially stretched nylon film having the thickness described in table 1A was prepared. Further, as a barrier layer, an aluminum foil (JIS H4160:1994A8021H-O, thickness 35 μm) was prepared, and both surfaces of the aluminum foil were subjected to a chemical surface treatment to form resist films (thickness 40 nm) having XPS peaks shown in Table 1A, respectively. Details of the processing liquid for forming the resist coating film are as follows. Then, a barrier laminate layer having a resist film on both sides is laminated on the surface of the base material layer by dry lamination. Specifically, a two-pack polyurethane adhesive (polyester polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum foil having a resist film, and an adhesive layer (thickness 3 μm) was formed. Then, the adhesive layer and the base material layer on the barrier layer having the resist film are laminated, and then cured, thereby producing a laminate of the base material layer/the adhesive layer/the barrier layer having the resist film on both sides.

Next, the resin composition constituting the adhesive layer described in table 1A was applied to the surface of the resist film formed on the barrier layer of the obtained laminate so that the thickness of the adhesive layer became 2 μm, and an unstretched polypropylene film (CPP) having the thickness described in table 1A was laminated thereon as a heat-fusible resin layer, and the film was bonded between 2 rolls after heating, whereby an adhesive layer/heat-fusible resin layer was laminated on the surface of the resist film. Then, the obtained laminate was cured (curing of the adhesive layer), whereby a battery packaging material was obtained in which a base material layer, an adhesive layer, a barrier layer having a resist coating on both sides, an adhesive layer, and a heat-fusible resin layer were laminated in this order.

Example 19A and comparative example 3A

As the base material layer, a biaxially stretched nylon film having the thickness described in table 1A was prepared. Further, as a barrier layer, an aluminum foil (JIS H4160:1994A8021H-O, thickness 35 μm) was prepared, and both surfaces of the aluminum foil were subjected to a chemical surface treatment to form resist films (thickness 40 nm) having XPS peaks shown in Table 1A, respectively. Details of the processing liquid for forming the resist coating film are as follows. Next, a barrier laminate layer having a resist film on both sides was laminated on the surface of the base layer by dry lamination. Specifically, a two-pack polyurethane adhesive (polyester polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum foil having a resist film, and an adhesive layer (thickness 3 μm) was formed. Then, the adhesive layer and the base material layer on the barrier layer having the resist film are laminated, and then cured, thereby producing a laminate of the base material layer/the adhesive layer/the barrier layer having the resist film on both sides.

Next, a maleic anhydride-modified polypropylene (PPa) as an adhesive layer (thickness 20 μm) and a random polypropylene (PP) as a heat-fusible resin layer (thickness 15 μm) were laminated on the surface of a resist film formed on the barrier layer of the laminate obtained by the coextrusion lamination method, and an adhesive layer/heat-fusible resin layer was laminated on the surface of the resist film to obtain a battery packaging material in which a base layer/adhesive layer/barrier layer having a resist film on both sides, an adhesive layer, and a heat-fusible resin layer were laminated in this order.

Analysis Using X-ray photoelectron Spectroscopy (XPS)

Analysis of the resist coating was performed in accordance with the following procedure. First, the barrier layer and the adhesive layer are peeled off from each other. At this time, it is not physically peeled off by water, an organic solvent, an aqueous solution of an acid or a base, or the like. After the separation between the barrier layer and the adhesive layer, the adhesive layer remains on the surface of the barrier layer, and the remaining adhesive layer is removed by etching with Ar-GCIB. The surface of the barrier layer thus obtained was analyzed for a resist film by XPS, and the following peaks were observed. Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C The presence or absence of a peak derived from the chromium compound, a peak derived from the phosphoric acid compound, and a peak derived from the fluorine compound are shown in Table 1A.

P _C-C :285eV peak from C1s of C-C bond. As described in the measurement conditions, the entire XPS data was corrected so that the maximum intensity of the main peak reached 285eV.

P _OCO : peak of C1s from O-c=o bond in the range of 287eV to 290eV

P _Cr :576eV to 581eV peak of Cr2p3/2 from chromium compound

P _P : peaks of P2P from phosphoric acid compounds in the range of 132eV to 135eV

P _F : peaks of F1s from fluorine compounds ranging from 685eV to 689eV

The details of the measurement device and measurement conditions of the X-ray photoelectron spectroscopy are as follows.

Measurement device: ESCA-3400 of Shimadzu corporation (Kratos Co., UK) "

Incident X-rays: mg kα (non-monochromic X-ray, hν= 1253.6 ev)

X-ray output: 10kV 20mA (200W)

Measurement area:

< evaluation of adhesion-measurement of initial peel Strength >

The obtained battery packaging materials were cut into strips having a width of 15mm×a length of 100mm, and the strips were used as test pieces. The barrier layer and the heat-fusible resin layer of the test piece were peeled apart from each other by about 20mm in the longitudinal direction. Then, the barrier layer side and the heat-fusible resin layer side of the test piece were each sandwiched between upper and lower chucks, and the test piece was stretched in the 180 ° direction at a speed of 50 mm/min by using a tensile tester (trade name AGS-XPlus manufactured by shimadzu corporation), and the initial peel strength (N/15 mm) of the test piece was measured. The results are shown in Table 1A.

< determination of peel Strength after electrolyte impregnation >

Cutting the obtained packaging material for batteries into strips with a width of 15mm×a length of 100mm, and peeling the space between the barrier layer and the heat-fusible resin layer in the longitudinal direction by about 20mm to obtain a testAnd (5) checking tablets. On the other hand, 1X 10 as an electrolyte was poured into a 100ml screw vial ³ mol/m ³ LiPF of (a) ₆ The solution (ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) =1/1/1 by volume ratio), and water was further added so that the water concentration in the electrolyte reached 1000ppm. Next, the test piece was placed in the above-mentioned threaded vial, and the test piece was immersed at 85℃for 24 hours. Next, the test piece was taken out of the electrolyte solution, immersed in water to sufficiently remove the electrolyte solution, and then, the barrier layer side and the heat-fusible resin layer side of the test piece were each sandwiched between upper and lower chucks, and the test piece was stretched in the 180 ° direction at a speed of 50 mm/min by using a tensile tester (trade name AGS-XPlus manufactured by shimadzu corporation), and the peel strength (N/15 mm) of the test piece after the electrolyte solution immersion was measured. The results are shown in Table 1A.

[ Table 1A ]

In table 1A, ny means biaxially stretched nylon film, DL means an adhesive layer formed by a dry lamination method, CPP means unstretched polypropylene, PPa means maleic anhydride-modified polypropylene, and PP means random polypropylene. The latter numerical value of the raw material constituting each layer means the thickness (μm) of each layer, and for example, "Ny15" means a biaxially stretched nylon film having a thickness of 15 μm.

The treatment liquid a was acrylic resin (polyacrylic acid (molecular weight: 1 ten thousand, acid value: 778)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid b was an acrylic resin (polyacrylic acid (molecular weight: 1 ten thousand, acid value: 778)) + chromium (III) fluoride. The treatment liquid c was acrylic resin (polyacrylic acid (molecular weight: 10 ten thousand, acid value: 764)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid d was an acrylic resin (polyacrylic acid (molecular weight: 80 ten thousand, acid value: 750)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid e was an acrylic resin (acrylic methacrylate copolymer (molecular weight: 2 ten thousand, acid value: 320)) + chromium (III) nitrate) +phosphoric acid. The treatment liquid f was an acrylic resin (acrylic maleic acid copolymer (molecular weight: 2 ten thousand, acid number: 800)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid g was an acrylic resin (acrylic methacrylate copolymer (molecular weight: 2 ten thousand, acid value: 250) +chromium fluoride (III) +phosphoric acid the treatment liquid h was an acrylic resin (acrylic styrene copolymer (molecular weight: 1.5 ten thousand, acid value: 180))+chromium fluoride (III) +phosphoric acid the treatment liquid i was a phenolic resin (amino-modified phenolic resin (molecular weight: 5 thousand, acid value: 0))+chromium fluoride (III) +phosphoric acid the treatment liquid j was an acrylic resin (ammonium polyacrylate salt (molecular weight: 2 ten thousand, acid value: 0))+chromium fluoride (III) +phosphoric acid the adhesive layer a was a glycidyl ether derivative of maleic anhydride-modified polypropylene (PPa: melting peak temperature: 68 ℃) +epoxy resin a (TMP (trimethylolpropane)), the adhesive layer B was a maleic anhydride-modified polypropylene (PPa: melting peak temperature: 87 ℃) +epoxy resin B (bisphenol F) the adhesive layer C was a modified polypropylene (PPa: melting peak temperature: 75 ℃) +isocyanate compound a (PDI (pentamethylene diisocyanate) and the molecular weights were averaged.

As is clear from the results shown in table 1A, the battery packaging materials of examples 1 to 19 had a resist film in contact with the adhesive layer on the surface of the adhesive layer side of the barrier layer, and the resist film detected peak P of C1s from o—c=o bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50. In the packaging material for a battery of these examples, the initial peel strength between the barrier layer and the heat-fusible resin layer was high, and the peel strength was also high after immersing in an electrolyte solution containing a large amount of water and immersing in water again, and the adhesion between the resist film and the adhesive layer was very excellent.

< evaluation of moldability >

The obtained packaging material for batteries was cut into strips having a width of 80mm×a length of 120mm, and test pieces were produced. The test piece was molded using a mold with a pressing pressure of 0.4MPa, which was varied from a molding depth of 0.5mm to a molding depth of 0.5 mm. As a mold, a male mold having a rectangular shape of width 30 mm. Times.length 50mm [ JIS B0659-1 of surface: 2002-attached document 1 (reference) the maximum height roughness (Rz nominal value) specified in table 2 of the surface roughness standard sheet for comparison is 1.6 μm ] and the clearance with the male die is 0.5mm of female die [ JIS B0659-1 of surface: 2002-attached document 1 (reference) describes a straight die having a maximum height roughness (Rz nominal value) of 3.2 μm as specified in table 2 of the surface roughness standard sheet for comparison. The 10 test pieces were cold-rolled and formed, and the deepest forming depth (limit forming depth (mm)) was obtained for each of the 10 test pieces after cold-rolling and forming, in which no pinholes or cracks were generated. Moldability was evaluated according to the following criteria. As a result, in examples 1A to 16A and 19A, the molding properties were evaluated as a. In examples 17A and 18A, the moldability was evaluated as a+ and was particularly good.

A+: the limit forming depth is more than 7.0mm;

a: the limit forming depth is more than 5.0mm and less than 7.0mm;

b: the limit forming depth is more than 4.0mm and less than 5.0mm;

c: the limit forming depth is less than 4.0mm.

< evaluation of insulation Property >)

The insulating properties of the barrier layer and the inside of each of the obtained battery packaging materials were evaluated in the case of biting into a foreign matter seal by the method of biting into a line seal described later. In the battery packaging materials of examples 15A, 16A, and 18A, the time until short-circuiting was 30 seconds or more, and there was no risk of short-circuiting during the sealing time (about several seconds) at the time of manufacturing the battery, and the battery packaging materials were particularly excellent in insulation (short-circuit prevention function). In addition, the battery packaging materials of examples 1A to 14A and 17A have excellent insulation properties, in which the time until short-circuiting is 20 seconds or more and less than 30 seconds. In example 19A, the adhesive layer did not use a curing agent, and the adhesive layer did not have such an excellent short-circuit prevention function, but it was a practically unproblematic level. The method for evaluating the insulation property is as follows. First, each of the obtained battery packaging materials was cut into a rectangular shape having a width of 40mm×a length of 100mm, and test pieces were produced. Further, an aluminum terminal having a thickness of 100 μm, a width of 30mm, and a length of 100mm Upper arrangementThe thermocouple of (c) was a lead wire made of nickel alloy (claiman chrome nickel alloy) and located at the center of the longitudinal end portions. At this time, the lead wire is arranged at the center of the terminal in the width direction and fixed to the terminal by an adhesive tape. Then, the heat-fusible resin layer side of the test piece was overlapped so as to be in contact with the lead wire fixed to the terminal, and the heat-sealed was performed using a 7 mm-wide aluminum metal plate sandwiched from above and below under conditions of 190 ℃ and 1.0MPa in surface pressure. At this time, the barrier layer and the terminal of the test piece were connected to the tester, respectively, and the time until the resistance value measured by the tester at 100V by heat sealing reached 200mΩ or less was taken as the time until the short circuit.

< evaluation of Water vapor Barrier Property >

The water vapor barrier properties of the respective battery packs obtained above were evaluated by the following methods, and the battery packs of examples 1A to 19A were found to have a water content of 20 to 30ppm and sufficiently excellent water barrier properties as a function of the battery packs. The water vapor barrier properties were evaluated according to the following procedures. First, each of the obtained battery packaging materials was cut into long pieces having a width of 120mm×a length of 120mm, and test pieces were produced. Then, the test piece was folded in half at the center so that the heat-fusible resin layers of the test piece faced each other. Then, the side opposite to the folded side was heat-sealed (temperature 190 ℃ C., face pressure 1.0MPa, 3 seconds) with a width of 7mm (length 120 mm), and the heat-sealed width of 7mm was accurately corrected to the remaining width of 3 mm. Then, one of the 2 sides of the folded sheet was heat-sealed to a width of 10mm (temperature 190 ℃ C., surface pressure 2.0MPa, 3 seconds) to form a package having 1 opening. Next, 3g of a mixed liquid of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) =1/1/1 (volume ratio) was injected from the opening of the package, and the package in which the mixed liquid was sealed was produced by heat-sealing the sides in which the opening was formed (temperature 190 ℃ c., surface pressure 2.0MPa, 3 seconds). Next, after each of the obtained packages was stored in an environment having a relative humidity of 90% and a temperature of 60 ℃ for 7 days, the water content of the electrolyte enclosed in the package was measured by the karl fischer method, and the water content in the electrolyte was calculated. The moisture content in the inner surface of the package and the moisture content in the electrolyte solution were measured in advance by the karl fischer method before storage, and the measured moisture content was used as a background subtraction.

(second invention)

Hereinafter, the second invention will be described in detail with reference to examples and comparative examples. However, the second invention is not limited to the embodiment.

< manufacturing of packaging Material for Battery >)

Examples 1B to 42B and comparative examples 1B to 3B

As the base material layer, a biaxially stretched nylon film (thickness 15 μm) or a polyethylene terephthalate film (thickness 25 μm) was prepared. Further, as a barrier layer, an aluminum foil (JIS H4160:1994A8021H-O, thickness 35 μm) or a stainless steel foil (SUS 304, austenitic stainless steel, thickness 35 μm) was prepared, and both sides of the barrier layer were subjected to chemical surface treatment to form resist films (thickness 40 nm) having XPS peaks shown in tables 1B and 2B, respectively. Details of the processing liquid for forming the resist coating film are as follows. Then, a barrier laminate layer having a resist film on both sides is laminated on the surface of the base material layer by dry lamination. Specifically, the resin compositions constituting the adhesive layers described in tables 1B and 2B were applied to one surface of an aluminum foil having a resist film, to form an adhesive layer (thickness 3 μm). Next, an adhesive layer and a base material layer on a barrier layer having a resist film are laminated, and then curing treatment (curing of the adhesive layer) is performed, thereby producing a laminate of the base material layer/the adhesive layer/the barrier layer having the resist film on both sides. Among them, as conditions for curing treatment (curing of adhesive), tests were conducted at 2 cases of 60℃for several tens of hours (condition (i)) and 120℃for several tens of hours (condition (ii)).

Next, an adhesive a was applied to the surface of the resist film formed on the barrier layer of the obtained laminate so that the thickness of the adhesive layer became 2 μm, and an unstretched polypropylene film (CPP) (thickness 30 μm) as a heat-fusible resin layer was laminated thereon, and the film was bonded between 2 rolls after heating, whereby an adhesive layer/heat-fusible resin layer was laminated on the surface of the resist film. Then, the obtained laminate was cured (curing of the adhesive layer), whereby a battery packaging material was obtained in which the base material layer, the adhesive layer, the barrier layer having a resist coating on both sides, the adhesive layer, and the heat-fusible resin layer were laminated in this order.

Analysis Using X-ray photoelectron Spectroscopy (XPS)

Analysis of the resist coating was performed in accordance with the following procedure. First, the barrier layer and the adhesive layer are peeled off from each other. At this time, it is not physically peeled off by water, an organic solvent, an aqueous acid or alkali solution, or the like. After the separation between the barrier layer and the adhesive layer, the adhesive layer remains on the surface of the barrier layer, and the remaining adhesive layer is removed by etching with ar—gcib. The surface of the barrier layer thus obtained was analyzed for a resist film by XPS, and the following peaks were observed. Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C The presence or absence of a peak derived from the chromium compound, a peak derived from the phosphoric acid compound, and a peak derived from the fluorine compound are shown in tables 1B and 2B.

P _OCO : peak of C1s from O-c=o bond in the range of 287eV to 290eV

P _Cr :576eV to 581eV peak of Cr2p3/2 from chromium compound

P _F : peaks of F1s from fluorine compounds ranging from 685eV to 689eV

The details of the measurement device and the measurement conditions of the X-ray photoelectron spectroscopy are the same as those of the first invention.

Hardness measurement Using nanoindentation method

A nanoindenter (TI 950 TriboIndexter manufactured by HYSITRON) was used as a indenter of the nanoindenter, and a Berkovich (Berkovich) type indenter having a right triangular pyramid shape with a front end formed of a diamond tip (TI-0037Cube Corner90 DEG Total included angle manufactured by HYSITRON, model: AA 11041012) was used. First, the pressure head was brought into contact with the surface of the adhesive layer 2 of the obtained battery packaging material in an environment having a relative humidity of 50% and a temperature of 23 ℃, the pressure head was pushed into the adhesive layer 2 from the surface until the load was 40 μn for 10 seconds, the pressure head was held for 5 seconds in this state, and then the load was removed for 10 seconds. Using maximum load P _max (mu N) and the contact projected area A (mu m) at the maximum depth ² ) By P _max The indentation hardness (MPa) was calculated. The position was changed and measured (n=5), and the average value of the obtained indentation hardness was used as the hardness of the adhesive layer 2 obtained by the nanoindentation method. Hardness was measured at the time of curing under the above-mentioned condition (i) and condition (ii), respectively. The surface of the press-fit indenter is a portion where the cross section of the adhesive layer 2 is exposed, the portion being cut in the thickness direction so as to pass through the center portion of the battery packaging material. The cutting can be performed by using a commercially available rotary microtome.

< evaluation of adhesion-measurement of initial peel Strength >

The obtained battery packaging materials were cut into strips having a width of 15mm×a length of 100mm, and test pieces were produced. The separation layer and the base material layer of the test piece were peeled apart by about 40mm in the longitudinal direction. Next, the barrier layer side and the base material layer side of the test piece were each mounted in a tensile tester (trade name AGS-XPlus manufactured by shimadzu corporation) so that the distance between the gauge lines became 50mm, and the test piece was stretched in the 180 ° direction at a speed of 50 mm/min, and the strength at which the distance between the gauge lines became 57mm was measured. The average of 3 measurements was taken as the initial peel strength (N/15 mm) between barrier layer and substrate layer. The results are shown in tables 1B and 2B.

< evaluation of adhesion-measurement of peel Strength at 120 ℃ >

According to JIS K7127:1999, the peel strength of the battery packaging material at each measured temperature in a 120 ℃ environment was measured according to the following procedure.

The obtained battery packaging materials were cut into strips having a width of 15mm in the width direction and a length of 100mm in the length direction, and test pieces were produced. The separation layer of the cut sheet and the base material layer were separated from each other by about 40mm in the longitudinal direction. Then, the barrier layer side and the base material layer side of the test piece were mounted in a tensile tester (trade name AGS-XPlus manufactured by shimadzu corporation) so that the distance between the gauge lines became 50mm, and left at 120 ℃ for 2 minutes. Thereafter, stretching was performed in the 180℃direction at a speed of 50 mm/min in an environment of 120℃to measure the strength at which the distance between the graticules reached 57 mm. The average of 3 measurements was taken as 120℃peel strength (N/15 mm) between barrier layer and substrate layer. The results are shown in tables 1B and 2B.

< evaluation of adhesion-delamination test under damp-heat >)

The obtained battery packaging materials were cut to prepare 80mm (TD). Times.120 Mm (MD) long sheets, which were used as test pieces. Among them, 10 test pieces were prepared for each battery packaging material. The MD of the battery packaging material corresponds to the Rolling Direction (RD) of the barrier layer, and the TD of the battery packaging material corresponds to the TD of the barrier layer. In addition, the direction perpendicular to MD and RD on the same plane is TD. The rolling direction of the barrier layer can be confirmed by the rolling mark of the barrier layer. The mold used was a rectangular male mold [ JIS B0659-1 of surface ] of 31.6Mm (MD). Times.54.5 mm (TD): the 2002-attached document 1 (reference) describes that the maximum height roughness (Rz nominal value) defined in table 2 of the surface roughness standard sheet for comparison is 1.6 μm. Angle r2.0mm, edge r1.0mm. And a female die having a clearance of 0.5mm from the male die [ JIS B0659-1 of surface: the 2002-attached document 1 (reference) describes that the maximum height roughness (Rz nominal value) defined in table 2 of the surface roughness standard sheet for comparison is 3.2 μm. Angle r2.0mm, edge r1.0mm. A mold made of the above materials. The test piece was placed on the female mold so that the heat-fusible resin layer side was located on the male mold side. The test piece was pressed with a face pressure of 0.25MPa to reach each of predetermined molding depths, and cold-roll molding (1-stage molding was conducted). As the molding depth, there are both the shallow case (a) and the deep case (B), specifically, regarding examples 1B to 28B and 36B to 42B and comparative examples 1B to 3B, 5.0mm (a) and 6.0mm (B); examples 29B to 35B were 2.5mm (A) and 3.5mm (B). Then, the cold-rolled sample was placed in a constant temperature and humidity tank at 65℃under an atmosphere of 90% RH, and allowed to stand for 72 hours. The molded samples were taken out of the constant temperature and humidity bath, and visually checked for occurrence of swelling (delamination of the base material layer) between the base material layer and the aluminum alloy foil, and the proportions of the swelled samples in the 10 test pieces are shown in tables 1B and 2B. In addition, the conditions of 65℃and 90% relative humidity in this test are very severe conditions, and particularly in the case of deep molding depth (B), it can be evaluated that excellent adhesion was achieved as long as the frequency of delamination was about 1 out of 10.

< evaluation of moldability >

The obtained packaging material for batteries was cut into strips having a width of 80mm×a length of 120mm, and test pieces were produced. The test piece was molded using a mold with a pressing pressure of 0.4MPa and a molding depth of 0.5mm was changed from a molding depth of 0.5 mm. As a mold, a male mold having a rectangular shape of width 30 mm. Times.length 50mm [ JIS B0659-1 of surface: 2002-attached document 1 (reference) the maximum height roughness (Rz nominal value) specified in table 2 of the surface roughness standard sheet for comparison is 1.6 μm ] and the clearance with the male die is 0.5mm of female die [ JIS B0659-1 of surface: 2002-attached document 1 (reference) describes a straight die having a maximum height roughness (Rz nominal value) of 3.2 μm as specified in table 2 of the surface roughness standard sheet for comparison. For 10 test pieces, cold rolling was performed, and the deepest forming depth (limit forming depth (mm)) was obtained for each of 10 test pieces after cold rolling, in which no pinholes or cracks were generated.

[ Table 1B ]

[ Table 2B ]

In tables 1B and 2B, ny means biaxially stretched nylon film, PET means polyethylene terephthalate film, ALM means aluminum foil, SUS means stainless steel foil, and CPP means unstretched polypropylene. The latter numerical value of the raw material constituting each layer means the thickness (μm) of each layer, and for example, "Ny15" means a biaxially stretched nylon film having a thickness of 15 μm.

The treatment liquid a was acrylic resin (polyacrylic acid (molecular weight: 1 ten thousand, acid value: 778)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid b was an acrylic resin (polyacrylic acid (molecular weight: 1 ten thousand, acid value: 778)) + chromium (III) fluoride. The treatment liquid c was acrylic resin (polyacrylic acid (molecular weight: 10 ten thousand, acid value: 764)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid d was an acrylic resin (polyacrylic acid (molecular weight: 80 ten thousand, acid value: 750)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid e was an acrylic resin (acrylic methacrylate copolymer (molecular weight: 2 ten thousand, acid value: 320)) + chromium (III) nitrate) +phosphoric acid. The treatment liquid f was an acrylic resin (acrylic maleic acid copolymer (molecular weight: 2 ten thousand, acid number: 800)) + chromium (III) fluoride) +phosphoric acid. The treatment liquid g was an acrylic resin (acrylic methacrylate copolymer (molecular weight: 2 ten thousand, acid value: 250) +chromium fluoride (III) +phosphoric acid the treatment liquid h was an acrylic resin (acrylic styrene copolymer (molecular weight: 1.5 ten thousand, acid value: 180))+chromium fluoride (III) +phosphoric acid the treatment liquid i was a phenolic resin (amino-modified phenolic resin (molecular weight: 5 thousand, acid value: 0))+chromium fluoride (III) +phosphoric acid the treatment liquid j was an acrylic resin (ammonium polyacrylate salt (molecular weight: 2 ten thousand, acid value: 0))+chromium fluoride (III) +phosphoric acid the adhesive layer a was a maleic anhydride-modified polypropylene (PPa): melting peak temperature 68 ℃ C. + epoxy resin A (glycidyl ether derivative of TMP (trimethylolpropane)) adhesive layer B is maleic anhydride-modified polypropylene (PPa: melting peak temperature 87 ℃ C.) + epoxy resin B (novolak type epoxy resin of bisphenol F). Adhesive layer C is maleic anhydride-modified polypropylene (PPa: melting peak temperature 75 ℃ C.) + urea acid ester of isocyanate compound A (PDI (pentamethylene diisocyanate)), adhesive layer D is polyester polyol compound + aromatic diisocyanate compound (polyester polyol compound: molecular weight 10000-40000, hydroxyl equivalent weight 0.7-1.9 per mol, trimethylolpropane (TMP) adduct of aromatic diisocyanate compound: toluene Diisocyanate (TDI), the mixing ratio by weight of the polyol compound and the aromatic diisocyanate compound: 1:3). Wherein the molecular weight is weight average molecular weight.

As is clear from the results shown in tables 1B and 2B, the battery packaging materials of examples 1B to 42B had a resist film in contact with the adhesive layer on the surface of the adhesive layer side, and the resist film detected peak P of C1s from o—c=o bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the case of the battery packaging material of these examples, the initial peel strength between the barrier layer and the base material layer was high, and after exposure to 120 ℃ environment, the peel strength was also high, and after exposure to high temperature and high humidity environment, the delamination resistance was excellent, and therefore the adhesion between the resist coating film and the adhesive layer was very excellent.

(third invention)

The third invention will be described in detail with reference to examples and comparative examples. However, the third invention is not limited to the embodiment.

< manufacturing of packaging Material >)

Examples 1C-18C and comparative examples 1C-2C

The same procedure as in examples 1A to 18A and comparative examples 1A to 2A was followed to obtain packaging materials of examples 1C to 18C and comparative examples 1C to 2C in which a base material layer, an adhesive layer, a barrier layer having a resist coating on both sides, an adhesive layer, and a heat-fusible resin layer were laminated in this order.

Example 19C and comparative example 3C

The packaging materials of example 19C and comparative example 3C were obtained by laminating a base material layer, an adhesive layer, a barrier layer having a resist coating on both sides, an adhesive layer, and a heat-fusible resin layer in this order in the same manner as in example 19A and comparative example 3A.

Analysis Using X-ray photoelectron Spectroscopy (XPS)

Analysis of the resist coating was performed in the same manner as in the first invention. Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C The presence or absence of a peak derived from the chromium compound, a peak derived from the phosphoric acid compound, and a peak derived from the fluorine compound are shown in Table 1C.

< evaluation of adhesion-measurement of initial peel Strength A >

Each of the obtained packaging materials was cut into strips having a width of 15mm×a length of 100mm, and test pieces were produced. The barrier layer and the heat-fusible resin layer of the test piece were peeled apart from each other by about 20mm in the longitudinal direction. Next, the barrier layer side and the heat-fusible resin layer side of the test piece were each sandwiched between upper and lower chucks, and the test piece was stretched in the 180℃direction at a speed of 50 mm/min by using a tensile tester (trade name Tensilon Universal Material tester RTG-1210 manufactured by A & D), and the initial peel strength A (N/15 mm) of the test piece was measured. The results are shown in Table 1C.

[ content-resistant Property 1]

< determination of peel Strength B after electrolyte impregnation >

Each of the obtained packaging materials was cut into a long strip having a width of 15mm×a length of 100mm, and then a test piece was produced by peeling the heat-fusible resin layer from the barrier layer by about 20mm in the longitudinal direction. On the other hand, 1X 10 as an electrolyte was poured into a 100ml screw vial ³ mol/m ³ LiPF of (a) ₆ The solution (ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) =1/1/1 by volume ratio), and water was further added so that the water concentration in the electrolyte reached 1000ppm. Next, the test piece was placed in the above-mentioned threaded vial, and the test piece was immersed at 85℃for 24 hours. Next, the test piece was taken out of the electrolyte solution, immersed in water to sufficiently remove the electrolyte solution, and then the barrier layer side and the heat-fusible resin layer side of the test piece were sandwiched between upper and lower chucks, respectively, and a tensile tester (a&D under the trade name Tensilon Universal Material tester RTG-1210), stretching at a speed of 50 mm/min in the 180℃direction, measuringThe peel strength B (N/15 mm) of the test piece after the electrolyte impregnation was determined. The results are shown in Table 1C.

[ content-resistant Property 2]

< determination of peel Strength after 9% aqueous Ammonia solution impregnation >

The peel strength B (N/15 mm) of each of the battery packaging materials of examples 1C, 3C and 4C after immersion in a 9% aqueous ammonia solution (alkaline aqueous solution) was measured in the same manner as in [ content resistance 1] except that a 9% aqueous ammonia solution was used instead of the electrolyte used in [ content resistance 1 ]. As a result, the peel strength was 8.0N/15mm in example 1C, 9.1N.15mm in example 3C, and 8.2N/15mm in example 4C.

[ calculation of the maintenance Rate of peel Strength ]

The initial peel strength A measured in [ content-resistant property 1] and [ content-resistant property 2] and the peel strength B after the electrolyte impregnation were used to calculate the retention rate (B/A) of the peel strength. The results are shown in Table 1C.

[ Table 1C ]

In table 1C, ny means biaxially stretched nylon film, DL means an adhesive layer formed by a dry lamination method, CPP means unstretched polypropylene, PPa means maleic anhydride-modified polypropylene, and PP means random polypropylene. The latter numerical value of the raw material constituting each layer means the thickness (μm) of each layer, and for example, "Ny15" means a biaxially stretched nylon film having a thickness of 15 μm.

The treatment liquids a to j are the same as the treatment liquids a to j of the first invention, respectively.

As apparent from the results shown in Table 1C, the packaging materials of examples 1C to 19C had a resist film in contact with the adhesive layer on the surface of the adhesive layer side of the barrier layer, and the resist film detected peak P of C1s from O-C=O bond in the range of 287eV to 290eV by analysis by X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C ，P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the packaging materials of these examples, the initial peel strength between the barrier layer and the heat-fusible resin layer was high, and the peel strength was also high after immersing in an electrolyte solution containing a large amount of water and immersing in water again, and the adhesion between the resist film and the adhesive layer was very excellent in an atmosphere in which a component such as the electrolyte solution causes corrosion of the barrier layer was present.

< evaluation of moldability >

The moldability evaluation was performed in the same manner as in the first invention. As a result, in examples 1C to 16C and 19C, the molding properties were evaluated as a. In examples 17C and 18C, the moldability was evaluated as a+ and was particularly good.

< evaluation of insulation Property >)

For each of the packaging materials obtained as described above, insulation properties between the barrier layer and the inside in the case of biting into a foreign matter seal were evaluated by a method of biting into a line seal described later. In the packaging materials of examples 15C, 16C, and 18C, the time until short-circuiting was 30 seconds or more, and there was no risk of short-circuiting during the sealing time (about several seconds) at the time of manufacturing the battery, and the packaging materials were excellent in insulation (short-circuit prevention function). The packaging materials of examples 1C to 14C and 17C also had excellent insulation properties even when the time to short circuit was 20 seconds or more and less than 30 seconds. In example 19C, the adhesive layer did not use a curing agent, and the adhesive layer did not have such an excellent short-circuit prevention function, but it was a practically unproblematic level. The method for evaluating the insulation property is as follows. First, each of the obtained packaging materials was cut into a rectangle having a width of 40mm×a length of 100mm, and test pieces were produced. Further, the aluminum terminals having a thickness of 100 μm, a width of 30mm, and a length of 100mm are arranged The thermocouple of (c) was a lead wire made of nickel alloy (claiman chrome nickel alloy) and located at the center of the longitudinal end portions. At this time, the lead is arranged at the center of the terminal in the width direction and fixed to the terminal by an adhesive tapeAnd (3) upper part. Next, the heat-fusible resin layer side of the test piece was overlapped so as to be in contact with the lead wire fixed to the terminal, and the heat-sealed was performed using a 7 mm-wide aluminum metal plate sandwiched between the upper and lower sides under conditions of 190 ℃ and a surface pressure of 1.0 MPa. At this time, the barrier layer and the terminal of the test piece were connected to the tester, respectively, and the time until the resistance value measured by the tester at 100V by heat sealing reached 200mΩ or less was taken as the time until the short circuit.

< evaluation of Water vapor Barrier Property >

The water vapor barrier properties of the respective packaging materials obtained above were evaluated by the following methods, and the packaging materials of examples 1C to 19C were found to have a water content of 20 to 30ppm and sufficiently excellent water barrier properties as functions of the packaging materials. The water vapor barrier properties were evaluated according to the following procedures. First, each of the obtained packaging materials was cut into long pieces 120mm wide by 120mm long, and test pieces were produced. Then, the test piece was folded in half at the center so that the heat-fusible resin layers of the test piece faced each other. Then, the side opposite to the folded side was heat-sealed (temperature 190 ℃ C., face pressure 1.0MPa, 3 seconds) by a width of 7mm (length 120 mm), and the heat-sealed width of 7mm was accurately corrected to the remaining width of 3 mm. Next, one of the 2 sides of the folded sheet was heat-sealed at a width of 10mm (temperature 190 ℃ c., surface pressure 2.0MPa, 3 seconds) to form a package having 1 opening. Next, 3g of a mixed liquid of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) =1/1/1 (volume ratio) was injected from the opening of the package, and the package in which the mixed liquid was sealed was produced by heat-sealing the sides in which the opening was formed (temperature 190 ℃ c., surface pressure 2.0MPa, 3 seconds). Next, after each of the obtained packages was stored in an environment having a relative humidity of 90% and a temperature of 60 ℃ for 7 days, the water content of the electrolyte enclosed in the package was measured by the karl fischer method, and the water content in the electrolyte was calculated. The moisture content in the inner surface of the package and the moisture content in the electrolyte solution were measured in advance by the karl fischer method before storage, and the measured moisture content was used as a background subtraction.

As described above, the first invention provides the invention of the following modes.

A packaging material for a battery comprising a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order,

The battery packaging material according to item 1, wherein the resist film detects a peak of Cr2p3/2 from the chromium compound in a range of 576eV to 581eV by analysis using X-ray photoelectron spectroscopy.

The battery packaging material according to item 1 or 2, wherein the resist film detects a peak of P2P from the phosphoric acid compound in a range of 132eV to 135eV by analysis by X-ray photoelectron spectroscopy.

The battery packaging material according to any one of items 1 to 3, wherein the resist film detects a peak of F1s from a fluorine compound in a range of 685eV to 689eV by analysis using X-ray photoelectron spectroscopy.

The battery packaging material according to any one of items 1 to 4, wherein the resist film is formed of a composition containing at least an acrylic resin having a COOH group, a chromium compound, and a phosphoric acid compound.

The battery pack according to item 5, wherein the acrylic resin is at least 1 selected from the group consisting of polyacrylic acid, an ammonium salt of polyacrylic acid, a sodium salt of polyacrylic acid, and an amine salt of polyacrylic acid.

The battery packaging material according to item 5, wherein the acrylic resin is at least 1 selected from the group consisting of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, an ammonium salt of the copolymer, a sodium salt of the copolymer, and an amine salt of the copolymer.

The battery pack according to any one of items 5 to 7, wherein the chromium compound is at least one of chromium (III) fluoride and chromium (III) nitrate.

The battery packaging material according to any one of items 1 to 8, wherein the resin constituting the adhesive layer has a polyolefin skeleton.

The battery packaging material according to any one of items 1 to 9, wherein the adhesive layer contains an acid-modified polyolefin.

The battery packaging material according to any one of items 1 to 10, wherein a peak derived from maleic anhydride is detected when the adhesive layer is analyzed by infrared spectroscopy.

The battery packaging material according to item 10, wherein the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene,

the heat-fusible resin layer contains polypropylene.

The battery packaging material according to any one of items 9 to 12, wherein the adhesive layer is a cured product of a resin composition containing at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.

The battery packaging material according to any one of items 9 to 12, wherein the adhesive layer is a cured product of a resin composition containing a curing agent having at least 1 selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a C-O-C bond.

The battery packaging material according to any one of items 1 to 12, wherein the adhesive layer contains at least 1 selected from the group consisting of polyurethane resins, ester resins, and epoxy resins.

A method for producing a packaging material for a battery, comprising a step of laminating at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order to obtain a laminate,

a resist film is provided on the surface of the barrier layer on the adhesive layer side so as to contact the adhesive layer,

As the above-mentioned resist film, the following film was used:

the resist film detects a peak P from an o—c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _COOH/C-C Is in the range of 0.10 to 0.50 inclusive.

The battery according to item 17, wherein a battery element having at least a positive electrode, a negative electrode, and an electrolyte is housed in the package formed of the battery packaging material according to any one of items 1 to 15.

The second invention provides the following embodiments.

A packaging material for a battery comprising a laminate comprising, in order, at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer,

The battery packaging material according to item 18, wherein the resist film detects a peak of Cr2p3/2 from the chromium compound in a range of 576eV to 581eV by analysis using X-ray photoelectron spectroscopy.

The battery packaging material according to item 18 or 19, wherein the resist film detects a peak of P2P from the phosphoric acid compound in a range of 132eV to 135eV by analysis by X-ray photoelectron spectroscopy.

The battery packaging material according to any one of items 18 to 20, wherein the resist film detects a peak of F1s from a fluorine compound in a range of 685eV to 689eV by analysis using X-ray photoelectron spectroscopy.

The battery packaging material according to any one of items 18 to 21, wherein the resist film is formed of a composition containing at least an acrylic resin having a COOH group, a chromium compound, and a phosphoric acid compound.

The battery pack according to item 22, wherein the acrylic resin is at least 1 selected from the group consisting of polyacrylic acid, an ammonium salt of polyacrylic acid, a sodium salt of polyacrylic acid, and an amine salt of polyacrylic acid.

The battery packaging material according to item 22, wherein the acrylic resin is at least 1 selected from the group consisting of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, an ammonium salt of the copolymer, a sodium salt of the copolymer, and an amine salt of the copolymer.

The battery pack according to any one of items 22 to 24, wherein the chromium compound is at least one of chromium (III) fluoride and chromium (III) nitrate.

The battery packaging material according to any one of items 18 to 25, wherein the hardness of the laminate when the indenter is pressed into the adhesive layer from the cross section thereof is 30 to 400MPa using a nanoindenter.

The battery packaging material according to any one of items 18 to 26, wherein the adhesive layer has a thickness of 0.5 to 10. Mu.m.

The battery packaging material according to any one of items 18 to 27, wherein the resin constituting the adhesive layer has a polar group.

The battery packaging material according to item 28, wherein the polar group is a nitrogen-containing binding group, an isocyanate group, an oxazoline group or an epoxy group.

The battery packaging material according to item 29, wherein the nitrogen-containing binding group is a urethane binding group.

The battery packaging material according to any one of items 18 to 30, wherein the adhesive layer is a cured product of a polyurethane resin composition containing a polyol compound and an isocyanate compound.

The battery packaging material according to any one of items 18 to 31, wherein the adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.

A method for producing a packaging material for a battery, comprising a step of laminating at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,

as the above-mentioned resist film, the following film was used:

The battery according to item 34, wherein a battery element having at least a positive electrode, a negative electrode, and an electrolyte is housed in the package formed of the battery packaging material according to any one of items 18 to 32.

The third invention provides the following embodiments.

Item 35. A resist coating, by analysis using X-ray photoelectron spectroscopy, detects peak P of C1s from O-C=O bond in the range of 287eV to 290eV _OCO And a bond from C-C was detected at 285eVPeak P of C1s of (C) _C-C ，

Item 36. The resist film of item 35, wherein the resist film detects a peak of Cr2p3/2 from a chromium compound in a range of 576eV to 581eV by analysis using X-ray photoelectron spectroscopy.

Item 37. The resist film of item 35 or 36, wherein the resist film detects a peak of P2P from a phosphoric acid compound in a range of 132eV to 135eV by analysis using X-ray photoelectron spectroscopy.

The resist film according to any one of items 35 to 37, wherein the resist film detects a peak of F1s from a fluorine compound in a range of 685eV to 689eV by analysis using X-ray photoelectron spectroscopy.

The resist film according to any one of items 35 to 38, wherein the resist film comprises at least a film having a COOX group (wherein X is a hydrogen atom or a compound with COO ^- Salt-forming ions), a combination of an acrylic resin, a chromium compound, and a phosphoric acid compound.

The resist film according to item 39, wherein the acrylic resin is at least 1 selected from the group consisting of polyacrylic acid, an ammonium salt of polyacrylic acid, a sodium salt of polyacrylic acid, and an amine salt of polyacrylic acid.

The resist film according to item 41, wherein the acrylic resin is at least 1 selected from the group consisting of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, an ammonium salt of the copolymer, a sodium salt of the copolymer, and an amine salt of the copolymer.

The resist film according to any one of items 39 to 41, wherein the chromium compound is at least one of chromium (III) fluoride and chromium (III) nitrate.

A packaging material comprising a laminate having at least a base layer, a barrier layer and a heat-fusible resin layer in this order,

The resist film according to any one of claims 35 to 42 provided on one surface of the barrier layer.

A packaging material comprising a laminate having at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order,

the resist film of any one of items 35 to 42 being provided on a surface of the barrier layer on the adhesive layer side in contact with the adhesive layer.

The packaging material according to item 44, wherein the resin constituting the adhesive layer has a polyolefin skeleton.

Item 46. The packaging material of item 44 or 45, wherein the adhesive layer comprises an acid-modified polyolefin.

The packaging material according to any one of items 44 to 46, wherein a peak derived from maleic anhydride is detected when the adhesive layer is analyzed by infrared spectroscopy.

The packaging material of item 48, wherein the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene,

the heat-fusible resin layer contains polypropylene.

The packaging material according to any one of items 44 to 48, wherein the adhesive layer is a cured product of a resin composition containing at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.

The packaging material according to any one of items 44 to 48, wherein the adhesive layer is a cured product of a resin composition containing a curing agent having at least 1 selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a C-O-C bond.

The packaging material according to any one of items 44 to 48, wherein the adhesive layer contains at least 1 selected from the group consisting of polyurethane resins, amide ester resins, and epoxy resins.

The packaging material according to any one of items 43 to 51, which is a packaging material for food, a packaging material for medical products, a packaging material for cosmetics or a packaging material for cleaning agents.

A method for producing a packaging material comprising a step of laminating at least a base layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,

when the barrier layer is laminated, a resist film is provided on one surface of the barrier layer,

as the above-mentioned resist film, any one of the resist films of claim 35 to 42 is used.

Item 54. A metal material with a resist coating, having:

a metal material; and

the resist film according to any one of items 35 to 42 provided on a surface of the metal material.

Item 55 is a metal material with a resin film, which has:

a metal material;

the resist film according to any one of items 35 to 42 provided on a surface of the metal material; and

and a resin film provided on the surface of the resist film.

Symbol description

1: a substrate layer; 2: an adhesive layer; 3: a barrier layer; 3a, 3b: a resist coating; 4: a heat-fusible resin layer; 5: an adhesive layer; 6: a surface covering layer; 7: a metal material; 8: a resin film; 10: packaging material for battery; 11: a metal material with a resist coating; 12: a metal material with a resin film; 13: packaging material.

Claims

1. A packaging material for a battery, characterized in that:

comprises a laminate comprising at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order,

a resist film in contact with the adhesive layer is provided on the surface of the barrier layer on the adhesive layer side,

the resist coating is in the range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopyPeak P from C1s of O-c=o bond was detected in the enclosure _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C ，

The peak P _OCO Divided by the height of the peak P _C-C The peak height ratio value P obtained by the height of (2) _OCO/C-C In the range of 0.10 to 0.50,

the thickness of the corrosion-resistant coating film is 1 nm-10 mu m,

the resist film is formed by applying a treatment liquid containing at least an acrylic resin having COOH groups, a chromium compound and a phosphoric acid compound to the surface of the barrier layer and performing a chemical surface treatment of sintering treatment.

2. The packaging material for a battery according to claim 1, wherein:

the resist film detects a peak of Cr2p3/2 from the chromium compound in a range of 576eV to 581eV by analysis using X-ray photoelectron spectroscopy.

3. The packaging material for a battery according to claim 1 or 2, characterized in that:

the resist film detects a peak of P2P from the phosphoric acid compound in a range of 132eV to 135eV by analysis using X-ray photoelectron spectroscopy.

4. The packaging material for a battery according to claim 1 or 2, characterized in that:

the resist film detects a peak of F1s from the fluorine compound in a range of 685eV to 689eV by analysis using X-ray photoelectron spectroscopy.

5. The packaging material for a battery according to claim 1, wherein:

The acrylic resin is at least 1 selected from the group consisting of polyacrylic acid, an ammonium salt of polyacrylic acid, a sodium salt of polyacrylic acid, and an amine salt of polyacrylic acid.

6. The packaging material for a battery according to claim 1, wherein:

the acrylic resin is at least 1 selected from the group consisting of a copolymer of acrylic acid and a dicarboxylic acid or dicarboxylic anhydride, an ammonium salt of the copolymer, a sodium salt of the copolymer, and an amine salt of the copolymer.

7. The packaging material for a battery according to claim 1, wherein:

the chromium compound is at least one of chromium (III) fluoride and chromium (III) nitrate.

8. The packaging material for a battery according to claim 1 or 2, characterized in that:

the resin constituting the adhesive layer has a polyolefin skeleton.

9. The packaging material for a battery according to claim 1 or 2, characterized in that:

the adhesive layer comprises an acid-modified polyolefin.

10. The packaging material for a battery according to claim 1 or 2, characterized in that:

when the adhesive layer was analyzed by infrared spectroscopy, a peak from maleic anhydride was detected.

11. The packaging material for a battery according to claim 9, wherein:

the acid-modified polyolefin of the adhesive layer is maleic anhydride-modified polypropylene,

The heat-fusible resin layer comprises polypropylene.

12. The packaging material for a battery according to claim 8, wherein:

the adhesive layer is a cured product of a resin composition containing at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.

13. The packaging material for a battery according to claim 8, wherein:

the adhesive layer is a cured product of a resin composition containing a curing agent having at least 1 selected from the group consisting of an oxygen atom, a heterocycle, a c=n bond, and a c—o—c bond.

14. The packaging material for a battery according to claim 1 or 2, characterized in that:

the adhesive layer includes at least 1 selected from polyurethane resin, ester resin, and epoxy resin.

15. A method for manufacturing a packaging material for a battery, characterized by:

comprises a step of laminating at least a base layer, a barrier layer, an adhesive layer and a heat-fusible resin layer in this order to obtain a laminate,

as the resist film, the following film was used:

The resist film detects a peak P from an O-c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of peak P _C-C The peak height ratio value P obtained by the height of (2) _COOH/C-C In the range of 0.10 to 0.50,

the thickness of the corrosion-resistant coating film is 1 nm-10 mu m,

16. A battery, characterized in that:

a package formed of the battery packaging material according to any one of claims 1 to 14, wherein a battery element having at least a positive electrode, a negative electrode, and an electrolyte is accommodated.

17. A packaging material for a battery, characterized in that:

comprises a laminate comprising at least a base layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order,

the resist film detects a peak P of C1s from an O-c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P of C1s from the C-C bond was detected at 285eV _C-C ，

the thickness of the corrosion-resistant coating film is 1 nm-10 mu m,

18. The packaging material for a battery as set forth in claim 17, wherein:

19. The packaging material for a battery according to claim 17 or 18, wherein:

20. The packaging material for a battery according to claim 17 or 18, wherein:

21. The packaging material for a battery as set forth in claim 17, wherein:

22. The packaging material for a battery as set forth in claim 17, wherein:

23. The packaging material for a battery as set forth in claim 17, wherein:

24. The packaging material for a battery according to claim 17 or 18, wherein:

the hardness of the pressure head pressed into the adhesive layer from the cross section of the laminate is 30 to 400MPa by using a nanoindenter.

25. The packaging material for a battery according to claim 17 or 18, wherein:

the thickness of the adhesive layer is 0.5-10 mu m.

26. The packaging material for a battery according to claim 17 or 18, wherein:

the resin constituting the adhesive layer has a polar group.

27. The packaging material for a battery as defined in claim 26, wherein:

the polar group is a nitrogen-containing binding group, an isocyanate group, an oxazoline group or an epoxy group.

28. The packaging material for a battery as defined in claim 27, wherein:

the nitrogen-containing binding group is a urethane binding group.

29. The packaging material for a battery according to claim 17 or 18, wherein:

the adhesive layer is a cured product of a polyurethane resin composition containing a polyol compound and an isocyanate compound.

30. The packaging material for a battery according to claim 17 or 18, wherein:

the adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and at least 1 selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.

31. A method for manufacturing a packaging material for a battery, characterized by:

comprises a step of laminating at least a base material layer, an adhesive layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,

As the resist film, the following film was used:

the resist film detects a peak P from an O-c=o bond in a range of 287eV to 290eV by analysis using X-ray photoelectron spectroscopy _OCO And peak P from the C-C bond was detected at 285eV _C-C Peak P _OCO Divided by the height of (2)Peak P _C-C The peak height ratio value P obtained by the height of (2) _COOH/C-C In the range of 0.10 to 0.50,

the thickness of the corrosion-resistant coating film is 1 nm-10 mu m,

32. A battery, characterized in that:

a package formed of the battery packaging material according to any one of claims 17 to 30, wherein a battery element having at least a positive electrode, a negative electrode, and an electrolyte is accommodated.

33. A resist film characterized by:

the thickness of the corrosion-resistant coating film is 1 nm-10 mu m,

the resist film is formed by a chemical surface treatment in which a treatment solution containing at least an acrylic resin having a COOX group, a chromium compound and a phosphoric acid compound is applied to the surface of a barrier layer and subjected to a sintering treatment, wherein X is a hydrogen atom or a compound having a COO group ^- Ions that form salts.

34. The resist coating of claim 33, wherein:

35. The resist coating of claim 33 or 34, wherein:

36. The resist coating of claim 33 or 34, wherein:

37. The resist coating of claim 33, wherein:

38. The resist coating of claim 33, wherein:

39. The resist coating of claim 33, wherein:

40. A packaging material, characterized in that:

comprises a laminate having at least a base layer, a barrier layer and a heat-fusible resin layer in this order,

a resist film according to any one of claims 33 to 39 provided on one surface of the barrier layer.

41. A packaging material, characterized in that:

the resist film according to any one of claims 33 to 39, wherein the surface of the barrier layer on the adhesive layer side is in contact with the adhesive layer.

42. The packaging material of claim 41, wherein:

the resin constituting the adhesive layer has a polyolefin skeleton.

43. The packaging material of claim 41 or 42, wherein:

the adhesive layer comprises an acid-modified polyolefin.

44. The packaging material of claim 41 or 42, wherein:

45. The packaging material of claim 43, wherein:

the heat-fusible resin layer comprises polypropylene.

46. The packaging material of claim 41 or 42, wherein:

47. The packaging material of claim 41 or 42, wherein:

48. The packaging material of claim 41 or 42, wherein:

the adhesive layer includes at least 1 selected from polyurethane resin, amide ester resin, and epoxy resin.

49. The packaging material of any one of claims 40 to 42, wherein:

it is a packaging material for food, a packaging material for medicinal products, a packaging material for cosmetics or a packaging material for cleaning agents.

50. A method of manufacturing a packaging material, characterized by:

comprises a step of laminating at least a base layer, a barrier layer and a heat-fusible resin layer in this order to obtain a laminate,

as the resist film, the resist film according to any one of claims 33 to 39 is used.

51. A metal material with a resist coating, comprising:

a metal material; and

the resist film according to any one of claims 33 to 39 provided on a surface of the metal material.

52. A metal material with a resin film, characterized by comprising:

a metal material;

the resist film according to any one of claims 33 to 39 provided on a surface of the metal material; and

And a resin film provided on the surface of the resist film.