JP2001229886A - Packaging material for polymer battery and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material having good protection property of packaging for a polymer battery and a method of good productivity thereof. SOLUTION: The housing material for the polymer battery is composed of at least the following components; a substrate layer, an adhesive layer, a chemically treated layer, aluminum, a chemically treated layer and the innermost resin layer. The adhesive layer has polypropylene resins modified with acid as the main component, and the innermost layer includes terpolymer comprising at least three components copolymer of ethylene, butene and propylene. Both the adhesive resin layer and the innermost resin layer are made through co- extrusion method. The method of manufacture is composed of the following procedures; both sides of aluminum are chemically treated, after one of both faces chemically treated is dry-laminated with the substrate, the other face of chemically treated aluminum is contacted with the adhesive resin and the innermost resin, then, co-extruded forming a film to give the multi-layered structure, which is heated at the temperature of equal on more than the softening point of the adhesive resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid organic electrolyte (polymer polymer electrolyte) having moisture resistance and content resistance.
The present invention relates to a polymer battery packaging material.

[0002]

2. Description of the Related Art A polymer battery, also called a lithium secondary battery, is a battery having a polymer electrolyte and generating an electric current by the movement of lithium ions, wherein the positive and negative electrode active materials are made of a polymer. Is included.
The structure of the lithium secondary battery is as follows: a positive electrode current collector (aluminum, nickel) / a positive electrode active material layer (a metal positive electrode material such as metal oxide, carbon black, metal sulfide, electrolyte solution, polyacrylonitrile) / an electrolyte layer (propylene) Carbonate-based electrolytes such as carbonate, ethylene carbonate, dimethyl carbonate, and ethylene methyl carbonate; inorganic solid electrolytes composed of lithium salts; gel electrolytes) / Negative electrode active materials (lithium metals, alloys, carbon, electrolytes, and polymers such as polyacrylonitrile) A negative electrode material) / a negative electrode current collector (copper, nickel, stainless steel) and an outer package that wraps them. Applications of polymer batteries include personal computers, mobile terminals (mobile phones, PDAs, etc.), video cameras, electric vehicles, storage batteries for energy storage, robots,
Used for satellites. As the outer package of the polymer battery, a metal can formed by pressing a metal into a cylindrical or rectangular parallelepiped container, or an outermost layer, aluminum, and a laminate formed of a sealant layer are formed into a bag shape. Was used.

[0003]

However, there have been the following problems as the exterior body of the polymer battery. In a metal can, the shape of the battery itself is determined because the outer wall of the container is rigid. Therefore, since the hardware side is designed to match the battery, the size of the hardware using the battery is determined by the battery, and the degree of freedom of the shape is reduced. Therefore, a pouch type in which the laminate is stored in a bag shape to accommodate the polymer battery main body, or an emboss type in which the laminate is press-formed to form a concave portion and the polymer battery main body is accommodated in the concave portion has been developed. The embossed type provides a more compact package as compared to the pouch type. Regardless of the type of the exterior body, the strength such as moisture resistance or puncture resistance, insulation properties, and the like of the polymer battery are indispensable as the exterior body of the polymer battery. The packaging material for a polymer battery is a laminate comprising at least a substrate layer, a barrier layer, and a heat-sealing film layer. Then, it has been confirmed that the adhesive strength between the layers affects the properties required for the outer package of the polymer battery. For example, if the adhesive strength between the barrier layer and the heat-sealing film layer is insufficient, moisture may enter from the outside, and the fluorine generated by the reaction between the electrolyte in the components forming the polymer battery and the moisture. The aluminum surface is corroded by hydrofluoric acid, and delamination occurs between the barrier layer and the heat-sealing film layer. Further, when forming the embossed type exterior body, the laminate is press-molded to form a concave portion. In this molding, delamination may occur between the outermost layer and the barrier layer. Then, the present inventors applied an emulsion of acid-modified polypropylene to the aluminum surface, baked to form a film, and laminated a heat-sealable film by a sandwich lamination method using an acid-modified polypropylene resin as an adhesive resin. Although it was confirmed that the adhesive strength was improved, baking after the emulsion coating of the acid-modified polypropylene was time-consuming and the production efficiency was not good.
An object of the present invention is to provide, as a material used for a polymer battery package, a production method having high productivity as well as protection physical properties of a polymer battery main body.

[0004]

According to the present invention, there is provided at least a substrate layer, an adhesive layer, a chemical conversion layer, aluminum, a chemical conversion layer, an adhesive resin layer, and an innermost resin layer, wherein the adhesive resin layer is an acid-modified polypropylene. Resin as a main component, the innermost resin layer contains at least a terpolymer composed of a ternary copolymer of ethylene, butene and propylene, and the adhesive resin layer and the innermost resin layer are layers formed by co-extrusion. A packaging material for a polymer battery, wherein the chemical conversion treatment is a phosphoric acid chromate treatment, the adhesive resin is an acid-modified polypropylene resin, and the innermost resin is a three-component copolymer of ethylene, butene, and propylene. A terpolymer, wherein the adhesive resin is an acid-modified PP resin, and the heat-sealing film layer is a polypropylene resin layer containing at least 5% of a terpolymer resin. Becomes possible, the adhesive resin is acid-modified PP resin, at least one polypropylene resin layer heat sealable film layer comprises a terpolymer resin 5% or more
The adhesive resin is made of an acid-modified PP resin containing at least 5% of a terpolymer resin, at least a substrate layer, an adhesive layer, aluminum, a chemical conversion treatment layer, an adhesive resin layer, and an innermost resin layer. Wherein the adhesive resin layer comprises an acid-modified polypropylene resin as a main component, and the innermost resin layer comprises at least ethylene, butene and propylene.
It includes a terpolymer comprising a component copolymer, and the adhesive resin layer and the innermost resin layer are layers formed by co-extrusion. Further, chemical conversion treatment is performed on both surfaces of the aluminum, and after the base material and one surface subjected to the chemical conversion treatment are dry-laminated, the adhesive resin and the innermost resin are co-extruded on the other surface subjected to the chemical conversion treatment. A method for producing a packaging material for a polymer battery, characterized in that a film is formed into a laminate, and the obtained laminate is heated by post-heating so that the adhesive resin has a softening point or higher.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a moisture-proof property,
And a packaging material for a polymer battery with good productivity,
A chemical conversion treatment is applied to both surfaces of the barrier layer, and an adhesive resin layer and an innermost resin layer are formed on the content side of the barrier layer using a co-extrusion method, and thereafter, the adhesive strength is improved by heating. . FIG. 1 is a cross-sectional view illustrating the configuration of a laminate in the packaging material for a polymer battery of the present invention. FIG.
FIG. 2 is a perspective view illustrating a pouch type exterior body of a polymer battery. FIG. 3 is a perspective view illustrating an embossed type exterior body of a polymer battery. 4A and 4B are views for explaining molding in an emboss type, (a) a perspective view, (b) an exterior body main body formed by embossing, (c) a cross-sectional view of a part X ₂ -X ₂ ,
(D) is a Y ₁ part enlarged view. FIG. 5 is a conceptual diagram of an apparatus for explaining a co-extrusion lamination method for producing a packaging material for a polymer battery. FIG. 6 is a perspective view illustrating a method of mounting an adhesive film in bonding a packaging material for a polymer battery to a tab.

When the packaging material for a polymer battery is, for example, nylon / adhesive layer / aluminum / adhesive layer / cast polypropylene, and the adhesive layer is formed by a dry laminating method, when the exterior body of the polymer battery is an embossed type, In press molding, delamination in which the aluminum and the base material layer are peeled off from each other often occurs at the side wall portion, and the polymer battery main body is housed in the outer package and the periphery thereof is heat-sealed. There was lamination. In addition, hydrogen fluoride generated by a reaction between an electrolyte, which is a component of the battery, and moisture may attack the inner surface of aluminum and cause delamination. Further, in the molding step, cracks may be formed in the surface layer on the sealing surface side of the cast polypropylene layer, and corrosion of aluminum may be promoted from the cracks. Furthermore, when the laminate was bent, cracks were sometimes formed in the cast polypropylene layer.

Therefore, the present inventors have proposed a method for embossing,
At the time of heat sealing, it is a laminate that does not generate delamination, and as a result of earnest research on a packaging material that can be satisfied as an outer package for a polymer battery with content resistance, subjected to chemical conversion treatment on both sides of aluminum, An acid-modified PP such as an unsaturated carboxylic acid-grafted random propylene is coated on the chemical conversion treated surface on the aluminum content side.
(Hereinafter sometimes referred to as PPa) is provided as an adhesive resin layer, and a terpolymer (hereinafter, referred to as a terpolymer) composed of a three-component copolymer of ethylene, butene and propylene is provided as an innermost layer.
T-PP), the inventors have found that the above problem can be solved, and completed the present invention. Further, as a method for producing the same, a chemical conversion treatment is performed on both surfaces of aluminum, and an acid-modified PP such as unsaturated carboxylic acid-grafted random propylene (hereinafter, referred to as PPa) may be formed on the chemical conversion treatment surface on the content side of aluminum. ) Was laminated together with a terpolymer resin as an adhesive resin by a co-extrusion method, and the obtained object was post-heated to find that the problem could be solved. Thus, the present invention was completed.

As shown in FIG. 1, the layer structure of the packaging material for a polymer battery according to the present invention comprises at least a substrate layer 11, an adhesive layer 16, a chemical conversion layer 15 (1), aluminum 12, and a chemical conversion layer 15 (2). ), An adhesive resin layer 13, and an innermost layer (a terpolymer film composed of a three-component copolymer of ethylene, butene, and polypropylene) 14; and the adhesive resin layer 13 and the innermost layer are formed by coextrusion. This is intended to improve the bonding strength by post-heating the obtained laminate to be described later.

According to the present invention, as shown in FIG.
2, a terpolymer film 14 made of a ternary copolymer of ethylene, butene and polypropylene is laminated on the inner surface side of the barrier layer 12 by coextruding an adhesive resin 13 and an innermost layer 14. Further, the formed laminate is heated to a temperature equal to or higher than the softening point of the adhesive resin by post-heating.

[0010] The packaging material for a polymer battery is an exterior body for wrapping a polymer battery body, and there are a pouch type as shown in FIG. 2 and an embossed type as shown in FIG. 3 depending on the type of the exterior body. The pouch type includes a bag type such as a three-side seal, a four-side seal, and a pillow type. FIG. 2 illustrates the pouch type as a pillow type.
In addition, as the emboss type, a concave portion may be formed on one side as shown in FIG. 3A, or a concave portion may be formed on both surfaces as shown in FIG. It may be housed and heat-sealed on the four sides of the periphery to seal. There is also a type in which a concave portion is formed on both sides of a folded portion as shown in FIG. 3C, a polymer battery is housed, and three sides are heat-sealed. The layer structure of the packaging material for a polymer battery in the present invention is, as shown in FIG. 1, a laminate comprising at least an outermost layer, a chemical conversion layer, a barrier layer, a chemical conversion layer, an adhesive resin layer, and an innermost layer. The inner layer is
It is laminated with a co-extrusion method together with an adhesive resin layer. The innermost layer is made of a terpolymer (hereinafter, Τ-PP) composed of a three-component copolymer of unstretched ethylene, butene and polypropylene. In the case of an embossed type exterior body, a laminate having excellent moldability is required in order to form a concave portion serving as a storage part for packaging the polymer battery body. Next, the materials constituting each layer of the laminate and the bonding will be described.

In the present invention, the outermost layer is made of a stretched polyester or nylon film. At this time, as the polyester resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, polycarbonate, etc. Is mentioned. Examples of the nylon include polyamide resins, that is, nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 6,10, and polymethaxylylene adipamide (MXD6).

When the outermost layer is used as a polymer battery, it is a portion which is in direct contact with the hardware, so that a resin layer having an insulating property is basically preferable. In consideration of the presence of pinholes in the film alone and the occurrence of pinholes during processing, the outermost layer needs to have a thickness of 6 μm or more,
The preferred thickness is 12 to 25 μm.

In the present invention, the outermost layer can be laminated to improve the pinhole resistance and the insulating property when the battery is used as an outer package. When the outermost layer is formed into a laminate, the outermost layer includes at least one resin layer of two or more layers, and each layer has a thickness of 6 μm or more, preferably 12 to
25 μm. Although not shown, examples of laminating the outermost layer include the following 1) to 7). 1) Stretched polyethylene terephthalate / stretched nylon 2) Stretched nylon / stretched stretched polyethylene terephthalate Also, mechanical suitability of the packaging material (stability of transportation in packaging machines and processing machines), surface protection (heat resistance, electrolyte resistance) ) When the exterior body for a polymer battery is embossed as a secondary process, the outermost layer is multilayered in order to reduce the frictional resistance between the mold and the outermost layer during embossing. It is preferable to provide a resin layer, an acrylic resin layer, a silicone resin layer, or the like. For example, 3) Fluorine-based resin / stretched polyethylene terephthalate (fluorine-based resin is formed into a film or liquid coating and then dried) 4) Silicone-based resin / stretched polyethylene terephthalate (silicone-based resin is film-like or liquid 5) Fluorine resin / stretched polyethylene terephthalate /
Stretched nylon 6) Silicone resin / Stretched polyethylene terephthalate / Stretched nylon 7) Acrylic resin / Stretched nylon (Acrylic resin is cured by drying after film-like or liquid coating)

The barrier layer 12 is a layer for preventing water vapor from particularly entering the inside of the polymer battery from the outside, and stabilizes the pinholes of the barrier layer alone and the workability (pouching, embossability). And a metal such as aluminum or nickel having a thickness of 15 μm or more to have a pinhole resistance, or an inorganic compound, for example, a film obtained by depositing silicon oxide, alumina, or the like. Aluminum having a thickness of 20 to 80 μm. In order to further improve the occurrence of pinholes and to make the type of the outer package of the polymer battery an embossed type, in order to eliminate the occurrence of cracks and the like in the embossing, the present inventors made use of aluminum used as a barrier layer. The material has an iron content of 0.3-9.
By setting the content to 0% by weight, preferably 0.7 to 2.0% by weight, the aluminum has good ductility and less occurrence of pinholes due to bending as a laminate, compared to aluminum containing no iron. It has been found that the side wall can be easily formed when the embossed type exterior body is molded. The iron content is 0.3% by weight
If less than the above, no effects such as prevention of pinholes and improvement in embossability are observed, and if the iron content of the aluminum exceeds 9.0% by weight, flexibility as aluminum is impaired. As a result, the bag-making properties of the laminate deteriorate.

[0015] Further, the aluminum produced by cold rolling has its flexibility and flexibility under the conditions of annealing (so-called annealing treatment).
Although the strength and hardness of the waist change, the aluminum used in the present invention is harder than the hard treated product without annealing.
Aluminum with a tendency to soften slightly or completely annealed is preferred. The degree of flexibility, waist strength, and hardness of aluminum, that is, the conditions of annealing,
What is necessary is just to select suitably according to workability (pouching, embossing). For example, in order to prevent wrinkles and pinholes during embossing, soft aluminum annealed according to the degree of forming can be used.

The inventors of the present invention have conducted intensive studies on the problems of the present invention, and as a result of conducting a chemical conversion treatment on the front and back surfaces of aluminum as a barrier layer of a packaging material for a polymer battery, the packaging material can be satisfied. A laminate could be obtained. The chemical conversion treatment is specifically to prevent delamination between aluminum and the substrate layer during embossing by forming an acid-resistant film such as a phosphate, a chromate, a fluoride, and a triazine thiol compound. And the hydrogen fluoride generated by the reaction between the electrolyte of the polymer battery and water, to prevent the dissolution and corrosion of the aluminum surface, especially the dissolution and corrosion of the aluminum oxide present on the aluminum surface, and Improves adhesion (wetability), prevents delamination between the base layer and aluminum during embossing and heat sealing, and prevents delamination on the inner surface of aluminum by hydrogen fluoride generated by the reaction between electrolyte and moisture The effect was obtained. As a result of studying the effect of chemical conversion treatment on the aluminum surface using various substances, among the above-mentioned acid-resistant film-forming substances, phenolic resin, chromium fluoride (3) compound, and phosphoric acid The phosphoric acid chromate treatment using the treated product was good.

In the case where the outer casing of the polymer battery is a pouch type, the chemical conversion treatment may be performed only on one side of the innermost layer of aluminum. When the exterior body of the polymer battery is an embossed type, delamination between aluminum and the base layer during embossing can be prevented by performing a chemical conversion treatment on both surfaces of aluminum. A laminate having a chemical conversion treatment on both surfaces of aluminum may be used for the pouch type.

The inner side of the barrier layer 12 in the polymer battery packaging material of the present invention is formed by co-extrusion using an apparatus as shown in FIG. And the innermost resin 14 are formed into a film by co-extrusion and adhered. The innermost resin layers 14 have heat sealing properties, and a terpolymer resin composed of a three-component copolymer of ethylene, butene, and polypropylene having necessary physical properties such as heat resistance, moisture resistance, and press moldability may be used. desirable. Then, an acid-modified PP and a terpolymer having good adhesion to the chemical conversion treated surface of aluminum are co-extruded, and the acid-modified PP layer is turned to the aluminum side to form a laminate.

In the packaging material for a polymer battery of the present invention, an acid-modified PP such as an unsaturated carboxylic acid-grafted random propylene or the like is provided on the chemical conversion treated surface on the content side of aluminum.
(Hereinafter sometimes referred to as PPa). The provision of the acid-modified PP layer has effects of preventing corrosion of aluminum and stabilizing the adhesion of the innermost terpolymer.

When the acid-modified PP and the innermost layer are co-extruded on a chemical conversion treated surface of aluminum, productivity as a laminating process is excellent, but the adhesive strength is necessary for use as a packaging material for polymer batteries. High strength cannot be obtained. Accordingly, the present inventors have conducted intensive studies on a lamination method showing stable adhesive strength, and as a result, dry-laminated the base material layer and one side of the barrier layer subjected to the chemical conversion treatment on both sides, and acid-modified the other side of the barrier layer. After forming an adhesive resin made of PP and a terpolymer consisting of a three-component copolymer of ethylene, butene, and polypropylene as the innermost layer into a laminate by a co-extrusion method, the laminate becomes above the softening point of the adhesive resin. By heating to the conditions, a laminate having a predetermined adhesive strength could be obtained. As a specific method of the heating, there are methods such as a hot roll contact type, a hot air type, near or far infrared rays, but any heating method may be used in the present invention, and as described above, the adhesive resin is softened. What is necessary is just to be able to heat above the point temperature.

Another method is to stabilize the adhesive strength by heating the surface temperature of the innermost layer of aluminum to the softening point of the acid-modified PP resin during the co-extrusion lamination. It was possible to obtain a laminated body.

The acid-modified PP is (1) a vigat softening point of 1
Homo type having a melting point of at least 15 ° C and a melting point of at least 150 ° C, and (2) a copolymer with ethylene-propylene having a softening point of at least 105 ° C and a melting point of at least 130 ° C (random copolymerization type)
(3) An ethylene butene-propylene copolymer (terpolymer) having a melting point of 110 ° C. or more is used as a base resin,
It is a simple substance or a blend obtained by acid-modified polymerization using an unsaturated carboxylic acid. The acid-modified PP has a density of 9%.
A low-crystalline ethylene butene copolymer of 00 kg / m ³ or less, a low-crystalline propylene butene copolymer, or an amorphous ethylene-propylene copolymer, an amorphous propylene-ethylene copolymer, An ethylene-butene-propylene copolymer or the like may be added in an amount of 5% or more to impart flexibility, improve bending resistance, and prevent cracking during molding.

Further, the acid-modified PP is added with a terpolymer composed of a ternary copolymer of ethylene, butene and propylene in an amount of 5% or more to impart more flexibility to improve the bending resistance. It is also possible to prevent cracks during molding.

As the laminate of the packaging material for a polymer battery of the present invention, the above-mentioned substrate layer, barrier layer, innermost layer (Τ-PP)
Alternatively, an intermediate layer may be provided between the barrier layer and the innermost layer. The intermediate layer may be laminated for improving strength as a packaging material for a polymer battery, improving and stabilizing barrier properties, and the like.

In each of the above-mentioned layers in the laminate of the present invention,
Appropriate surface activation such as corona treatment, blast treatment, oxidation treatment, ozone treatment, etc. for the purpose of improving and stabilizing the suitability for film forming, lamination processing, and final processing of secondary products (pouching, embossing) as appropriate. Processing may be performed.

Τ-PP is preferably used as the innermost layer of the laminate in the packaging material for a polymer battery of the present invention. The use of Τ-PP for the innermost layer has good heat-sealing properties between Τ-PPs, and has the required protective physical properties as the innermost layer of a polymer battery packaging material such as moisture resistance and heat resistance. Further, it is a desirable material because of its good laminating processability, good embossing processability, and the like. As the 用 い る -PP, it is desirable to use a terpolymer composed of a three-component copolymer of ethylene, butene and propylene having a thickness of 30 to 100 μm and a melting point (120 ° C. or higher). Preferably, a polypropylene resin layer containing at least 5% of a terpolymer, or a multilayer structure containing at least one polypropylene resin layer containing at least 5% of a terpolymer. Specific examples of the layer structure are as follows: (1) Terpolymer alone (2) Terpolymer + polypropylene (3) Terpolymer / LLDPE / terpolymer (4) Terpolymer + polypropylene / LLDPE / terpolymer + polypropylene (5) ) Terpolymer + polypropylene / polypropylene / terpolymer + polypropylene (6) terpolymer + polypropylene / polypropylene + LLDPE / terpolymer + polypropylene (7) terpolymer + polypropylene / polypropylene + terpolymer / terpolymer + polypropylene : In the case of a blend, a blend of a terpolymer and polypropylene, the terpolymer content is 5% or more, // indicating co-extrusion, and all of the polypropylenes are random polymerization types.

The density of the Τ-PP is 900 k.
g / m ³ or less low-crystalline ethylene butene copolymer,
Adds 5% or more of low-crystalline propylene butene copolymer, amorphous ethylene-propylene copolymer, amorphous propylene-ethylene copolymer, etc. Improving the properties and preventing cracks during molding may be performed.

However, since Δ-PP has no heat-sealing property to metal, the heat-sealing of the tab portion in the polymer battery requires the heat-sealing properties shown in FIGS. 6 (a), 6 (b) and 6 (b).
As shown in (c), between the tab and the innermost layer of the laminate,
By interposing an adhesive film having heat sealing properties to both the metal and the Τ-PP, the sealing property at the tab portion is also ensured. The adhesive film is shown in FIG.
As shown in FIGS. 6E and 6F, the tab may be wound around a predetermined position. As the adhesive film,
A film made of the unsaturated carboxy-grafted polyolefin, metal cross-linked polyethylene, or a copolymer of ethylene or propylene with acrylic acid or methacrylic acid can be used.

It is desirable that the base material and the chemical conversion treated surface of the barrier layer in the packaging material for a polymer battery of the present invention be bonded by a dry lamination method. As the adhesive used for dry lamination of the substrate and the phosphate chromate-treated surface of aluminum, polyester, polyethyleneimine, polyether, cyanoacrylate, urethane, organic titanium, polyether urethane, Epoxy, polyester urethane, imide,
Various isocyanate-based, polyolefin-based, and silicone-based adhesives can be used.

[0030]

EXAMPLES The packaging material for a polymer battery of the present invention is described below.
Examples will be described more specifically. Chemical conversion treatment
Displacement may also be caused by phenol resin, chromium fluoride
(Ii) Roll coating of aqueous solution consisting of compound and phosphoric acid
Condition by which the coating temperature is 180 ℃ or higher
Baked in Chromium coating amount is 10mg / m^Two
(Dry weight). Packaging material for polymer battery of the present invention
Will be described more specifically with reference to examples. Implementation
In both the example and the comparative example, the base material layer is nylon 25 μm, and the barrier is
The layer was 40 μm of aluminum. Innermost used in Examples
The layer is made of ethylene butene-propylene copolymer described below.
Containing layer. Also, the embossing should be embossed on one side,
The shape of the concave part (cavity) of the shape is 30 mm x 50 m
m, depth 3.5mm and evaluate formability
Was. The acid-modified PP used in the examples had a softening point of 105
℃, random type polypropylene base with melting point 146 ℃
An unsaturated carboxylic acid-modified PP was used. [Example 1] Chemical conversion treatment on both sides of aluminum 40 µm
Coated with 25 μm nylon on one side.
Laminated by Ilaminate method, and then subjected to chemical conversion treatment
On the other surface, use an acid-modified PP with a thickness of 20 μm as an adhesive resin.
And an etch consisting of the following (1) to (6) with a thickness of 30 μm
The co-extrusion laminator is composed of a
Specimen example 1 was obtained by laminating by the minate method. (1) Terpolymer (2) Terpolymer 5% + PP95% (3) Terpolymer 50% + PP50% (4) Terpolymer 80% + PP20% (5) Terpolymer / PP / terpolymer (6) Terpolymer / PP + LLDPE / Terpolymer 説明 Description of abbreviations, etc. +: Blend, /: Co-extrusion, PP:
Random polymerization type polypropylene, LLDPE: straight
Chain low-density polyethylene. The obtained laminate was heated to a surface temperature of 140 ° C.
The sample was heated to obtain Sample Example 1. [Example 2] Chemical conversion treatment on both sides of 40 μm aluminum
Coated with 25 μm nylon on one side.
Laminated by Ilaminate method, and then subjected to chemical conversion treatment
On another side, terpolymer 1 was added to an acid-modified PP having a thickness of 20 μm.
0% added resin and 30μm thick (terpolymer
5% + 95% PP)
Specimen Example 2 was obtained by laminating by the coating method. [Example 3] Chemical conversion treatment on both sides of 40 μm aluminum
Coated with 25 μm nylon on one side.
Laminated by Ilaminate method, and then subjected to chemical conversion treatment
On the other side, a terpolymer 5 was added to an acid-modified PP having a thickness of 20 μm.
0% added resin and 30μm thick (terpolymer
5% + 95% PP)
Specimen Example 2 was obtained by laminating by the coating method. [Comparative Example 1] Chemical conversion treatment on both sides of 40 μm aluminum
Coated with 25 μm nylon on one side.
Laminated by Ilaminate method, and then subjected to chemical conversion treatment
On the other surface, a 20 μm thick acid-modified PP and a 30 μm thick
Co-press with polypropylene (homo type, melting point 151 ° C)
And then laminate the resulting laminate
Heat the minium surface temperature to 150 ° C for inspection.
Body comparative example 1 was obtained. [Comparative Example 2] Nylon was applied to one surface of aluminum 40 µm.
25 μm together by dry lamination
On the other side of aluminum, a thickness of 20 μm and a softening point of 1
An acid-modified PP at 20 ° C. is used as an adhesive resin, with a thickness of 30 μm,
The terpolymers (1) to (6) used in Example 1
Laminated with co-extrusion lamination method
And the obtained laminate was treated with an aluminum surface temperature of 1
The sample was heated to 50 ° C. to obtain Sample Comparative Example 2. <Embossing and packaging> Each sample obtained is press-molded
Then, wrap each polymer battery body and evaluate the following.
went. <Evaluation method> 1) Delamination during molding Immediately after molding, delamination between aluminum and substrate layer
Was checked. 2) Content resistance As a storage condition, each sample was subjected to a constant temperature of 60 ° C. and 90% RH.
After storage in the tank for 7 days, aluminum and Τ-PP
The presence or absence of delamination was confirmed. 3) Delamination during heat sealing Delamination between aluminum and innermost resin layer immediately after heat sealing
The presence or absence of the termination was confirmed. <Results> The laminates of Example 1, Example 2 and Example 3
There is no problem during molding and heat sealing.
No delamination between ruminium and substrate layer
Was. Also, there is no delamination of content resistance.
Was. In addition, cracking and bending of the innermost layer during molding
There was no crack in the innermost layer at the time. However, in Comparative Example 1,
There is no problem during molding or heat sealing.
No delamination between minium and substrate layer
Was. In addition, there was no delamination of the content resistance.
However, the cracks in the innermost layer during molding were all 100
Cracks in the innermost layer during bending
Had a body outbreak. Comparative Example 2 was heat-sealed during molding.
48 samples out of 100 samples at each stage
And delamination was seen. In terms of content resistance
Indicates that delamination is observed in all 100 samples.
Was. Also, cracks in the innermost layer during molding and bending
Of cracks in the innermost layer was not observed in 100 samples
Was.

[0031]

The chemical conversion treatment applied to both surfaces of aluminum in the packaging material for polymer batteries of the present invention prevents the occurrence of delamination between the base material layer and aluminum during embossing and heat sealing. In addition, by preventing corrosion of the aluminum surface due to hydrogen fluoride generated by the reaction between the electrolyte of the polymer battery and moisture, a significant effect of preventing delamination of aluminum with the content side layer can be prevented. Is shown.
In addition, the innermost layer of the Τ-PP film has good productivity because the acid-modified PP can be laminated with the adhesive resin by a co-extrusion method, and the adhesive strength as a packaging material for a polymer battery can be obtained by post-heating treatment. It can be used as an outer package of a polymer battery.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating the configuration of a laminate in a packaging material for a polymer battery of the present invention.

FIG. 2 is a perspective view illustrating a pouch type exterior body of a polymer battery.

FIG. 3 is a perspective view illustrating an embossed type exterior body of a polymer battery.

FIG. 4 illustrates molding in an emboss type.
(A) a perspective view, (b) an embossed exterior body body,
(C) X ₂ -X ₂ parts cross-sectional view, an enlarged view (d) Y ₁ parts.

FIG. 5 is a conceptual diagram of an apparatus for explaining a co-extrusion method for producing a packaging material for a polymer battery.

FIG. 6 is a perspective view illustrating a method of mounting an adhesive film in bonding a packaging material for a polymer battery and a tab.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Polymer battery 2 Polymer battery main body 3 Cell (power storage part) 4 Tab (electrode) 5 Outer body 6 Adhesive film (tab part) 7 Concave part 8 Side wall part 9 Seal part 10 Laminated body (packaging material for polymer batteries) 11 Base material layer 12 Aluminum (barrier layer) 13 Adhesive resin layer 14 Innermost layer (3 of ethylene, butene and polypropylene)
15 Chemical conversion treatment layer 16 Adhesive layer 20 Press forming part 21 Male type 22 Female type 23 Cavity 30 Coextrusion laminating device 31 Extruder 32 Die 33 Molten resin film 34 Chill roll 35 Compression roll 36 Laminate

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Kazuki Yamada 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Hiroshi Miyama 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. F-term (reference) 4F100 AA04B AA22B AB10B AK01D AK04D AK04G AK04J AK07C AK07D AK07G AK07J AK09D AK09G AK09J AK80D AK80G AL01D AL05D AL07EBAE BAE AT02A00 EJ681 EJ69B GB41 JD04 JJ03 JL11C JL12D YY00D 4F207 AA04E AA11E AA11J AA12E AD03 AG01 AG03 AH33 AR06 KA01 KA17 KB26 KK83 KL65 KW50 4J040 DA101 DA102 DA121 DA122 DA151 DA152120406 ABA12 BA11 BA04 A0211 CC02 CC06 CC10 DD13 DD14

Claims (8)

[Claims] (1) at least a substrate layer, an adhesive layer, a chemical conversion treatment layer,
Aluminum, a chemical conversion layer, an adhesive resin layer, an innermost resin layer, wherein the adhesive resin layer is mainly composed of an acid-modified polypropylene resin, and the innermost resin layer is at least a three-component copolymer of ethylene, butene and propylene. A packaging material for a polymer battery, comprising a terpolymer, wherein the adhesive resin layer and the innermost resin layer are layers formed by co-extrusion. 2. The packaging material for a polymer battery according to claim 1, wherein the chemical conversion treatment is a phosphoric acid chromate treatment. 3. The method according to claim 1, wherein the adhesive resin is an acid-modified polypropylene resin, and the innermost resin is a terpolymer comprising a ternary copolymer of ethylene, butene and propylene. Packaging materials for polymer batteries. 4. The method according to claim 1, wherein the adhesive resin comprises an acid-modified PP resin, and the heat-sealing film layer comprises a polypropylene resin layer containing at least 5% of a terpolymer resin.
Or the packaging material for a polymer battery according to claim 2. 5. The multi-layer structure according to claim 1, wherein said adhesive resin has an acid-modified PP resin, and said heat-sealing film layer has at least one polypropylene resin layer containing 5% or more of a terpolymer resin. Item 4. A packaging material for a polymer battery according to Item 2. 6. The packaging material for a polymer battery according to claim 1, wherein the adhesive resin comprises an acid-modified PP resin containing 5% or more of a terpolymer resin. 7. At least a substrate layer, an adhesive layer, aluminum, a chemical conversion layer, an adhesive resin layer, and an innermost resin layer, wherein the adhesive resin layer contains an acid-modified polypropylene resin as a main component, and the innermost resin layer is A packaging material for a polymer battery, comprising a terpolymer comprising at least a three-component copolymer of ethylene, butene and propylene, wherein the adhesive resin layer and the innermost resin layer are layers formed by coextrusion. 8. A chemical conversion treatment is performed on both surfaces of aluminum, and after a base material and one surface subjected to the chemical conversion treatment are dry-laminated, an adhesive resin and an innermost resin are coated on the other surface subjected to the chemical conversion treatment. A method for producing a packaging material for a polymer battery, comprising: co-extrusion forming a film to form a laminate; and heating the resulting laminate by post-heating under conditions where the adhesive resin has a softening point or higher.