JP2001229885A - Packaging material for polymer battery and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material having a good protection property of packaging for a polymer battery and a method of good productivity thereof. SOLUTION: The packaging material for the polymer battery is composed of a substrate layer, an adhesive layer, a chemically treating layer, aluminum, a chemically treated layer, an adhesive resin layer and a heat-sealing film layer. The heat-sealed film layer is a laminate layer in which a heat sealed film layer of a ter-polymer comprising at least three component copolymers of ethylene, butene and propylene, is sandwiched by an adhesive resin of acid modified PP resin as the main component. The method of manufacturing the material is composed of the following steps; both faces of aluminum are treated with chemicals, then, the base substrate is dry laminated with the one face of the chemically treated aluminum. The other face of the chemically treated aluminum is laminated with such the heat-sealed layer as polypropylene film and such the adhesive resin as PP resin denatured with acid, to give the multi- layered structure by laminating by means of sandwich-laminating method, which is heated under the conditions that its temperature is equal or 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]

The present invention comprises a base material layer, an adhesive layer, a chemical conversion layer, aluminum, a chemical conversion layer, an adhesive resin layer, and a heat-sealing film layer. A heat-sealing film layer containing a terpolymer comprising a component copolymer is a layer laminated by sandwiching with an adhesive resin containing an acid-modified PP resin as a main component. The treatment is a phosphoric acid chromate treatment, the adhesive resin is an acid-modified polypropylene resin, the heat-sealable film layer is a terpolymer composed of a ternary copolymer of ethylene, butene and propylene, and the adhesive resin is an acid-modified PP resin, heat sealing film layer is a polypropylene resin layer containing 5% or more of terpolymer resin Rukoto, wherein the adhesive resin is acid-modified PP
The resin and the heat-sealable film layer have a multilayer structure having at least one polypropylene resin layer containing 5% or more of a terpolymer resin, and the adhesive resin comprises an acid-modified PP resin containing 5% or more of a terpolymer resin. Also, both surfaces of aluminum are subjected to a chemical conversion treatment, and after dry-laminating the substrate and one surface subjected to the chemical conversion treatment, the other surface subjected to the chemical conversion treatment and a heat-sealable film layer are formed of a polypropylene film. And acid-modified PP
A method for producing a packaging material for a polymer battery, characterized in that a laminate obtained by laminating a resin by an sandwich lamination method using a resin as an adhesive resin is heated by post-heating so that the adhesive resin has a softening point or higher. It is.

[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 performed on both surfaces of the barrier layer, the heat-sealing film layer is laminated by a sandwich lamination method, and then 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. 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 , and (d).
Y ₁ part an enlarged view. FIG. 5 is a conceptual diagram illustrating a sandwich laminate 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.

Accordingly, the present inventors have performed chemical conversion treatment on both surfaces of aluminum, and acid-modified PP such as unsaturated carboxylic acid-grafted random propylene (hereinafter referred to as PPa) on the chemical conversion treatment surface on the aluminum content side. Is found to be able to solve the above problems by providing a terpolymer composed of a three-component copolymer of ethylene, butene and propylene as the heat-sealing layer. Reached. 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 extruded as an adhesive resin, a terpolymer film was laminated by a sandwich lamination method, and the obtained laminate was post-heated to find that the above-mentioned 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). ), A heat-sealing layer (terpolymer film made of a three-component copolymer of ethylene, butene and polypropylene) 14, and a three-component film of ethylene, butene and polypropylene formed by the adhesive resin layer 13. A terpolymer film 14 made of a copolymer is sandwich-laminated, and the post-heating described later improves the adhesive strength.

According to the present invention, as shown in FIG.
2, a chemical conversion treatment layer 15 is provided on both surfaces, and 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 extruding the adhesive resin 13 by sandwich lamination. Further, the formed laminate is heated by post-heating to a temperature higher than the softening point of the adhesive resin.

The packaging material for a polymer battery is used as an exterior body for wrapping a polymer battery body. Depending on the type of the exterior body, a pouch type as shown in FIG. 2 and an embossed type as shown in FIG. There is. 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 according to the present invention is, as shown in FIG. 1, a laminate comprising at least an outermost layer, a chemical conversion treatment layer, a barrier layer, a chemical conversion treatment layer, an adhesive resin layer, and a heat seal layer. The heat seal layer is laminated by a sandwich lamination method. The heat-sealing film 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 at the time of 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 chemical conversion treatment of aluminum surface using various substances and studying its effect, among the above-mentioned acid-resistant film-forming substances, it is composed of phenol resin, chromium fluoride (■) 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.

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). Providing the acid-modified PP layer has effects of preventing corrosion of aluminum and stabilizing the adhesion of the terpolymer serving as the heat seal layer.

Further, the inventors of the present invention have conducted intensive studies on a laminating method exhibiting stable adhesive strength. As a result, the base layer and one side of the chemical conversion treated barrier layer are dry-laminated, and the other side of the barrier layer is subjected to dry lamination. A terpolymer film comprising a three-component copolymer of ethylene, butene, and polypropylene (hereinafter, referred to as a heat seal layer) using acid-modified PP as an adhesive resin.
T-PP may be sandwich-laminated to form a laminate, and then the laminate is heated to a condition at which the adhesive resin has a softening point or higher, thereby obtaining a laminate having a predetermined adhesive strength. And could be. As a specific method of the heating, hot roll contact type, hot air type,
Although there are methods such as near or far infrared rays, any heating method may be used in the present invention, as long as the adhesive resin can be heated to the softening point temperature or higher as described above.

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

The terpolymer is based on an ethylene-butene-propylene copolymer as a base resin.
P is (1) a bigat softening point of 115 ° C. or higher and a melting point of 150 ° C.
The above homo-type, (2) copolymer with ethylene-propylene having a vigat softening point of 105 ° C. or more and a melting point of 130 ° C. or more (random copolymerization type) (3) Acid modification using an unsaturated carboxylic acid having a melting point of 110 ° C. or more It is a polymerized simple substance or a blend. Further, the acid-modified PP has a low crystalline ethylene butene copolymer having a density of 900 kg / m ³ or less, a low crystalline propylene butene copolymer,
Alternatively, 5% or more of amorphous ethylene-propylene copolymer, amorphous propylene-ethylene copolymer or ethylene-butene-propylene copolymer is added to impart flexibility, Improvement and crack prevention during molding may be performed.

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 further impart flexibility, thereby improving bending resistance. It is also possible to prevent cracks during molding.

As a laminate of the polymer battery packaging material of the present invention, an intermediate layer may be provided between the barrier layer and the heat seal layer, in addition to the base layer, the barrier layer, and the heat seal 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.

Each of the above-mentioned layers in the laminate of the present invention includes:
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 for the heat seal layer of the laminate in the packaging material for a polymer battery of the present invention. The use of Τ-PP for the heat seal layer is based on Τ-P
P has good heat-sealing properties, moisture-proof properties, heat-resistance, and other protective properties required for heat-sealing layers of polymer battery packaging materials. It is a desirable material due to its goodness and the like. The thickness of the Τ-PP is 30 to 100 μm,
It is desirable to use a terpolymer composed of a ternary copolymer of ethylene, butene and propylene having a melting point (120 ° C. or higher). Preferably, a polypropylene resin layer containing 5% or more of terpolymer, or 5% of terpolymer
This is a multilayer structure including at least one polypropylene resin layer including the above. 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.

Also, the Δ-PP has a density of 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 with respect to a metal, the heat-sealing of the tab portion in the polymer battery involves the steps shown in FIGS. 6 (a), 6 (b) and 6
As shown in (c), an adhesive film having heat sealing properties for both metal and Τ-PP is interposed between the tab and the heat seal layer of the laminated body, so that sealing at the tab portion is achieved. Sex is also ensured. The adhesive film is shown in FIG.
(D) As shown in FIGS. 6 (e) and 6 (f), the tab may be wound around a predetermined position. As the adhesive film, the unsaturated carboxylic graft polyolefin,
A film made of metal cross-linked polyethylene or a copolymer of ethylene or propylene and 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.

[0029]

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, a 20 μm thick
Then, extrude the following ethylene butene (1) to (6)
-Film composed of propylene copolymer (innermost layer thickness
30 μm) by the sandwich lamination method
Sample Example 1 was obtained. (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 the other side, 10% of an acid-modified PP terpolymer was added.
Is extruded to a thickness of 20 μm as an adhesive resin.
(5% terpolymer + 95% PP) blended resin
Film (innermost layer thickness 30μm) sandwich
Specimen Example 2 was obtained by laminating by a lamination 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, 50% of an acid-modified PP terpolymer was added.
Is extruded to a thickness of 20 μm as an adhesive resin.
(5% terpolymer + 95% PP) blended resin
Film (innermost layer thickness 30μm) sandwich
Specimen Example 3 was obtained by laminating by a laminating 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
Extruded into cast polypropylene (homotype,
(Melting point 151 ° C) by the sandwich lamination method
Then, the obtained laminate was heated to a surface temperature of aluminum of 150.
C. to obtain a sample comparative example 1. [Comparative Example 2] Nylon was applied to one surface of aluminum 40 µm.
25 μm together by dry lamination
The other surface of the aluminum is acid-modified at a softening point of 120 ° C.
Extruded to a thickness of 20 μm using PP as an adhesive resin,
Including the terpolymers (1) to (6) used in Example 1
, 30μm thick film sandwich laminated
Then, the obtained laminate was heated to a surface temperature of aluminum of 150.
C. to obtain a 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.
45 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, cracking and bending of the innermost layer during molding
Cracking of the innermost layer was not observed in 100 samples.
won.

[0030]

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.
The Τ-PP film of the heat seal layer is made of an acid-modified P
Since P can be laminated as an adhesive resin by a sandwich lamination method, the productivity is good, and the post-heating treatment allows
Adhesive strength as a polymer battery packaging material can be obtained, and 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 illustrating a sandwich laminate for producing a polymer battery packaging material.

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 DESCRIPTION OF SYMBOLS 12 Aluminum (barrier layer) 13 Adhesive resin layer 14 Heat seal layer (terpolymer film which consists of ternary copolymer 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 DESCRIPTION OF SYMBOLS 30 Sandwich laminating apparatus 31 Extruder 32 Die 33 Molten resin film 34 Chill roll 35 Pressure roll 36 Laminate base material 37 Laminate

 ──────────────────────────────────────────────────続 き Continued on the front page (72) 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) 4K044 AA16 AB10 BA10 BA15 BA17 BA20 BA21 BB05 BB06 BC02 CA62 5H011 AA09 BB03 CC02 CC06 CC10

Claims (7)

[Claims] 1. A terpolymer comprising a base material layer, an adhesive layer, a chemical conversion layer, aluminum, a chemical conversion layer, an adhesive resin layer, and a heat-sealing film layer, and at least a three-component copolymer of ethylene, butene and propylene. A packaging material for a polymer battery, wherein the heat-sealing film layer containing: is a layer laminated by sandwiching with an adhesive resin containing an acid-modified PP resin as a main component. 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 heat-sealing film layer is a terpolymer comprising a three-component copolymer of ethylene, butene and propylene. A packaging material for a polymer battery according to the above. 4. The method according to claim 1, wherein the adhesive resin is an acid-modified PP resin, and the heat-sealing film layer is a polypropylene resin layer containing 5% or more 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. A chemical conversion treatment is applied to both surfaces of aluminum, and a base material and one surface subjected to the chemical conversion treatment are dry-laminated, and then the other surface subjected to the chemical conversion treatment and the heat-sealable film layer are made of polypropylene. Film and acid-modified P
A method for producing a packaging material for a polymer battery, wherein a laminate obtained by laminating by a sandwich lamination method using a P resin as an adhesive resin is heated by post-heating so that the adhesive resin has a softening point or higher. Method.