JP2011138793A - Packaging material for polymer battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material used for a case for storing a polymer battery, which is excellent in water vapor and other gas barrier properties, has mechanical strength such as puncture resistance, and can be used even at high temperatures. However, a stable laminate structure is provided.
A laminate comprising an outermost layer / barrier layer / innermost layer or an outermost layer / barrier layer / intermediate layer / innermost layer, wherein the outermost layer has heat resistance, pinhole resistance, moldability, It is composed of a base material with insulating properties, and the barrier layer is composed of a barrier base material with water vapor barrier properties, moldability and acid resistance, and the intermediate layer is an intermediate with insulating properties and moldability. A polymer battery packaging material is formed of a base material, and the innermost layer is formed of a heat-sealable base material having heat-fusibility, cold resistance, electrolyte suitability, and insulation.
[Selection] Figure 1

Description

  The present invention relates to a laminate using an adhesive having acid resistance and organic solvent resistance, and more particularly to application to a pouch for a polymer battery.

  Currently, pouches using various laminates obtained by laminating various materials are mainly used as packaging materials. On the other hand, recently, a polymer battery in which a polymer battery body is housed in a pouch made of a laminate has been developed. The polymer battery is also referred to as a lithium secondary battery, is said to have a polymer electrolyte, and generates a current by the movement of lithium ions, and includes a positive electrode / negative electrode active material made of a polymer. The composition of the lithium battery is as follows: positive electrode current collector (aluminum, nickel) / positive electrode active material layer (made of polymer positive electrode material such as metal oxide, carbon black, metal sulfide, electrolyte, polyacrylonitrile) / electrolyte layer / ( Carbonate electrolyte such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethylene methyl carbonate, inorganic solid electrolyte composed of lithium salt, gel electrolyte, etc./negative electrode active material layer (lithium metal, alloy, carbon, electrolyte, polyacrylonitrile Polymer negative electrode materials / negative electrode current collectors (copper, nickel, stainless steel) and outer packaging that wraps them, etc. Applications of polymer batteries include personal computers, portable terminal devices (cell phones, PDAs, etc.), video cameras Used for electric vehicles, energy storage batteries, robots, satellites, etc. The polymer battery has a positive electrode current collector made of aluminum, nickel, etc., a positive electrode active material layer made of a polymer positive electrode material such as metal oxide, carbon black, metal sulfide, electrolyte, polyacrylonitrile, etc. Carbonate electrolytes such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl carbonate, ethylene methyl carbonate, inorganic solid electrolytes consisting of lithium salts, electrolyte layers consisting of gel electrolytes, lithium metals, alloys, carbon, electrolytes, poly It consists of a polymer battery body composed of a negative electrode active material layer such as acrylonitrile, a negative electrode current collector such as copper, nickel, stainless steel, etc., and an exterior body that wraps the polymer battery. Metal cans that are made into containers in the shape of a cuboid or cuboid, or That the multi-layer film composed of an outer layer / aluminum / sealant layer was in a bag shape it has been used.

  However, there have been the following problems as the outer package of the polymer battery. In a metal can, since the outer wall of the container is rigid, the shape of the battery itself is determined. Therefore, since the hardware side is designed in accordance with the battery, the size of the hardware using the battery is determined by the battery, and the degree of freedom in shape is reduced. In addition, the bag-shaped outer package made of a multilayer film is not limited in the degree of freedom of the shape of the hardware using the battery, as in the metal can, but the physical properties required for the outer package of the polymer battery The present condition is that the packaging material which can fully satisfy a function has not been developed yet. The required physical properties and functions are as follows. For example, as an exterior body of a polymer battery, it is necessary to hold a part of an electrode that connects the base part of the polymer battery body, the hardware, and the battery body in a sealed system that is cut off from the outside air. The innermost layer needs to have adhesiveness with the electrode, particularly heat sealability. Since the electrode is made of metal, the innermost layer is required to have heat sealability with the metal. In addition, the polymer battery has a heat seal stability and a sealing system due to the temperature rise of the battery, which is the content of the battery due to charging / discharging, and the environmental temperature used is, for example, a car dashboard in the summer or cold in the winter. Heat resistance and cold resistance are required in addition to hardware used to withstand use on the ground, etc. Even under the severe environment described above, it is required to ensure heat seal stability and a sealing system as an exterior body. In the case of a polymer battery, an electrolyte composed of a carbonate-based solvent and a lithium salt as a battery content may adversely affect the exterior body and reduce the adhesive strength between the multilayer film layers. That is, since it contains a solvent (carbonate type), the solvent swells the adhesive layer between the multilayer film layers and decreases the adhesive strength. Furthermore, acid and heat are generated by hydrolysis of the electrolyte, and the barrier layer made of metal is corroded to lower the adhesion strength between the layers. Further, the battery may ignite due to the generated heat. Moreover, the battery electromotive force is lowered due to the temperature rise, and the connected device may stop or break down. The hydrolysis of the electrolyte, which causes these problems, is due to the penetration of moisture from the outside into the battery sealing system. Therefore, the exterior body is required to block water vapor from the outside (barrier property). Further, not only polymer batteries but also battery outer bodies are required to have a structure that does not energize equipment (hardware) around the outer body and that the electrodes do not contact each other and short-circuit. In addition to the metal can and the bag, a shape sealed with a molding tray and a lid material is also conceivable as an outer package of the polymer battery. Also in this case, selection of the innermost layer resin having heat sealability and a laminate having good moldability when molding the tray have been demanded. The present invention is excellent in water vapor and other gas barrier properties as a packaging material used for a case containing a polymer battery, and has mechanical strength such as puncture resistance, and can be used even at high temperatures. In contrast, the present invention provides a stable laminate.

  The present invention relates to an aluminum foil having a thickness of 15 μm or more of phosphoric acid in a laminate comprising an outermost layer / barrier layer / intermediate layer / innermost layer or an outermost layer / barrier layer / intermediate layer / innermost layer. After forming an acid-resistant film made of salt, chromate, chromium phosphate, zinc phosphate and / or coupling treatment made of a silane, organic titanium, or organic aluminum material, a protective layer is provided, Resin that can be used when the layers on the innermost layer side of the barrier layer are laminated by a dry lamination method is an acid-resistant adhesive, and the innermost layer can be thermally bonded at least between the innermost layers A polymer battery packaging material comprising: an epoxy resin, a phenol resin, a melamine resin, an unsaturated carboxylic acid grafted polyolefin resin, an acrylic resin, The acid-resistant adhesive is composed of a main agent and a curing agent, and the main agent is an acid component containing at least two kinds of sebacic acid, isophthalic acid, terephthalic acid, octatannic acid, nonannic acid, undecanoic acid, and palmitic acid, and ethylene glycol. , A blend of a polyester resin composed of an alcohol component containing at least one kind of hexanediol and diethylene glycol, and a bisphenol A type epoxy resin, the curing agent is a composition composed of a polyisocyanate component, and the intermediate layer is thick. Resin having at least one layer of polyester resin, polyolefin resin, etc. having a thickness of 5 μm or more, or a resin formed from these modified products and mixtures, and a resin having adhesiveness to the innermost layer is an unsaturated carboxylic acid Graft polyolefin, metal ion cross-linked polyethylene The polyester resin used in the innermost layer and / or the intermediate layer is a polyethylene terephthalate copolymer or a polybutylene terephthalate copolymer. Is included.

  The pouch-type exterior body formed of the polymer battery packaging material of the present invention allows the polymer battery itself to be flexible, can be lighter than using a metal can, and can reduce the total layer thickness. As a result, it was possible to save space as a battery. In particular, it has excellent barrier properties as a polymer battery packaging material, can maintain the barrier properties for a long time, and can be a packaging material excellent in heat resistance, cold resistance, content resistance, and the like.

Example of packaging material for polymer battery of the present invention, (a) Basic layer structure, (b) Perspective view explaining structure of polymer battery, (c) Cross section of X ₁ -X ₁ part, (d FIG. 4 is a cross-sectional view taken along a line X ₂ -X ₂ . Another embodiment of the polymer battery packaging material of the present invention, (a) basic layer configuration, (b) perspective view explaining the structure of the polymer battery, (c) perspective view of the polymer battery of an embossed type exterior body. Figure is a cross-sectional view of (d) X ₃ -X ₃ parts. It is sectional drawing which shows another Example of the laminated body of this invention. It is explanatory drawing which shows another Example of adhesion | attachment with the exterior body and tab in this invention, (a) The perspective view of a polymer battery, (b) The perspective view of the polymer battery main body which adhere | attached the heat bondable tab material, (c) ) A perspective view of another polymer battery main body to which a heat-adhesive tab material is bonded, and (d) and (e) are X ₄ -X ₄ part cross-sectional views when the respective heat-adhesive tab materials are used. It is the top view which shows the shape of the pouch type exterior body of the polymer battery using the laminated body of this invention, and sectional drawing of each type. Perspective view of the bottom member of Embossed type shows the shape of the exterior body of (a) one surface embossed type polymer battery using a laminate of the present _{invention, (a ') X 9 -X} 9 parts cross-sectional view, (b) double-sided embossing Type perspective view, (b ′) X ₁₀ -X ₁₀ cross-sectional view, (c) conceptual view of another example showing the position of the tab in the embossed tie, (d) example of providing the tab in another position It is a conceptual diagram.

The polymer battery packaging material according to the present invention will be described in more detail with reference to the drawings. Figure 1 shows an embodiment of a polymer battery packaging material of the present invention, (a) the basic layer structure, (b) a perspective view illustrating a structure of a polymer battery, (c) X ₁ -X ₁ part cross-section Figure is a cross-sectional view of (d) X ₂ -X ₂ parts. FIG. 2 shows another embodiment of the packaging material for a polymer battery of the present invention, (a) a basic layer structure, (b) a perspective view explaining the structure of the polymer battery, and (c) an embossed type exterior body. perspective view of a polymer battery, a cross-sectional view of (d) X ₃ -X ₃ parts. FIG. 3 is a cross-sectional view showing another embodiment of the laminate of the present invention. FIGS. 4A and 4B are explanatory views showing another embodiment of the adhesion between the outer package and the tab in the present invention. FIG. 4A is a perspective view of a polymer battery, and FIG. Figure, (c) Perspective view of another polymer battery main body to which a heat-adhesive tab material is bonded, (d) and (e) are cross-sectional views taken along line X ₄ -X ₄ when the respective heat-adhesive tab materials are used. It is. FIG. 5 is a plan view showing the shape of a pouch-type exterior body of a polymer battery using the laminate of the present invention and a cross-sectional view of each type. FIG. 6 shows the shape of an embossed type exterior body of a polymer battery using the laminate of the present invention, (a) a perspective view of a single-sided embossed type bottom material, (a ′) a cross-sectional view of X ₉ -X ₉ part, b) a perspective view of a double-sided embossed _{type, (b ') X 10 -X} 10 parts cross-sectional view, (conceptual diagram of another example showing the location of the tab in c) embossing Taib, in yet another position (d) is tab It is a conceptual diagram of the example provided.

  As a result of diligent research, the present inventors have found that the present invention can solve the problems of the present invention by forming a multilayer material composed of each of the materials described below, as a result of diligent research. The present invention has been completed. In the polymer battery according to the present invention, as shown in FIGS. 1B and 1C, the polymer battery body 2 is enclosed in a pillow type (hereinafter referred to as a pouch type) exterior body 4 to form an electrode. This is a structure in which a part of is exposed outside the exterior body. Alternatively, as shown in FIGS. 2 (b) and 2 (d), at least one-sided laminate is molded (hereinafter referred to as embossing) to form a bottom material, and the polymer battery body 2 is attached to the embossed portion 8 of the bottom material. The polymer battery main body 2 is covered with another laminate as the lid member 7, and the periphery is heat-sealed and sealed. The form of the exterior body relating to the pouch type and the embossed type (hereinafter sometimes referred to as cup type) will be described in detail later. The laminate is basically composed of three layers of outermost layer / barrier layer / innermost layer, and may have a four-layer structure in which an intermediate layer is provided between the barrier layer and the innermost layer. FIG. 1A shows the four-layer laminate. Each layer is made of a material that will be sequentially described below. The polymer battery of the present invention forms a heat seal part including a part of the electrode 3 as shown in FIG.

  The outermost layer 11 of the laminate 10 in the present invention is composed of stretched polyester or stretched nylon. At this time, as the polyester resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymer polyester, Examples include polycarbonate. Nylon is a polyamide resin, that is, nylon 6, nylon 6,6, a copolymer of nylon 6,6 and nylon 6, nylon 6,10, crystalline nylon such as polymetaxylylene atodipamide (MXD6) And amorphous nylon.

  When the outermost layer 11 is used as a polymer battery, the outermost layer 11 is a portion that is in direct contact with the hardware. Considering the existence of pinholes in a single film and the occurrence of pinholes during processing, the outermost layer needs to have a thickness of 6 μm or more, and a preferred thickness is 12 to 25 μm.

In the present invention, the outermost layer 11 can be laminated in order to improve pinhole resistance and insulation with the hardware when used as a battery outer package. In that case, the outermost layer 11 includes at least one resin layer of two or more layers, and the thickness of each layer is 6 μm or more, preferably 12 to 25 μm. Examples of laminating the outermost layer 11 include the following 1) to 3) although not shown.
1) Stretched polyethylene terephthalate / stretched nylon 2) Stretched polyethylene terephthalate / polyethylene 3) Stretched nylon / polyethylene

  The outermost layer 11 is bonded to the barrier layer 12 by dry lamination, extrusion lamination, or the like.

  The barrier layer 12 is a layer for preventing water vapor from entering the inside of the polymer battery 1 from the outside, and stabilizes pinholes and processability (pouching, embossing formability) of the barrier layer alone, In order to provide pinhole resistance, a metal such as aluminum or nickel having a thickness of 15 μm or more, or an inorganic compound such as silicon oxide or alumina can be used. The barrier layer is preferably soft aluminum having a thickness of 20 to 80 μm. In order to further improve the generation of pinholes, and to make the polymer battery exterior body an embossed type, there is no generation of cracks in the embossed part. The aluminum material used has an iron content of 0.3 to 9.0%, preferably 0.7 to 2.0%, so that the aluminum has ductility compared to aluminum that does not contain iron. As a result, it has been found that a pinhole is not easily generated by bending as a laminated body, and a side wall portion during embossing for the embossed type exterior body can be easily formed. When the iron content is less than 0.3%, effects such as prevention of pinholes and improvement of formability are not recognized, and when the iron content of the aluminum exceeds 9.0% Further, the flexibility as aluminum is hindered, and the bag-making property is deteriorated as a laminate.

  Furthermore, the present inventors have prevented the dissolution and corrosion of the aluminum surface by hydrofluoric acid (chemical formula: HF) generated by the reaction between the electrolyte of the polymer battery and moisture, and the adhesion (wetting) of the aluminum surface. In order to improve the stability of the adhesion between aluminum and the innermost layer when forming a laminate, the formation of an acid-resistant film and the formation of a protective layer on the aluminum surface It has been found that there is a remarkable effect in solving the above-mentioned problems.

  Examples of the acid-resistant modified film provided on the aluminum surface include phosphate-based and chromic acid-based films. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate. Examples of the chromic acid system include chromium chromate.

In addition, examples of the adhesion improving treatment include an aluminum surface coupling treatment and / or roughening. As the coupling treatment, silane coupling agents, organotitanium coupling agents, and organoaluminum coupling agents can be utilized. Tetraalkoxy titanium, titanium acylate, titanium chelate and the like can be used as the organic titanium coupling agent, and trialkoxyaluminum, aluminum chelate, aluminum acylate and the like can be used as the organic aluminum coupling agent. Roughening of the aluminum surface is also effective as an adhesion improving treatment. In other words, the aluminum surface is etched to remove aluminum oxide (chemical formula: AL ₂ O ₃ ) present on the aluminum surface, increase the surface roughness, increase the surface area, and develop an anchor effect to improve adhesion. Alternatively, it can be washed with an alkali.

  The protective layer is formed on the aluminum surface by any one of the epoxy-based, phenol-based, melamine-based, polyester-based, unsaturated carboxylic acid grafted polyolefin-based materials containing the acid resistance modifier, and modified products thereof. The resin layer containing is provided.

Also, the above surface treatments can be used in combination. For example,
(1) Formation of aluminum / acid-resistant film (2) Formation of aluminum / acid-resistant film / formation of protective layer

In the present invention, an epoxy resin, a phenonol resin, a melamine resin, an olefin resin unsaturated carboxylic acid grafted polyolefin not containing the acid resistance modifier in addition to the protective layer containing the acid resistance modifier. You may form the 2nd protective layer containing any one of resin, acrylic resin, and these modified substances. As a method for forming the second protective layer in this case, for example,
(1) Formation of aluminum / acid-resistant film / formation of second protective layer (2) Formation of aluminum / acid-resistant film / formation of protective layer / formation of second protective layer.

  In the present invention, an intermediate layer 13 may be provided between the barrier layer 12 or the protective layer and the innermost layer 14. In the intermediate layer, the innermost layer 14 which is a heat seal layer is thinned by the heat protection and pressure of the heat seal at the time of bag making, and the electrode 3 and the aluminum (barrier layer 12) are in contact with each other (short circuit occurs). ). The intermediate layer 13 is laminated in order to stabilize the environmental suitability (heat resistance, cold resistance) of the battery. The polyester resin has a thickness of 10 μm or more and a melting point of 80 ° C. or more, preferably 12 to 25 μm. And at least one layer formed from a polyolefin-based resin, or a modified product and a mixture thereof. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, and copolymers or modified products thereof. Examples of the polyolefin resin include polypropylene, ethylene propylene copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using a single site catalyst. Copolymers, metal ion-containing polyethylene, copolymers of ethylene and methacrylic acid or acrylic acid derivatives, polybutene, unsaturated carboxylic acid grafted polyethylene, unsaturated carboxylic acid grafted polypropylene, unsaturated carboxylic acid grafted polymethylpentene and their modified products Can be mentioned. These resins can be used in either a stretched or unstretched state.

The innermost layer 14 of the polymer battery packaging material in the present invention comprises an unsaturated carboxylic acid grafted polyolefin, an ethylene and acrylic acid derivative, a copolymer resin of ethylene and a methacrylic acid derivative, a metal ion crosslinked polyethylene, and a modified product thereof. Formed from a mixture. The thickness of the innermost layer is preferably 20 μm or more, the melting point of the resin forming the innermost layer is preferably 70 ° C. or higher, and the Vicat softening point is preferably 60 ° C. or higher. For the innermost layer, it is possible to use a polyolefin-based resin 14 'having no metal adhesion, but in this case, the unsaturated carboxylic acid graft graft polyolefin, metal ion cross-linked polyethylene between the electrode 3 and the innermost layer is used. By using a heat-adhesive tab material (thickness of 15 μm or more) 16 formed from ethylene or propylene and acrylic acid or propylene and acrylic acid or methacrylic acid or methacrylic acid derivative copolymer, Fully glued and can be sealed. Specifically, as shown in FIG. 4B, a heat-adhesive tab material 16 having a width wider than that of the electrode is placed on the heat-bonding portion of the electrode, inserted into the exterior body, and thermally bonded to be sealed. FIG. 4D schematically shows a cross section of the X ₄ -X ₄ part after thermal bonding in this case (however, the outermost layer, the barrier layer, and the intermediate layer are shown as one layer). FIG. 4C is an example in which the heat-adhesive tab material 16 is wound around the heat-bonding portion of the electrode 3 and inserted into the exterior body and thermally bonded and sealed. FIG. FIG. 4 schematically shows a cross section of the X ₄ -X ₄ part after heat bonding in this case as in FIG.

Further, the innermost layer 14 forms a sealed system in a state where electrode tabs are sandwiched by a thermal welding method for both the pouch type and the embossed type. However, the olefin resin as the innermost layer of the heat-welded portion becomes brittle because of its characteristics, and cracks and pinholes are easily generated. Also, at the time of thermal welding, the end portion of the electrode tab eliminates pinholes by crushing the innermost layer by the thickness of the tab, but the olefin has a high melting point in order to increase the heat resistance of the innermost layer. When a single-layer resin is used, it must be welded at high temperature, high pressure and for a long time. In this case, the function of the packaging material is deteriorated by reducing the characteristics of the battery in which the heat welding itself is the content or by causing thermal contraction of other constituent layers of the packaging material such as polyester or nylon of the outermost layer. Wake up. As a result of various studies, the present inventors have found that the innermost layer is multi-layered and found that the problem is effective, and have completed the present invention. Specifically, the innermost layer is multilayered.
(1) Olefin resins and their modified products / unsaturated carboxylic acid grafted polyolefins (2) Olefin resins and their modified products / ethylene and acrylic acid derivatives or ethylene and methacrylic acid derivative copolymers (3) Olefin And the innermost layer having a constitution of a modified resin / metal ion crosslinked polyethylene, metal ion crosslinked polypropylene, or the like.
As the typical olefin-based resin, a) as a polypropylene-based resin,
1) Homotype polypropylene (melting point 150 ° C or higher, Vicat softening point 140 ° C or higher)
2) Ethylene-propylene copolymer (random type propylene or block propylene or butene copolymerized random propylene resin = terpolymer having a melting point of 110 ° C. or higher and a Vicat softening point of 100 ° C. or higher)
b) As a polyethylene type,
3) Low-density polyethylene having a melting point of 90 ° C or higher and a bigat softening point of 80 ° C or higher, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-propylene-diene copolymer, ethylene-propylene-butene copolymer, An ethylene-α / olefin copolymer polymerized using a single-site catalyst and acid-modified polyolefin (melting point 90 ° C. or higher, Bigat softening point 80 ° C. or higher)
A) Ethylene-vinyl acetate copolymer b) Metal ion cross-linked polyethylene, metal ion cross-linked polypropylene c) Unsaturated carboxylic acid grafted polyethylene, unsaturated carboxylic acid grafted polypropylene, unsaturated carboxylic acid grafted polymethylpentene, etc. Polyolefin and modified products thereof.
D) As copolymers of ethylene or propylene and methacrylic acid or acrylic acid derivatives, ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl methacrylate (EMA), ethylene-methyl acrylate copolymer (EMAA) , Ethylene-ethyl acrylate (EEA), ethylene-acrylic acid copolymer (EAA), propylene-ethyl methacrylate (PMA), propylene-ethyl acrylate (PAA), and the like.

As a more specific example of the multilayering of the innermost layer 14, the following configuration can be given.
(1) low density polyethylene or linear low density polyethylene / copolymer of ethylene and methacrylic acid or acrylic acid derivative (2) ethylene-propylene copolymer / copolymer of propylene and methacrylic acid or acrylic acid derivative ( 3) Low density polyethylene or linear low density polyethylene / metal cross-linked polyethylene (4) ethylene-propylene copolymer / metal cross-linked polypropylene (5) random propylene-based / unsaturated carboxylic acid grafted homo-type propylene (6) block propylene-based / Unsaturated carboxylic acid grafted homotype propylene (7) Homopropylene / unsaturated carboxylic acid grafted random type, or grafted type propylene (8) Random or block propylene / homopropylene type (9) Ethylene-propylene copolymer Polyethylene / ethylene-propylene copolymer (10) ethylene-propylene copolymer / polyethylene / unsaturated carboxylic acid grafted polyethylene (11) homopropylene system / random propylene system (12) random propylene system / homopropylene system / random propylene system (13) Random propylene / block propylene / random propylene (14) Random propylene / butene copolymerization Random propylene (15) Homopropylene / butene copolymerization random propylene

  Further, in order to stabilize the embossing formability, the innermost layer 14 has a dynamic friction coefficient and a static friction coefficient of 0.5 or less, preferably 0.2 or less. In order to achieve the friction coefficient, fatty acid amide type lubricants such as fatty acid amides such as erucic acid amide, stearic acid amide, and oleic acid amide are 500 ppm or more, or dimethyl silicone and methylphenyl silicone type silicone lubricants having a molecular weight of 100,000 or more. It is preferable to add 1000 ppm or more, or 3% or more of a powdery silicone resin.

  For each layer of the laminate constituting the polymer battery packaging material of the present invention, for the purpose of improving and stabilizing film forming properties, lamination processing, suitability for final product secondary processing (embossing, pouching) as appropriate. In addition, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

  The outermost layer, the barrier layer, or the outermost layer, the barrier layer, the intermediate layer, and the innermost layer of the laminate of the present invention are specifically formed by the T-die method, the inflation method, or the coextrusion method. The secondary film can be formed by a technique such as coating, vapor deposition, ultraviolet curing, electron beam curing, etc. if necessary, and laminating can be performed by dry lamination, It can be laminated by methods such as extrusion lamination, coextrusion lamination, thermal lamination (thermal lamination) and the like. In the case of the dry lamination, in the lamination outside the barrier layer, the lamination may be carried out using a normal dry lamination adhesive. However, when dry lamination is performed on the innermost layer side of the barrier layer, it is preferable to use an adhesive having a composition as described below.

  Hydrogen fluoride generated by delamination by a carbonate-based solvent that is an electrolyte component of a polymer battery and reaction between a lithium salt and water when the structure of the laminate forming the exterior body for the polymer battery is adhesion by a dry laminate method As a result of diligent research, the present inventors, as a result of diligent research, addressed problems such as peeling of the adhesive surface on the innermost layer side surface of the barrier layer by the adhesion when dry-laminating the adhesion of each layer inside the barrier layer By setting the component of the agent to the following composition, it was possible to obtain a laminate excellent in heat resistance without delamination and adhesion surface peeling on the barrier layer surface. The adhesive consists of a main agent and a curing agent. The main agent is sebacic acid, isophthalic acid, terephthalic acid, octatanic acid, nonannic acid, undecanoic acid, an acid component containing at least two kinds of palmitic acid, ethylene glycol, hexane It is composed of a blend of a polyester resin composed of an alcohol component containing at least one diol and diethylene glycol and a bisphenol A type epoxy resin, and the curing agent is composed of a polyisocyanate component (TDI, MDI, IPDI, HDI, XDI).

  Further, by using an unsaturated carboxylic acid grafted polyolefin as a resin for the extrusion lamination or thermal lamination, the content resistance and the physical property resistance are improved.

  In addition, in the case of the extrusion lamination, as an adhesion promotion method for stabilizing the adhesive force between the respective layers to be bonded, a polyester-based, polyether-based, urethane-based, polyether-urethane-based, polyester-urethane is applied to the bonding surface of the layer to be bonded. About 1 μm or ozone treatment of resin such as epoxy, isocyanate, polyolefin, polyethyleneimine, cyanoacrylate, organotitanium compound, epoxy, imide, silicone and their modified products or mixtures A surface activation treatment can be performed by the above.

As a method of laminating the laminate of the present invention, in the case of a three-layer structure, as a method of laminating the laminate of the present invention, typically, the following three methods:
1) As a 1st base material, the 2nd base material laminated body which consists of a laminated body of an outermost layer / barrier layer, and an innermost layer is prepared, respectively, and heat lamination is carried out.
2) A method of preparing an outermost layer / barrier layer as a first base material and an innermost layer as a second base material and extruding lamination (including coextrusion), in this case, subjecting to a heat lamination step again if necessary.
3) Any method of pasting all together by dry lamination may be used.

In the case of a four-layer configuration, the following three methods are typically used as a method of stacking:
1) Prepare and thermally laminate a laminate of outermost layer / barrier layer and a second substrate laminate comprising an intermediate layer / innermost layer as the first substrate 2) Outermost layer / barrier layer as the first substrate, As a second substrate, a part of the intermediate layer / innermost layer laminate or only the innermost layer is prepared, and extrusion lamination (including coextrusion) is performed with the intermediate layer. In this case, the thermal lamination process is again performed 3 ) Any method of bonding all together by dry lamination may be used.

  In addition, as an intermediate layer, gas, liquid, ion permeation prevention thin film layer is formed by sputtering, chemical vapor deposition, physical vapor deposition, metal thin film layer such as aluminum layer, metal oxide such as aluminum oxide or tin oxide. By forming a vinylidene chloride layer or the like using a layer or a coating method, it is possible to further prevent permeation of the electrolyte constituent material to the barrier layer and to provide stable adhesion.

  The layer structure of the laminate as the polymer battery packaging material of the present invention described above was prepared as described below, and was specifically evaluated as a packaging material for polymer batteries as a pouch type and an emboss type. . In the following description, the following abbreviations are used for film names, substance names, processing methods, and the like.

<Abbreviation>
Stretched polyester: OPET, stretched polyamide: ON, aluminum: AL, copolymer stretched polyester: COPET, chromium phosphate coating: PC, trivalent chromium coating: 3C, zinc phosphate coating: PZ, calcium phosphate coating: PCa, polyester polyurethane Adhesive: PUD, polyether urethane adhesive: PED, unsaturated carboxylic acid grafted random propylene adhesive: PAD, unsaturated carboxylic acid grafted polyethylene adhesive: PEAD, thermal lamination: TL, dry lamination: DL, resin melt extrusion Lamination: EC, anchor coat: ANC, epoxy: EP, phenol: FN, melamine: MR, acrylic: AC, polyester: PET, unsaturated carboxylic acid grafted random propylene: PPA, unsaturated carboxylic acid group Polyethylene: PPEA, ethylene-methyl methacrylate copolymer: EAM, homopropylene: PH, random propylene: PR, butene copolymerization random propylene: BR, high density polyethylene: HD, low density polyethylene: LD, = is a laminate Indicates the name of the substance used. Further, only the dry laminate and not the name of the used adhesive are laminated using a polyester urethane adhesive.

<Evaluation details>
Pouches or cups were prepared using the following packaging materials and evaluated for the following performance.
1. Appropriateness of electrolyte solution After injecting and sealing the pseudo electrolyte solution, the presence or absence of delamination between the barrier layer and the innermost layer, or between the barrier layer and the intermediate layer when stored at 60 ° C for 30 days was examined.
2. Water vapor barrier property 40 ° C., 90% RH, water content at 30 days storage is 300 ppm or less.
3. Inner layer seal strength change -40 N for 30 days, after standing at room temperature (23 ° C.) for 1 hour, the strength is 15 mm wide and 9.8 N (1 kgf) or more.
4). Electrode tab short-circuit prevention property When the electrode tab is sandwiched between the innermost layers and the portion sandwiched between the electrode tabs is sealed at 190 ° C., 3.5 seconds, 0.3 MPa,
(1) Confirm that there is no pinhole in the outermost layer and that it is not peeled off from the barrier layer.
(2) Inspecting the contact between the electrode tab and the barrier layer.
5. Formability in case of molded product (cup): Press molding is performed in a cold state using a male mold and a female mold so as to have a depth of 3.1 mm. At this time, the clear run of the male type and the female type was 1 mm. Then, the occurrence of pinholes in the molded part when 100 pieces were formed was inspected. The simulated electrolyte is a solution obtained by adding 1M 6 lithium fluorophosphate (LiPF ₆ ) to ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1: 1: 1 (weight ratio).
Basic heat seal conditions are 190 ° C, 3.5 seconds, 0.3 MPa

<Example of pouch type>
・ Pouch: 4-way seal type ・ Packaging form dimensions: 40 mm x 60 mm (seal width 5 mm)
-The order of lamination is not limited to the examples and can be changed as appropriate.
<Configuration of Laminate as Example> In all the descriptions, the left is the outer surface, and the right is the inner side (polymer battery main body side).

The outermost layer of the stretched polyester film 12 μm and the aluminum 20 μm provided with an acid-resistant film made of a trivalent chromium film are dry-laminated, the stretched polyester 6 μm is dry-laminated as an intermediate layer on the acid-resistant film surface, and the intermediate The packaging material of Example 1 was obtained by dry-laminating 50 μm of unsaturated carboxylic acid grafted random propylene as the innermost layer on the surface of the layer. In terms of abbreviations, OPET12 / PUD / AL20 / 3C / PUD / OPET6 / PUD / PPA50
In the following, the created examples are also indicated by abbreviations. The number described after the abbreviation indicates the layer thickness μm. // indicates the interlayer of coextrusion film formation, and + indicates blend.

The layers were laminated in the same manner as in Example 1 except that the outermost layer was drawn nylon 15 μm, the aluminum thickness was 15 μm, the intermediate layer was homopropylene 10 μm, and the innermost layer thickness was 70 μm.
ON15 / PUD / AL15 / 3C / PUD / PH10 / PUD / PPA70

The barrier layer had a thickness of 25 μm, an acrylic film was laminated as a protective layer on the innermost layer side of the barrier layer by a dry laminating method, and a coextruded film of random propylene, homopropylene and random propylene was heat laminated as the innermost layer. Except for the above, lamination was performed in the same manner as in Example 1.
OPET12 / PUD / AL25 / 3C / PUD / AC5 / PUD / OPET6 / TL / PR5 // PH30 // PR10

As an outermost layer, dry lamination of 12 μm of stretched polyester film and 15 μm of stretched nylon and 20 μm of aluminum provided with an acid-resistant film composed of a trivalent chromium film is dry-laminated on the stretched nylon surface using a polyester urethane adhesive, 6 μm of stretched polyester was dry-laminated as an intermediate layer on the acid-resistant film surface, and 60 μm of unsaturated carboxylic acid grafted random propylene was dry-laminated as the innermost layer on the surface of the intermediate layer.
OPET12 / PUD / ON15 / PUD / AL20 / 3C / PUD / OPET6 / PUD / PPA60

Lamination was performed in the same manner as in Example 4 except that the thickness of aluminum was 25 μm, the acid-resistant coating was a chromium phosphate coating, and the thickness of the innermost layer was 40 μm.
OPET12 / PUD / ON15 / PUD / AL25 / PC / PUD / OPET6 / PUD / PPA40

Lamination was performed in the same manner as in Example 5 except that the acid-resistant coating was a zinc phosphate coating and the innermost layer thickness was 50 μm.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / PUD / OPET6 / PUD / PPA50

Lamination was performed in the same manner as in Example 6 except that the acid-resistant film was a calcium phosphate film.
OPET12 / PUD / ON15 / PUD / AL25 / PCa / PUD / OPET6 / PUD / PPA50

As the outermost layer, stretched polyester film 12 μm and stretched nylon 15 μm are dry-laminated, aluminum 20 μm provided with an acid-resistant film made of a trivalent chromium film on the stretched nylon surface is dry laminated, and the innermost layer side of the aluminum is coated. A protective layer of 5 μm of epoxy resin was provided, 6 μm of stretched polyester was dry-laminated as an intermediate layer on the surface of the protective layer, and 50 μm of unsaturated carboxylic acid grafted random propylene was dry-laminated as the innermost layer on the surface of the intermediate layer.
OPET12 / PUD / ON15 / PUD / AL20 / 3C / EP5 / PUD / OPET6 / PUD / PPA50

The protective layer was laminated in the same manner as in Example 8 except that the phenol resin was 3 μm.
OPET12 / PUD / ON15 / PUD / AL20 / 3C / FN3 / PUD / OPET6 / PUD / PPA50

Lamination was performed in the same manner as in Example 8 except that the adhesive of the dry laminate between the outermost layer and aluminum was a polyether urethane adhesive, and the protective layer was 4 μm of melamine resin.
OPET12 / PUD / ON15 / PED / AL20 / 3C / MR4 / PUD / OPET6 / PUD / PPA50

The protective layer was laminated in the same manner as in Example 8 except that the polyester resin was 10 μm.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / PET10 / PUD / OPET6 / PUD / PPA50

It laminated by the same method as Example 8 except having made the protective layer into 5 micrometers of acrylic resins.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC5 / PUD / OPET6 / PUD / PPA50

Lamination was performed in the same manner as in Example 8 except that a polyether urethane adhesive was used as the dry laminate adhesive of the stretched polyester and stretched nylon of the outermost layer, and the protective layer was an unsaturated carboxylic acid grafted random propylene 4 μm.
OPET12 / PED / ON15 / PUD / AL25 / 3C / PPA4 / PUD / OPET6 / PUD / PPA50

The protective layer was laminated in the same manner as in Example 8 except that the unsaturated carboxyl grafted polyethylene was 4 μm.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / PEA4 / PUD / OPET6 / PUD / PPA50

Lamination was performed in the same manner as in Example 12 except that a polyether urethane adhesive was used as an adhesive for dry lamination of the outermost layer and aluminum, and the innermost layer was 70 μm of unsaturated carboxylic graft polyethylene.
OPET12 / PUD / ON15 / PED / AL25 / 3C / AC5 / PUD / OPET6 / PUD / PEA70

The innermost layer was laminated in the same manner as in Example 12 except that the ethylene-methyl methacrylate copolymer was 50 μm.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC5 / PUD / OPET6 / PUD / EAM50

Lamination was performed in the same manner as in Example 12 except that the innermost layer was 30 μm homopropylene.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC3 / PUD / OPET6 / PUD / PH30

It laminated by the same method as Example 12 except having changed innermost layer into 40 micrometers of random propylene.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC5 / PUD / OPET6 / PUD / PR40

The innermost layer was laminated in the same manner as in Example 12 except that the butene copolymerized random propylene was 90 μm.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC5 / PUD / OPET6 / PUD / BR90

As the outermost layer, 25 μm aluminum provided with an acid-resistant film made of a trivalent chromium film by dry lamination of 12 μm of stretched polyester film and 15 μm of stretched nylon is dry-laminated on the stretched nylon surface, and acrylic resin is applied to the acid-resistant film surface. A protective layer having a thickness of 2 μm was provided, and on the surface of the protective layer, unsaturated carboxylic acid grafted random propylene was used as a heat-adhesive resin, and 60 μm of the innermost random propylene was thermally laminated.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC2 / PUD / OPET6 / TL = PAD / PR60

The adhesive of the dry laminate of the outermost layer and aluminum is a polyether urethane adhesive, 5 μm of an epoxy resin is provided as a protective layer, and an unsaturated carboxylic acid grafted polyethylene adhesive is used as a heat adhesive resin on the protective layer surface, The innermost layer was laminated in the same manner as in Example 20 except that the ethylene-methyl methacrylate copolymer was 50 μm.
OPET12 / PUD / ON15 / PED / AL25 / 3C / EP5 / TL = PEAD / EAM50

The protective layer was laminated by the same method as in Example 20 except that the unsaturated carboxylic acid grafted random propylene was 5 μm, and the innermost layer unsaturated carboxylic acid grafted random propylene was directly heat laminated to the protective layer surface.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / PPA5 / TL / PPA50

Lamination was performed in the same manner as in Example 20 except that the acid-resistant coating was a zinc phosphate coating, the protective layer was 2 μm of phenol resin, and the innermost layer resin was 70 μm of butene copolymerized random propylene.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / FN2 / TL = PAD / BR70

Lamination was performed in the same manner as in Example 20 except that the acid-resistant coating was a zinc phosphate coating and the protective layer was formed as a blend of epoxy resin and melamine resin (blend ratio 5: 1) to a thickness of 6 μm.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / EP + MR / TL = PAD / PR60

The outermost layer and aluminum dry laminate adhesive was polyether urethane adhesive, the acrylic resin protective layer thickness was 4μm, the innermost layer was co-extrusion of homopropylene 40μm and random propylene 10μm The film was laminated by the same method as in Example 20 except that the protective layer surface and the homopropylene surface were dry laminated.
OPET12 / PUD / ON15 / PED / AL25 / 3C / AC4 / PUD / OPET6 / PUD / PH40 // PR10

The thickness of the protective layer of the acrylic resin was 4 μm, the innermost layer was a co-extruded film of 30 μm of homopropylene and 25 μm of unsaturated carboxylic acid grafted random propylene, and the protective layer surface and the homopropylene surface were dry laminated. Except for this, the layers were laminated in the same manner as in Example 20.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC4 / PUD / OPET6 / PUD / PH30 // PPA25

The thickness of the protective layer of acrylic resin is 4 μm, the innermost layer is a co-extruded film of homopropylene 40 μm and random propylene 10 μm, and the protective layer surface and the homopropylene surface are bonded with unsaturated carboxylic acid grafted random propylene Lamination was performed in the same manner as in Example 20 except that the heat-adhesive resin was heat laminated.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC4 / TL = PAD / PH40 // PR10

A zinc phosphate film is formed as an acid resistant film, and the innermost layer is a co-extruded film of 5 μm random propylene, 20 μm homopropylene and 10 μm random propylene, and the acid resistant film surface, the random propylene 5 μm surface and an unsaturated carboxylic acid. It laminated | stacked by the same method as Example 20 except having laminated | stacked by the same method as Example 20 except having grafted the graft random propylene adhesive as a thermoadhesive resin.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / TL = PAD / PR5 // PH20 // PR10

The protective layer is an unsaturated carboxylic acid grafted polyethylene 3 μm, the innermost layer is a coextruded film of low density polyethylene 15 μm and an ethylene-methyl methacrylate copolymer 50 μm, and the low density polyethylene surface of the coextruded film is a laminated surface. Except that, the layers were laminated in the same manner as in Example 28.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / PPEA3 / TL = PAD / LD15 // EAM50

As the outermost layer, stretched polyester and stretched nylon are dry-laminated using a polyetherurethane-based adhesive, and 25 μm aluminum formed with a trivalent chromium film as an acid-resistant film and the stretched nylon surface of the outermost layer are dry-laminated, On the acid-resistant film surface, 4 μm of a phenol resin is formed as a protective layer, 10 μm of high-density polyethylene is dry-laminated as an intermediate layer, and 70 μm of an ethylene-methyl methacrylate copolymer film is heat-laminated as an innermost layer to form a laminate. Obtained.
OPET12 / PED / ON15 / PUD / AL25 / 3C / FN4 / PUD / HD10 / TL / EAM70

As the outermost layer, a polyester urethane adhesive was used as the adhesive between stretched polyester and stretched nylon, acrylic resin was 4 μm as the protective layer, homopropylene was 15 μm as the intermediate layer on the protective layer surface, The inner layer was laminated in the same manner as in Example 30 except that the unsaturated carboxylic acid grafted random propylene was 50 μm.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC4 / PUD / PH15 / TL / PPA50

The same method as in Example 31 was used except that the protective layer was an acrylic resin of 3 μm, the homopropylene thickness of the intermediate layer was 6 μm, and the innermost layer was an unsaturated carboxylic acid grafted random propylene of 50 μm.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / AC3 / PUD / PH6 / TL / PPA50

As the outermost layer, stretched polyester and stretched nylon are dry-laminated using a polyetherurethane-based adhesive, and 25 μm aluminum formed with a trivalent chromium film as an acid-resistant film and the stretched nylon surface of the outermost layer are dry-laminated, Acrylic resin 4 μm is formed as a protective layer on the acid-resistant film surface, and stretched polyester 6 μm is dry-laminated as an intermediate layer on the protective layer surface. Random propylene of a co-extruded film of random propylene 40 μm and butene copolymer random propylene 20 μm The surface and the intermediate layer were dry laminated to obtain a laminate.
OPET12 / PED / ON15 / PUD / AL25 / 3C / AC4 / PUD / OPET6 / PUD / PR40 // BR20

As the outermost layer, the adhesive of the dry laminate of stretched polyester and stretched nylon was a polyester urethane adhesive, and the innermost layer was a co-extruded film of random propylene 10 μm, homopropylene 20 μm and butene copolymerized random propylene 20 μm, Lamination was performed in the same manner as in Example 33 except that the random propylene surface was a laminated surface.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / AC4 / PUD / OPET6 / PUD / PR10 // PH20 // BR20

Example 34 except that the protective layer was 5 μm of epoxy resin, the innermost layer was a coextruded film of 15 μm of low density polyethylene and 50 μm of ethylene-methyl methacrylate copolymer, and the low density polyethylene surface was the laminate side. It laminated | stacked by the same method.
OPET12 / PUD / ON15 / PUD / AL25 / 3C / EP5 / PUD / OPET6 / PUD / LD15 // EAM50

As the outermost layer, stretched polyester and stretched nylon are dry-laminated using a polyetherurethane-based adhesive, and 25 μm aluminum formed with a trivalent chromium film as an acid-resistant film and the stretched nylon surface of the outermost layer are dry-laminated, Acrylic resin 2 μm was formed as a protective layer on the acid-resistant film surface. On the surface of the protective layer, as a first intermediate layer, stretched polyester 6 μm as a low density polyethylene second intermediate layer and random propylene 50 μm as an innermost layer were sequentially dry laminated to form a laminate.
OPET12 / PED / ON15 / PUD / AL25 / 3C / AC2 / PUD / LD20 / PUD / OPET6 / PUD / PR50

As the outermost layer, stretched polyester and stretched nylon are dry-laminated, aluminum 25 μm on which a zinc phosphate film is formed as an acid-resistant film and the stretched nylon surface are dry-laminated, and polyester is used as a protective layer on the acid-resistant film surface. 3 μm of resin is formed, on the surface of the protective layer, as a first intermediate layer, 15 μm of random propylene is used as an unsaturated carboxylic acid grafted random propylene adhesive as a heat-adhesive resin, and as a second intermediate layer, polyester is applied to a stretched polyester film 6 μm A laminate was obtained by thermally laminating the anchor-coated surface coated with a urethane-based adhesive and thermally laminating with 50 μm of unsaturated carboxylic acid grafted random propylene as the innermost layer on the second intermediate layer.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / PET3 / TL = PAD / PR15 / ANC = PUD / OPET6 / PUD / PPA50

The polyester resin 3 μm was provided as a protective layer, the thickness of random propylene as the first intermediate layer was 10 μm, and the innermost layer was a co-extruded film of 30 μm homopropylene and 25 μm unsaturated carboxylic acid grafted random propylene. Lamination was performed in the same manner as in Example 37 except that the 30-μm homopropylene surface was used as a laminate surface and dry laminated with the second intermediate layer.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / PET3 / TL = PAD / PR10 / ANC = PUD / OPET6 / PUD / PH30 // PPA25

Example 38 except that the protective layer was 3 μm of acrylic resin, the innermost layer was a co-extruded film of 10 μm of random propylene, 20 μm of homopropylene and 20 μm of random propylene, and the 10 μm surface of random propylene was the laminated surface. It laminated | stacked by the method.
OPET12 / PUD / ON15 / PUD / AL25 / PZ / AC3 / TL = PAD / PR10 / ANC = PUD / OPET6 / PUD / PR10 // PH20 // BR20

As the outermost layer, 25 μm of aluminum provided with an acid resistant film made of a trivalent chromium film by dry lamination of 12 μm of stretched polyester film and 15 μm of stretched nylon is dry laminated on the stretched nylon surface, and a protective layer is formed on the acid resistant film surface. As an intermediate layer, a co-extruded film made of random propylene 5 μm, homopropylene 30 μm and random propylene 5 μm is formed, and the protective layer and the random propylene surface of the intermediate layer are unsaturated carboxylic acid. The laminate was obtained by heat laminating a graft random propylene adhesive as a heat-adhesive resin and thermally laminating 20 μm of unsaturated carboxylic acid graft random propylene as the innermost layer.
OPET12 / PED / ON15 / PUD / AL25 / 3C / AC4 / TL = PAD / PR5 // PH30 // PR5 / TL / PPA20

The acid-resistant coating was a zinc phosphate coating, the protective layer was a polyester resin of 5 μm, and the intermediate layer was formed as a co-extruded film of low-density polyethylene 5 μm, high-density polyethylene 30 μm, and low-density polyethylene 5 μm. The layers were laminated in the same manner as in Example 40 except that the layer and the intermediate layer were dry laminated, and the innermost layer was changed to 20 μm of ethylene-methyl methacrylate copolymer.
OPET12 / PED / ON15 / PUD / AL25 / PZ / PET5 / PUD / LD5 // HD30 // LD5 / TL / EAM20

<Pouch type specification evaluation>
The result evaluated in each item about the said Example was as follows, and the favorable performance was obtained in all.
1. Electrolyte suitability: No delamination 2. 2. Water vapor barrier property: 300 ppm or less Innermost layer seal strength −40 ° C. holding 9.8 N / 15 mm width or more 120 ° C. holding 9.8 N / 15 mm width or more Electrode tab short circuit prevention No delamination between outermost layer and barrier layer No pinhole in outermost layer No contact between electrode tab and barrier layer

<Example of cup type>
・ Cup: Rectangular tray container ・ Packaging form dimensions: 42 mm x 58 mm x depth 3.1 mm (seal width 5 mm) However, molded part dimensions 30 mm x 45 mm x depth 3.1 mm (side wall taper 5 degrees)
The dynamic friction coefficient μ of the innermost layer is described in [] at the end. <Structure of the laminated body as an example> In the description, the left side is the outer surface and the right side is the inner side (polymer battery as in the case of the pouch). Main body side).

As the outermost layer, the trivalent chromium film surface of 50 μm aluminum and the stretched nylon surface formed by dry laminating 16 μm of copolymer stretched polyester and 15 μm of stretched polyamide using a polyester urethane adhesive and forming a trivalent chromium film The laminate was dry-laminated and sequentially laminated with 16 μm of copolymer stretched polyester on the trivalent chromium film surface and 30 μm of unsaturated carboxylic acid grafted random propylene as the innermost layer.
COPET16 / PUD / ON15 / PUD / AL (# 1) 50 / 3C / PUD / COPET16 / PUD / PPA30 [0.29]
AL (# 1) contains 1.0% iron, 0.10% silicon, and 0.01% manganese as fine components.

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 50 μm of aluminum with a trivalent chromium film formed thereon, 10 μm of homopropylene as an intermediate layer on the surface of the trivalent chromium film of aluminum, and then unsaturated as the innermost layer Carboxylic acid grafted random propylene 30 μm was sequentially dry laminated to obtain a laminate.
COPET16 / PUD / AL (# 1) 50 / 3C / PUD / PH10 / PUD / PPA30 [0.25]

Dry laminate of 16 μm of copolymerized stretched polyester as the outermost layer and 50 μm of aluminum with a trivalent chromium film formed thereon, and sequentially dry 30 μm of unsaturated carboxylic acid grafted random propylene as the innermost layer on the surface of the trivalent chromium film of aluminum. Lamination was performed to obtain a laminate.
COPET16 / PUD / AL (# 1) 50 / 3C / PUD / PPA30 [0.28]

Lamination was performed in the same manner as in Example 44 except that the thickness of aluminum was 40 μm.
COPET16 / PUD / AL (# 1) 40 / 3C / PUD / PPA30 [0.2]

Lamination was performed in the same manner as in Example 44 except that the thickness of aluminum was 80 μm.
COPET16 / PUD / AL (# 1) 80 / 3C / PUD / PPA30 [0.2]

Dry laminate of 16 μm of copolymerized stretched polyester as the outermost layer and 40 μm of aluminum with a trivalent chromium film formed thereon, forms 2 μm of acrylic resin as a protective layer on the surface of the trivalent chromium film of aluminum. As an inner layer, 30 μm of random propylene was thermally laminated using an unsaturated carboxylic acid grafted polyethylene adhesive as a heat-adhesive resin to obtain a laminate. The aluminum AL (# 2) used contained 1.2% iron, 0.15% silicon, and 0.002% manganese as fine components.
COPET16 / PUD / AL (# 2) 40 / 3C / AC2 / TL = PEAD / PR30 [0.2]

The thickness of the protective layer of trivalent chromium film is 1 μm, and the aluminum AL (# 3) used contains 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components. The film was laminated in the same manner as in Example 47 except that
COPET16 / PUD / AL (# 3) 40 / 3C / AC2 / TL = PEAD / PR30 [0.2]

The aluminum AL (# 4) used was laminated in the same manner as in Example 48 except that it contained 1.5% iron, 0.15% silicon, and 0.5% manganese as the minor components.
COPET16 / PUD / AL (# 4) 40 / 3C / AC2 / TL = PEAD / PR30 [0.2]

The aluminum AL (# 5) used was laminated in the same manner as in Example 48 except that it contained 0.8% iron, 0.1% silicon, and 0.01% manganese as the minor components.
COPET16 / PUD / AL (# 5) 40 / 3C / AC2 / TL = PEAD / PR30 [0.2]

The aluminum AL (# 6) used was laminated in the same manner as in Example 48 except that it contained 0.5% iron, 0.2% silicon, and 1.1% manganese as the minor components.
COPET16 / PUD / AL (# 6) 40 / 3C / AC2 / TL = PEAD / PR30 [0.2]

The aluminum AL (# 7) used was laminated in the same manner as in Example 48, except that it contained 6.0% iron, 1.1% silicon, and 0.1% manganese as the minor components.
COPET16 / PUD / AL (# 7) 40 / 3C / AC2 / TL = PEAD / PR30 [0.13]

Lamination was performed in the same manner as in Example 48 except that the thickness of the aluminum used was 50 μm.
COPET16 / PUD / AL (# 3) 50 / 3C / AC2 / TL = PEAD / PR30 [0.2]

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 50 μm of aluminum with a trivalent chromium film formed as an acid resistant film, and dry laminate of 40 μm of random propylene as the innermost layer on the acid resistant film surface of aluminum. Got the body. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / PUD / PR40 [0.2]

Lamination was performed in the same manner as in Example 54 except that the acid-resistant coating was a zinc phosphate coating.
COPET16 / PUD / AL (# 3) 50 / PZ / PUD / PR40 [0.2]

Lamination was performed in the same manner as in Example 54 except that the acid-resistant film was a calcium phosphate film.
COPET16 / PUD / AL (# 3) 50 / PCa / PUD / PR40 [0.2]

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 50 μm of aluminum formed with a trivalent chromium film as an acid resistant film, and 5 μm of epoxy resin as a protective layer is formed on the surface of the acid resistant film of aluminum, and the protection A laminate was obtained by dry laminating a layer and 30 μm of random propylene as the innermost layer. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / EP5 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being 3 micrometers of phenol resins.
COPET16 / PUD / AL (# 3) 50 / 3C / FN3 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being 4 micrometers of melamine resin.
COPET16 / PUD / AL (# 3) 50 / 3C / MR4 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being 10 micrometers of polyester resins.
COPET16 / PUD / AL (# 3) 50 / 3C / PET10 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being 5 micrometers of acrylic resins.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being unsaturated carboxylic acid graft random polypropylene 4micrometer.
COPET16 / PUD / AL (# 3) 50 / 3C / PPA4 / PUD / PR30 [0.2]

It laminated by the same method as Example 57 except a protective layer being unsaturated carboxylic acid graft | grafting polyethylene 4 micrometers.
COPET16 / PUD / AL (# 3) 50 / 3C / PPEA4 / PUD / PR30 [0.2]

Copolymer-stretched polyester 16 μm as the outermost layer and aluminum 50 μm with a trivalent chromium film formed as an acid-resistant film are dry-laminated, and an acrylic resin 5 μm is formed as a protective layer on the acid-resistant film surface of the aluminum. A laminate was obtained by dry-laminating 16 μm of copolymerized stretched polyester as an intermediate layer on the layer surface and dry-laminating 40 μm of unsaturated carboxylic acid grafted random polypropylene as the innermost layer on the intermediate layer surface. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / COPET16 / PUD / PPA40 [0.2]

The innermost layer was laminated in the same manner as in Example 64 except that the unsaturated carboxylic acid grafted polyethylene was 30 μm.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / COPET16 / PUD / PPEA30 [0.25]

The innermost layer was laminated in the same manner as in Example 64 except that the ethylene-methyl methacrylate copolymer was 50 μm.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / COPET16 / PUD / EAM50 [0.3]

Copolymer-stretched polyester 16 μm as the outermost layer and aluminum 50 μm with a trivalent chromium film formed as an acid-resistant film are dry-laminated, and an acrylic resin 2 μm is formed as a protective layer on the acid-resistant film surface of the aluminum. Low-density polyethylene 10μm is laminated as a first intermediate layer via a polyester polyurethane adhesive on the layer surface to form an intermediate laminate, and polyester urethane-based adhesive is bonded to a copolymerized stretched polyester 16μm as a second intermediate layer. The anchor coat surface coated with an agent and the low-density polyethylene surface as the first intermediate layer are heat-laminated, and 50 μm of random propylene as the innermost layer is dry-laminated on the second intermediate layer to obtain a laminate. It was. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC2 / PUD / LD10 / ANC = PUD / COPET16 / PUD / PR50 [0.4]

The layers were laminated in the same manner as in Example 64 except that the thickness of the protective layer was 3 μm and the innermost layer was 30 μm of homopropylene.
COPET16 / PUD / AL (# 3) 50 / 3C / AC3 / PUD / COPET16 / PUD / PH30 [0.13]

The innermost layer was laminated by the same method as in Example 68 except that the random propylene was 40 μm.
COPET16 / PUD / AL (# 3) 50 / 3C / AC3 / PUD / COPET16 / PUD / PR40 [0.1]

The innermost layer was laminated in the same manner as in Example 68 except that butene copolymerized random propylene was 90 μm.
COPET16 / PUD / AL (# 3) 50 / 3C / AC3 / PUD / COPET16 / PUD / BR90 [0.5]

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 50 μm of aluminum having a trivalent chromium film formed thereon, forming 2 μm of acrylic resin as a protective layer on the surface of the trivalent chromium film of aluminum, As the innermost layer, 30 μm of random propylene was thermally laminated using an unsaturated carboxylic acid grafted random polypropylene adhesive as a heat-adhesive resin to obtain a laminate. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC2 / TL = PAD / PR30 [0.2]

The same method as in Example 71, except that the protective layer was an epoxy resin of 5 μm, the innermost layer was an ethylene-methyl methacrylate copolymer of 50 μm, and the thermal adhesive resin was an unsaturated carboxylic acid grafted polyethylene adhesive. Were laminated.
COPET16 / PUD / AL (# 3) 50 / 3C / EP5 / TL = PEAD / EAM50 [0.2]

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 40 μm of aluminum formed with a trivalent chromium film, 4 μm of phenol resin as a protective layer is formed on the surface of the trivalent chromium film of aluminum, As an intermediate layer, 10 μm of high-density polyethylene was heat-laminated using an unsaturated carboxylic acid grafted random polypropylene adhesive as a heat-adhesive resin, and 70 μm of ethylene-methyl methacrylate copolymer was heat-laminated as the innermost layer to obtain a laminate. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 40 / 3C / FN4 / TL = PAD / HD10 / TL = PEAD / EAM70 [0.1]

The protective layer was made of acrylic resin 4 μm, the intermediate layer was made of homopropylene 15 μm, the thermal adhesive resin used for thermal lamination of the protective layer and the intermediate layer was an unsaturated carboxylic acid grafted polyethylene adhesive, The inner layer was laminated in the same manner as in Example 73 except that the unsaturated carboxylic acid grafted random polypropylene was 30 μm.
COPET16 / PUD / AL (# 3) 40 / 3C / AC4 / TL = PEAD / PH15 / TL = PEAD / PPA30 [0.2]

The protective layer was made of unsaturated carboxylic acid grafted random polypropylene 5 μm, the innermost layer was made of unsaturated carboxylic acid grafted random polypropylene 30 μm, and the unsaturated carboxylic acid grafted polyethylene was used for thermal lamination of the protective layer and the innermost layer. Except for the above, lamination was performed in the same manner as in Example 71.
COPET16 / PUD / AL (# 3) 50 / 3C / PPA5 / TL = PAD / PPA30 [0.5]

Lamination was performed in the same manner as in Example 71 except that the acid-resistant coating was a zinc phosphate coating, the protective layer was 2 μm of phenol resin, and the innermost layer was 70 μm of butene copolymerized random propylene.
COPET16 / PUD / AL (# 3) 50 / PZ / FN2 / TL = PAD / BR70 [0.6]

Copolymer-stretched polyester 16 μm as an outermost layer and aluminum 50 μm with a zinc phosphate film formed as an acid-resistant film are dry-laminated, and a polyester resin 3 μm is formed as a protective layer on the acid-resistant film surface of the aluminum. 10 μm of random propylene as a first intermediate layer is laminated on the layer surface as an adhesive resin with an unsaturated carboxylic acid grafted random polypropylene adhesive, and a polyester urethane adhesive is anchored to a copolymerized stretched polyester of 16 μm as a second intermediate layer. The coated anchor coat surface and the random propylene surface as the first intermediate layer are heat laminated at the same time, and the second intermediate layer is dry laminated with 50 μm of unsaturated carboxylic acid grafted random polypropylene as the innermost layer. Got. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / PZ / PET3 / TL = PAD / PR10 / ANC = PUD / COPET16 / PUD / PPA50 [0.2]

The acid-resistant film was a zinc phosphate film, the protective layer was a blend resin of epoxy resin and melamine resin (blend ratio 5: 1) 6 μm, and the innermost layer was an unsaturated carboxylic acid grafted random polypropylene 50 μm Except for the above, lamination was performed in the same manner as in Example 71.
COPET16 / PUD / AL (# 3) 50 / PZ / EP + MR / TL = PAD / PPA50 [0.15]

Examples except that the acid-resistant coating is a zinc phosphate coating, the protective layer is 3 μm of acrylic resin, the intermediate layer is 10 μm of homopropylene, and the innermost layer is 50 μm of unsaturated carboxylic acid grafted random polypropylene. It laminated by the same method as 74.
COPET16 / PUD / AL (# 3) 40 / PZ / AC3 / TL = PAD / PH10 / TL = PAD / PPA50 [0.3]

Dry laminate of 16 μm of copolymer stretched polyester as the outermost layer and 50 μm of aluminum formed with 2 μm of trivalent chromium film as an acid resistant film, and 5 μm of acrylic resin as a protective layer on the acid resistant film surface of aluminum, Copolymer-stretched polyester 16 μm is dry-laminated as an intermediate layer on the protective layer surface, and random propylene 5 μm, homopropylene 30 μm, and random propylene 10 μm are coextruded to form an innermost layer, and the intermediate layer and innermost random propylene 5 μm. The laminate was obtained by dry laminating the surface. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / COPET16 / PUD / PR5 // PH30 // PR10 [0.2]

The same method as in Example 80 except that the thickness of the acrylic resin of the protective layer was 4 μm, the innermost layer was a co-extruded film of random propylene 40 μm and butene copolymerized random propylene 20 μm, and random propylene was used as the laminate surface. Were laminated.
COPET16 / PUD / AL (# 3) 50 / 3C / AC4 / PUD / COPET16 / PUD / PR40 // BR20 [0.18]

The innermost layer was laminated in the same manner as in Example 80, except that 10 μm of random propylene, 20 μm of homopropylene, and 20 μm of butene copolymerized random propylene were used, and the random propylene surface was a laminated surface.
COPET16 / PUD / AL (# 3) 50 / 3C / AC5 / PUD / COPET16 / PUD / PR10 // PH20 // BR20 [0.5]

Example 80 except that the protective layer was an epoxy resin of 5 μm, the innermost layer was a coextruded film of 15 μm of low density polyethylene and 50 μm of ethylene-methyl methacrylate copolymer, and the low density polyethylene surface was a laminated surface. It laminated | stacked by the same method.
COPET16 / PUD / AL (# 3) 50 / 3C / EP5 / PUD / COPET16 / PUD / LD15 // EAM50 [0.3]

The outermost layer of 16 μm of stretched polyester and 50 μm of aluminum with a trivalent chromium film formed as an acid-resistant film are dry laminated, and an acrylic resin of 4 μm is formed as a protective layer on the acid-resistant film surface of the aluminum. As a result, 40 μm of homopropylene and 10 μm of random propylene were coextruded to form a film, and the protective layer surface and the homopropylene surface of the innermost layer were dry laminated to obtain a laminate. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC4 / PUD / PH40 // PR10 [0.22]

As the innermost layer, a co-extruded film of 30 μm of homopropylene and 25 μm of unsaturated carboxylic acid grafted random polypropylene was laminated by the same method as in Example 84 except that the homopropylene surface was a laminated surface.
COPET16 / PUD / AL (# 3) 50 / 3C / AC4 / PUD / PH30 // PPA25 [0.3]

The innermost layer is a co-extruded film of 30 μm homopropylene and 10 μm random propylene, and the protective layer surface and the homopropylene surface of the innermost layer are heat laminated using an unsaturated carboxylic acid grafted random polypropylene adhesive as a heat adhesive resin. Except for the above, lamination was performed in the same manner as in Example 84.
COPET16 / PUD / AL (# 3) 50 / 3C / AC4 / TL = PAD / PH30 // PR10 [0.2]

The protective layer was an unsaturated carboxylic acid grafted random polypropylene 6 μm, the innermost layer was a co-extruded film of 5 μm random propylene, 30 μm homopropylene and 10 μm random propylene, and the random propylene 5 μm surface of the protective layer and the innermost layer was laminated. Was laminated in the same manner as in Example 86, except that it was heat laminated.
COPET16 / PUD / AL (# 3) 50 / 3C / PPA6 / TL = PAD / PR5 // PH30 // PR10 [0.2]

The protective layer is an unsaturated carboxylic acid grafted polyethylene 3 μm, the innermost layer is a coextruded film of 15 μm low density polyethylene and 50 μm ethylene-methyl methacrylate copolymer, and the protective layer and the innermost low density polyethylene are laminated. Was laminated by the same method as in Example 84, except that it was heat laminated.
COPET16 / PUD / AL (# 3) 50 / 3C / PPEA3 / TL / LD15 // EAM50 [0.5]

Copolymer-stretched polyester 16 μm as an outermost layer and aluminum 50 μm with a zinc phosphate film formed as an acid-resistant film are dry-laminated, and a polyester resin 3 μm is formed as a protective layer on the acid-resistant film surface of the aluminum. 10 μm of random propylene as a first intermediate layer is laminated on the layer surface as an adhesive resin with an unsaturated carboxylic acid grafted random polypropylene adhesive, and a polyester urethane adhesive is anchored to a copolymerized stretched polyester of 16 μm as a second intermediate layer. Coated and heat-laminated simultaneously with the anchor coat surface, as the innermost layer, a co-extruded film of 30 μm homopropylene and 25 μm unsaturated carboxylic acid grafted random propylene, and the second intermediate layer with a polyester urethane adhesive as a dryer To obtain a laminate with sulfonates. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / PZ / PET3 / TL = PAD / PR10
/ANC=PUD/COPET16/PUD/PH30//PPA25[0.24]

Except that the protective layer was 3 μm of acrylic resin, the innermost layer was a co-extruded film of 10 μm of random propylene, 20 μm of homopropylene, and 20 μm of butene copolymerized random propylene, and the random propylene surface of the innermost layer was a laminated surface Lamination was performed in the same manner as in Example 89.
COPET16 / PUD / AL (# 3) 50 / PZ / AC3 / TL = PAD / PR10
/ANC=PUD/OPET6/PUD/PR10//PH20//BR20[0.4]

Dry laminate of 16 μm of copolymerized stretched polyester as the outermost layer and 50 μm of aluminum with a trivalent chromium film formed as an acid resistant film, and 4 μm of acrylic resin as a protective layer is formed on the surface of the acid resistant film of aluminum. Is a co-extruded film of 5 μm of random propylene, 30 μm of homopropylene and 5 μm of random propylene, and the protective layer and the intermediate layer are thermally laminated using an unsaturated carboxylic acid grafted random polypropylene adhesive as a heat adhesive resin, and the innermost layer is formed. The intermediate layer and the heat laminate laminate were obtained as unsaturated carboxylic acid grafted random polypropylene 20 μm. The aluminum AL (# 3) used contained 1.5% iron, 0.09% silicon, and 0.5% manganese as fine components.
COPET16 / PUD / AL (# 3) 50 / 3C / AC4 / TL = PAD / PR5 // PH30 // PR5 / TL / PPA20 [0.19]

The acid-resistant coating was a zinc phosphate coating, the intermediate layer was a co-extruded film of 5 μm low density polyethylene, 30 μm high density polyethylene and 5 μm low density polyethylene, dry-laminated with the protective layer, and the innermost layer was ethylene-methacrylic A 20-μm acid methyl copolymer was laminated in the same manner as in Example 91 except that the intermediate layer and the innermost layer were thermally laminated.
COPET16 / PUD / AL (# 3) 50 / PZ / AC4 / PUD / LD5 // HD30 // LD5 / TL / EAM20 [0.18]

<Cup type specification evaluation>
The result evaluated in each item about the said Example was as follows, and the favorable performance was obtained in all.
1. Electrolyte suitability: No delamination 2. 2. Water vapor barrier property: 300 ppm or less Innermost layer seal strength −40 ° C. holding 9.8 N / 15 mm width or more 120 ° C. holding 9.8 N / 15 mm width or more 4. Electrode tab short-circuit prevention property No delamination between outermost layer and barrier layer No pinhole in outermost layer No contact between electrode tab and barrier layer Formability: No pinholes

  FIG. 3 shows another embodiment as a specific layer structure. In this laminate, the base material layer and the barrier layer are dry-laminated, and the barrier layer is subjected to surface treatment TR to provide a protective layer 15 as a first base material, and the intermediate layer is dry-laminated (DL-2). Further, a heat laminate film TL is formed by thermally laminating a second base material obtained by dry lamination (DL-3) of the innermost layer 14 with a heat adhesive film interposed therebetween.

  Form of polymer battery (pouch-type exterior body) The form of the exterior body when the laminate of the present invention is used as a packaging material constituting the exterior body of the polymer battery includes a pouch type or an embossed type (cup type). . In addition to the pillow type described above, the pouch type includes a three-side seal type shown in FIG. 5A and a four-side seal type shown in FIG. 5B. In any form, the seal end part is a hermetic seal including a part of the tab (electrode), and a part of the tab is exposed to the outside of the exterior body. Further, the tab may be exposed to the outside from an arbitrary position of the seal portion of the exterior body, as shown in FIG. 5C, FIG. 5D, or FIG.

  In the packaging material for a polymer battery of the present invention, the shape of the outer package 4 may be an embossed type as shown in FIG. In this case, the bottom material 6 includes an embossed portion 8 that serves as a storage portion for the battery body, and a flange portion 9 that seals and seals the lid material 7. As shown in FIG. 2 (a), the bottom packaging material 6 is basically a four-layer laminate, and a polyester resin used for the outermost layer 11 and / or the intermediate layer 13 is made of a polyethylene terephthalate copolymer or It is preferable to use a polybutylene terephthalate copolymer and reduce the draw ratio in film formation. By using the copolymer, the shape of the bottom material becomes sharp, and when the container is used, the opening width (T) and depth (D) shown in FIG. 1/50 or more and the side taper θ can be set to 130 ° or less, which facilitates molding. Further, when aluminum is used for the barrier layer, it is desirable that the thickness is 30 μm or more as a thickness that does not cause a pinhole due to molding. When embossing only one side, the lid member 7 does not need to be a copolymer because it does not emboss. When embossing on both sides, a laminate of the bottom material may be used on both sides. By making the exterior body of the polymer battery an embossed type, the battery body can be stored better. Note that the tabs in the embossed type exterior body may be exposed to the outside from any position of the seal portion of the exterior body as shown in FIG. 6C or 6D, as in the pouch type. Good.

DESCRIPTION OF SYMBOLS 1 Polymer battery 2 Polymer battery main body 3 Electrode 4 Exterior body 5 Heat seal part 5f Back seal part 6 Bottom material 7 Lid material 8 Embossed part 9 Flange part 10 Laminated body (packaging material)
DESCRIPTION OF SYMBOLS 11 Outermost layer 12 Barrier layer 13 Intermediate layer 14 Innermost layer 15 Protective layer 16 Thermal-adhesive tab material TR Surface treatment layer DL Dry laminate layer TL Thermal laminate layer

Claims (14)

A laminate composed of an outermost layer / barrier layer / innermost layer, or an outermost layer / barrier layer / intermediate layer / innermost layer, the outermost layer having heat resistance, pinhole resistance, moldability, and insulation. The barrier layer is composed of a barrier substrate having water vapor barrier properties, moldability and acid resistance, and the intermediate layer is composed of an intermediate substrate having insulation properties and moldability. A polymer battery packaging material, wherein the innermost layer is composed of a heat-sealable substrate having heat-fusibility, heat resistance, cold resistance, electrolyte suitability, and insulation. 2. The packaging material for a polymer battery according to claim 1, wherein an adhesive layer is interposed between the layers of the laminate. 3. The polymer battery packaging material according to claim 1 or 2, wherein the substrate constituting the outermost layer is composed of either a stretched polyester resin or a stretched polyamide resin. The said outermost layer is comprised with the some base material, The packaging material for polymer batteries of Claims 1-3 characterized by the above-mentioned. The polymer battery packaging material according to claim 1, wherein the barrier layer is made of an aluminum foil having a thickness of at least 15 μm. 6. The polymer battery packaging material according to claim 5, wherein an acid-resistant film made of phosphate, chromate, chromium phosphate and zinc phosphate is formed on the aluminum foil constituting the barrier layer. 6. The polymer battery packaging material according to claim 5, wherein a protective layer is formed on the aluminum surface constituting the barrier layer. 8. The protective layer according to claim 7, wherein the protective layer contains at least one of an epoxy resin, a phenol resin, a melamine resin, an unsaturated carboxylic acid graft polyolefin resin, an acrylic resin, and a modified product thereof. The packaging material for polymer batteries as described. The intermediate base material forming the intermediate layer comprises at least one resin formed from a polyester resin, a polyolefin resin, or a modified product or a mixture thereof. Item 9. A polymer battery packaging material according to Item 1-8. The polymer battery packaging material according to claim 1, wherein the intermediate layer has a thickness of 5 μm or more. The heat-sealable base material constituting the innermost layer is composed of an acid-modified polyolefin resin, an unsaturated carboxylic acid grafted polyolefin resin, a polypropylene resin, a metal ion crosslinked polyethylene, ethylene and an acrylic acid derivative, and ethylene and a methacrylic acid derivative. The polymer battery packaging material according to claim 1, wherein the polymer battery packaging material is made of any one of a copolymer-based resin. The said innermost layer is comprised from the several base material, The packaging material for polymer batteries of Claims 1-11 characterized by the above-mentioned. The polymer battery according to claim 1, wherein the adhesive layer is composed of any one of a polyester urethane resin, a polyether urethane resin, an isocyanate resin, and an unsaturated carboxylic acid graft polyolefin resin. Packaging materials. The adhesive layer is composed of a main agent and a curing agent, and the main agent is an acid component containing at least two or more of sebacic acid, isophthalic acid, terephthalic acid, octatannic acid, nonannic acid, undecanoic acid, palmitic acid, ethylene glycol, 14. A blend of a polyester resin comprising an alcohol component containing at least one kind of hexanediol and diethylene glycol and a bisphenol A type epoxy resin, wherein the curing agent has a composition comprising a polyisocyanate component. Polymer battery packaging material.

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