JP2006069039A - Laminate and package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which prevents the lowering of laminate strength even when contents comprising a substance of high permeability are packed and a package. <P>SOLUTION: The laminate is constituted of at least a thermoplastic resin layer (1)/an adhesive layer/an aluminum foil layer/a primer layer/and a thermoplastic resin layer (2) arranged from the outside. The primer layer is formed from a specified silane compound in which at least one of substituents R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>, and R<SB>4</SB>is a reactive functional group (A), and the other substituents are selected from hydrogen, halogens, alkyl groups, alkoxyl groups, a(meth)acryloxyl group, an allyl group, a vinyl group, and their derivatives. The thermoplastic resin layer (2) is formed from the acid-modified product, the epoxy-modified product, the silane-modified product, or the mixture of at least two of the products of a polyolefin resin including polyethylene, an ethylene-α-olefin copolymer, polypropylene, and a propylene-α-olefin copolymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

 The present invention is excellent in adhesion to aluminum foil, and even in cases where the packaging material deteriorates due to the contents in the conventional packaging material configuration, such as a lithium battery packaging material, a bathing agent, and a foaming agent. The present invention relates to a laminate and a package that are excellent in content-resistant contents that can be developed.

  2. Description of the Related Art In recent years, lithium batteries that can be made ultra-thin and miniaturized have been actively developed as batteries used in mobile terminal devices such as personal computers and mobile phones, video cameras, and satellites. Unlike the metal can conventionally used as a battery packaging material, this lithium battery has a multilayer film (for example, outermost layer / barrier layer) because it is lightweight and can freely select the shape of the battery. / A structure like a sealant layer) has been used in the form of a bag.

  Lithium batteries include a positive electrode material and a negative electrode material as battery contents, an electrolyte solution in which a lithium salt is dissolved in an aprotic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, or an electrolyte solution thereof. An electrolyte layer comprising an impregnated polymer gel is included. When such a strongly permeable solvent passes through the sealant layer, there is a problem that the laminate strength between the aluminum foil layer and the sealant layer is lowered, and the electrolyte solution eventually leaks. It is essential to increase the adhesion strength between layers and to have content resistance.

Moreover, as lithium salt which is an electrolyte of a battery, substances such as LiPF ₆ and LiBF ₄ are used, and these salts generate hydrofluoric acid by hydrolysis reaction with moisture, which means that the metal surface Corrosion of the multi-layer film, resulting in a decrease in laminate strength between layers. By using aluminum foil for the barrier layer, moisture intrusion from the surface of the packaging material is substantially blocked. However, the outer packaging material for lithium batteries has a structure in which multilayer films are bonded together by heat sealing, and it cannot completely block the penetration of moisture from the end face of the seal part of the sealant layer, which is the innermost layer. It is necessary to further strengthen the laminate strength between the foil layer and the sealant layer so that the laminate strength is not lowered by the generated hydrofluoric acid.

  In addition, lithium batteries are often used for portable mobile phones, and the usage environment may be as high as 60-70 ° C., such as in a midsummer car. It is also important to have heat resistance that can maintain the heat resistance.

  The most common method for producing a multilayer film is dry lamination. However, the adhesive for the laminate uses polyester, polyester polyurethane, or polyether polyurethane, etc., and these have the disadvantage that they have low resistance to strongly permeable contents and cause a decrease in laminate strength. .

Patent documents are described below.
JP 2001-1727779 A JP2003-123707A.

Thus, in order to impart resistance to strongly permeable contents, studies have been made particularly on the surface treatment of aluminum foil. Among them, as described in Patent Document 1, chromate treatment such as chromate chromate and phosphate chromate is mentioned as an effective means for surface treatment of aluminum foil. However, the treatment liquid used for chromate treatment has an adverse effect on the environment and the human body, and at present, its alternative technology is screamed in the form of dechromation. On the other hand, the method described in Patent Document 2 has already been applied for a packaging material for a lithium battery using a hydrothermal modification treatment (boehmite treatment) as a treatment method for an aluminum foil and laminating a thermoplastic resin layer. . However, this method has a low processing capacity, and has problems of productivity and processing cost.

  The present invention has been made in order to solve the above-mentioned problems, and even when a content made of a highly permeable substance is packaged, the adhesion strength is not reduced without lowering the laminate strength between the aluminum foil layer and the thermoplastic resin layer. It aims at providing the outstanding laminated body and package.

In order to solve the above problems, the present invention
The invention according to claim 1 is at least a laminate composed of a thermoplastic resin layer (1) / adhesive layer / aluminum foil layer / primer layer / thermoplastic resin layer (2) from the outside,
In the chemical formula represented by the following general formula, at least one of R ₁ , R ₂ , R ₃ , R ₄ is a reactive functional group (A), and the other substituents are hydrogen, halogen, alkyl. A layer formed from a compound comprising a substituent selected from a group, an alkoxyl group, a (meth) acryloxyl group, an allyl group, a vinyl group, or a derivative thereof, and the thermoplastic resin layer (2) is made of polyethylene , A layer formed from an acid modified product, an epoxy modified product, a silane modified product, or a mixture of two or more of these, such as an ethylene-α-olefin copolymer, polypropylene, and a propylene-α-olefin copolymer. It is a laminated body characterized by comprising.

  The invention according to claim 2 is characterized in that between the primer layer and the thermoplastic resin layer (2), a polymer complex comprising a polyethyleneimine and a polysaccharide having a carboxyl group, or a polyethyleneimine and a monomer having an ethylene and a carboxyl group. The laminate according to claim 1, further comprising an anchor coat layer (1) comprising a layer formed from any one of the polymer complexes comprising the above copolymer or a mixture thereof.

  The invention according to claim 3 is that an anchor coat layer (2) comprising a layer formed from a crosslinked polymer ion containing a zirconium compound is provided between the primer layer and the anchor coat layer (1). It is a laminated body of Claim 2 characterized by the above-mentioned.

  In the invention according to claim 4, the reactive functional group (A) in the primer layer is reactive with at least one of the anchor coat layer (1), the anchor coat layer (2), and the thermoplastic resin layer (2). It is a laminated body of Claim 2 or 3 characterized by the above-mentioned.

  The invention according to claim 5 is the laminate according to any one of claims 2 to 4, wherein the anchor coat layer (1) is reactive with the thermoplastic resin layer (2). is there.

  The invention according to claim 6 is the laminate according to any one of claims 1 to 5, wherein the reactive functional group (A) is an epoxy group or an amino group.

  The invention according to claim 7 is characterized in that the anchor coat layer (2) is a polymer ion cross-linked body mainly composed of polyacrylic acid and ion-crosslinked with a zirconium compound. It is a laminated body of any one item.

  Invention of Claim 8 consists of a laminated body of any one of Claims 1-7, It is a package body characterized by the above-mentioned.

  The invention according to claim 9 is a package characterized by using the laminate according to any one of claims 1 to 7 as an exterior material for a lithium battery.

  The laminate of the present invention is provided with an “polyethyleneimine polymer” on the anchor coat layer (1) in that an aluminum foil is provided with an epoxy-based or amino-based silane coupling agent as a primer layer and the adhesion is further improved. “Complex”, “Polymerized polymer crosslinked with polyacrylic acid as a main component and ion-crosslinked with a zirconium compound” is used as anchor coat (2), and further, reactivity such as maleic anhydride as thermoplastic resin (2) By using a polyolefin resin modified with a functional group, it is possible to obtain a laminate having excellent electrolyte solution resistance.

  Moreover, since the combined effect of the functional group contained in each layer of a primer layer, an anchor coat layer (1), an anchor coat layer (2), and a thermoplastic resin (2) is produced, a laminate having excellent electrolyte resistance is obtained. Can do.

  From the above, the laminate of the present invention can impart the electrolyte resistance required as a packaging material for lithium batteries, and is safer for the environment and the human body than conventional chromate treatment. Furthermore, since the treatment process is simple as compared with the hydrothermal transformation treatment, it can be applied not only to the outer packaging material for a lithium battery but also to various packaging bodies.

  An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a laminate of the present invention. As shown in FIG. 1, as a laminate of the present invention, a thermoplastic resin layer (1) a, an aluminum foil layer b, a primer layer c, an anchor coat layer (1) d, an anchor coat (2) e, a thermoplastic resin It is composed of layer (2) f. Among these, the essential layers are the thermoplastic resin layer (1) a, the aluminum foil layer b, the primer layer c, and the thermoplastic resin layer (2) f, and the aluminum foil layer b and the thermoplastic resin layer (2). In order to improve adhesiveness with f, an anchor coat layer (1) d and an anchor coat layer (2) e are provided as necessary.

  The thermoplastic resin layer (1) a in the present invention corresponds to the outermost layer in the laminate or the package. The material used here is preferably a film made of polypropylene, a film formed from a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a film formed from a polyamide resin such as aliphatic polyamide or aromatic polyamide. Although it is used, a film made of a polyamide resin is preferable in consideration of the moldability of the lithium battery packaging material described later, and a film having a thickness of 6 to 40 μm, more preferably 15 to 25 μm is used.

As the aluminum foil b in the present invention, one having a thickness of 5 to 200 μm, preferably 7 to 100 μm, can be used in consideration of barrier properties, pinhole resistance and workability. In addition, a general soft aluminum foil can be used as the material. However, particularly in the case of a packaging material for lithium batteries, the iron content is 0. 0 for the purpose of imparting further pinhole resistance and extensibility during molding. An aluminum foil in the range of 1 to 9.0 wt%, preferably 0.5 to 2.0 wt% may be used. If the iron content is less than 0.1 wt%, sufficient pinhole resistance and spreadability cannot be imparted, and if it exceeds 9.0 wt%, the flexibility is impaired. Furthermore, in order to avoid the influence of contaminants such as oil used at the time of rolling aluminum foil as much as possible, the aluminum foil primer layer side is subjected to primer treatment on the aluminum foil immediately after annealing, or even if the contaminated aluminum foil is a strong acid or It is preferable to apply a primer layer after washing the surface contamination by degreasing the surface with strong alkalinity. Depending on the device specifications, corona discharge treatment is also effective as a method for cleaning surface contamination.

In the primer layer c provided on the aluminum foil b with less surface contamination described above, at least one of R ₁ , R ₂ , R ₃ and R _{4 in} the compound represented by the following general formula is a reactive functional group (A). Other substituents consist of substituents selected from hydrogen, halogen compounds, alkyl groups, alkoxyl groups, (meth) acryloxyl groups, allyl groups, vinyl groups, or derivatives thereof, in terms of handling and control of reactivity. The alkoxy group is the most versatile. The reactive functional group is preferably an epoxy group or an amino group in consideration of the reactivity with the anchor coat layer and the thermoplastic resin (2) described later.

  At this time, the compound represented by the following general formula interacts with the condensation reaction between silanol groups formed by hydrolysis of alkoxyl groups and the outermost hydroxyl group present on the aluminum foil formed by adsorbed water. By forming the silica layer, it is possible to form a silica layer having a reactive functional group on the surface of the aluminum foil b by a sol-gel reaction. At this time, the compound represented by the following general formula may be used alone, but if necessary, a silane compound having no reactive functional group such as tetramethoxysilane or tetraethoxysilane, or silica Other inorganic compounds such as alkoxides such as aluminum and titanium may also be used, and a silica / alumina mixed compound may also be used from the viewpoint of controlling the hydrolysis rate and condensation reaction rate. The compound represented by the following general formula is usually a simple substance such as water or various alcohols or a solution adjusted to a solid content of 0.01 to 10.00 wt% in a mixed solvent, and acetic acid as necessary. The solution is adjusted by adjusting the pH in the range of 2 to 13, more preferably in the range of pH 3 to 9, with hydrochloric acid, ammonia, sodium hydroxide, or the like. The aqueous solution thus obtained is applied by various coating methods such as gravure coating, reverse coating, spin coating, bar coating, etc., with a coating film thickness of preferably 5 μm or less, more preferably 1 μm or less when dried. If necessary, a thermosetting step of several minutes to several hours may be performed at a temperature of 100 ° C. or higher. However, in the laminated body of the present invention, for example, when a layer made of a compound represented by the following general formula is formed with a coating thickness of 1 μm or less in gravure coating, the temperature range of the lowest level at which the solvent can be removed However, it has been confirmed that the adhesion between the aluminum foil and the compound represented by the following general formula is good.

The anchor coat layer (1) d and anchor coat layer (2) e shown below in the present invention are provided as necessary in order to improve the adhesion between the aluminum foil and the thermoplastic resin (2). The anchor coat layer (1) is preferably provided. There are two types of anchor coat (1) layers. One is a polymer chelate complex formed by blending a polysaccharide having a polyethyleneimine as a main component and a carboxyl group. Examples of the polysaccharide at this time include starch, cellulose, chitin, pectin, and vegetable gum (for example, gum arabic), but are not limited thereto. Those obtained by derivatizing these polysaccharides with carboxyl groups are used. The other is a chelate complex of a copolymer of ethyleneimine as a main component and ethylene and a monomer having a carboxyl group. Typical examples of the monomer having a carboxyl group include acrylic acid such as α, β-unsaturated carboxylic acid and methacrylic acid, and an ionomer obtained by copolymerizing these with ethylene or the like to form a chelate complex. Furthermore, fumaric acid, maleic acid, and the like can also be used by copolymerizing with ethylene, α-olefin, and the like. These anchor coat layers (1) are based on polyethyleneimine and are formed with a chelate complex with a compound having a carboxyl group. Compared with polyethyleneimine alone, it has moisture resistance, heat resistance, and content resistance characteristics. Excellent. Furthermore, the reaction of the epoxy group or amino group in the primer layer with the terminal amine and carboxyl group in the polyethyleneimine of the anchor coat layer (1) is expected, which is advantageous in terms of adhesion. These coating methods can also use the various coating methods described above, and the coating thickness is 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less. When the coating thickness is thicker than 5 μm, the anchor coat layer (1) may be deteriorated to the contents.

The anchor coat layer (2) e in the present invention contains at least “water-soluble zirconium compound”, “water-soluble or water-dispersible acrylic resin, polyester resin, or polyurethane resin or a mixture thereof” and is dried. 0.8~35mg / m ² of a water-soluble zirconium compound as zirconium as weight, 1~60mg / m ² containing water-soluble or water-dispersible acrylic resins, polyester resins, or polyurethane resins or mixtures thereof as a solid A film is formed. As a more preferable component, a polymer ion cross-linked product containing polyacrylic acid as a main component and ion-crosslinked with a zirconium compound can be mentioned. The purpose of providing the anchor coat layer (2) is to improve the adhesion between the primer layer and the anchor coat layer (1), and the reactive functional group (A) in the primer layer and the anchor coat layer (2) Adhesion can be improved by reactivity and reactivity between the anchor coat layer (1) and the anchor coat layer (2) and intermolecular interaction via ions.

  The thermoplastic resin layer (2) f in the present invention is a polyolefin resin such as polyethylene, ethylene-α-olefin copolymer, polypropylene, propylene-α-olefin copolymer, ethylene-vinyl acetate copolymer or ethylene-α. , Β-unsaturated carboxylic acid copolymers and the like are formed from an acid-modified product of an ethylene copolymer, an epoxy-modified product, a silane-modified product, or a mixture of two or more of the resins described above. The definition of the acid-modified product is a copolymer polymer such as an ethylene-α, β-unsaturated carboxylic acid copolymer or its ionic cross-linked product, or an acid-modified polyolefin in which maleic anhydride or acrylic acid is introduced by a graft reaction. Is also included. In addition, epoxy modified products and silane modified products can be obtained by introducing compounds such as glycidyl (meth) acrylate and γ- (meth) acryloxypropyltrimethoxysilane into polyolefins and ethylene copolymers by graft reaction. The obtained one is also included. These resins may be blended with an unmodified polyolefin resin and an ethylene copolymer as necessary. For lamination of these resins, an extrusion lamination method is preferably used.

  The laminated body of the present invention obtained above is more preferably subjected to heat treatment such as thermal lamination for the purpose of further improving the adhesion between the respective layers, if necessary. As the heat laminating method, a known laminating technique can be used. For example, a method in which a heat and pressure treatment is performed by passing between a heating roll and a press roll after the above-described laminated body is produced is used. However, since these heat treatment methods are intended to improve the adhesion of each correlation by applying heat, there are no restrictions on other methods. By this heat treatment, the adhesion between the aluminum foil and the thermoplastic resin layer is further improved, and the resistance to a strongly permeable content such as an electrolyte of a lithium battery is remarkably improved.

The laminate of the present invention can be developed not only for a lithium battery exterior material but also for various types of packaging.

  Although the specific Example of this invention is shown below, it is not limited to it.

[Materials used]
The following materials were used.
-Primer layer-
(P-1): Epoxycyclohexylethyltrimethoxysilane (P-2): γ-aminopropyltrimethoxysilane-anchor coat layer (1)-
AC (1): Polyethyleneimine-based chelate complex-anchor coat layer (2)-
AC (2): polymer ion crosslinked product comprising polyacrylic acid as a main component and ion-crosslinked with a zirconium compound -thermoplastic resin (2)-
R-1: Maleic anhydride modified random PP (MFR = 23)
R-2: Random PP (MFR = 23)
[Solution preparation]
As the solution for forming the primer layer, a solution prepared by stirring in a water / methanol mixed solvent (adjusted to pH = 4 with acetic acid) to a solid content of 3 wt% for 6 hours at room temperature was used. The solution used as the anchor coat layer (1) was adjusted to a solid content of 0.5 wt% in a water / methanol mixed solvent. The solution used as the anchor coat layer (2) contains 8 mg / m ² as zirconium in the zirconium compound and 30 mg / m ² as a resin component containing polyacrylic acid as a main component in a water / methanol mixed solvent. What was adjusted so that it might become 0.5 wt% of solid content was used.

[Manufacturing method of laminate]
<Creation of substrate-1>
A biaxially stretched nylon film having a thickness of 25 μm was used as the thermoplastic resin (1). A soft aluminum foil (degreased) having a thickness of 40 μm was used as the aluminum foil.

The primer layer was applied on an aluminum foil that had been previously degreased by gravure coating so that the thickness of the dried coating film was 0.5 μm, and then dried in an oven at 120 ° C. At this time, the processing is performed in-line, and the processing speed is 20 m / min. I went there. The thermoplastic resin (1) was laminated on the opposite side of the aluminum foil provided with the primer layer by a dry laminating method using a urethane adhesive. The base material-1 formed at this time is as follows. In addition, the base material which has not provided the primer layer is set to base material-0.
Thermoplastic resin layer (1) / urethane adhesive / aluminum foil layer / primer layer <Preparation of substrate-2>
Using the base material-1, an anchor coat layer (2) was further provided on the primer-treated layer by gravure coating. Also at this time, coating and drying were performed in-line, and drying was performed in an oven at 120 ° C. The processing speed is 20 m / min. It is. The base material-2 formed at this time is as follows.
Thermoplastic resin layer (1) / urethane adhesive / aluminum foil layer / primer layer / anchor coat layer (2)
<Creation of laminate>
The said base material-1 and the base material-2 were set to the unwinding part of the extrusion laminating machine. The solution of the anchor coat layer (1) was set on the anchor coat coating unit of the extrusion laminator. The thermoplastic resin (2) was processed at a temperature of 280 to 290 ° C. and a processing speed of 80 m / min. Extrusion conditions were set so that the thickness would be 40 μm, and anchor coat (1
The thermoplastic resin (2) was extruded so as to have or not. Thereafter, a sample that had been heat-treated by passing the laminated body that had been aged at 50 ° C. for 4 days in-line to hold the drum heated to 200 ° C. was used for the following evaluation.

[Evaluation methods]
The initial laminate strength between the aluminum foil and the thermoplastic resin layer of the sample for evaluation and the laminate strength after the electrolyte solution was applied were measured. In that case, the sample width is 15 mm, T-type peeling, peeling speed is 300 mm / min. I went there. For the evaluation of the electrolytic solution dripping, an evaluation sample cut to a width of 15 mm was immersed in an electrolytic solution for lithium battery prepared so that LiPF ₆ was 1.5 N in an ethylene carbonate / ethyl methyl carbonate = 1/1 solution. Then, after storing at 85 ° C. for 2 weeks, the laminate strength between the aluminum foil and the thermoplastic resin layer was measured.

  The laminate of the present invention based on the above-described method for producing a laminate using a material comprising the substrate-1 as a substrate, the P-1 as a primer layer, and the R-1 as a thermoplastic resin layer (2). The laminate strength was measured based on the above evaluation method. The results are shown in Table 1.

  The layered product of the present invention based on the above method for producing a layered product using the above-mentioned substrate-1 as a substrate, P-2 as a primer layer, and R-1 as a thermoplastic resin layer (2). The laminate strength was measured based on the above evaluation method. The results are shown in Table 1.

  Using the above-mentioned base material-1 as a base material, the above-mentioned P-1 as a primer layer, the above-mentioned AC (1) as an anchor coat layer (1), and the material consisting of the above-mentioned R-1 as a thermoplastic resin layer (2) The laminate of the present invention was prepared based on the laminate production method, and the laminate strength was measured based on the evaluation method described above. The results are shown in Table 1.

  Using the above-mentioned base material-1 as a base material, the above-mentioned P-2 as a primer layer, the above-mentioned AC (1) as an anchor coat layer (1), and the material consisting of the above-mentioned R-1 as a thermoplastic resin layer (2) The laminate of the present invention was prepared based on the laminate production method, and the laminate strength was measured based on the evaluation method described above. The results are shown in Table 1.

  Base material-2 as a base material, P-1 as a primer layer, AC (1) as an anchor coat layer (1), AC (2) as an anchor coat layer (2), thermoplastic resin layer (2) As described above, the laminate of the present invention was prepared based on the above-described method for producing a laminate using the material consisting of R-1, and the laminate strength was measured based on the above-described evaluation method. The results are shown in Table 1.

As a comparative example for comparing the performance of the laminate of the present invention,
A laminate is prepared based on the method for producing a laminate using a material comprising the substrate-1 as a substrate, the P-1 as a primer layer, and the R-2 as a thermoplastic resin layer (2). The laminate strength was measured based on the above evaluation method. The results are shown in Table 1.

As a comparative example for comparing the performance of the laminate of the present invention,
Using the above-mentioned base material-1 as a base material, P-1 as a primer layer, AC (1) as an anchor coat layer (1), and R-2 as a thermoplastic resin layer (2), the above materials are used. A laminate was prepared based on the laminate manufacturing method, and the laminate strength was measured based on the evaluation method described above. The results are shown in Table 1.

As a comparative example for comparing the performance of the laminate of the present invention,
Using the above-mentioned base material-2 as a base material, the above P-1 as a primer layer, the above AC (2) as an anchor coat layer (2), and the above R-1 as a thermoplastic resin layer (2) A laminate was prepared based on the laminate manufacturing method, and the laminate strength was measured based on the evaluation method described above. The results are shown in Table 1.

As a comparative example for comparing the performance of the laminate of the present invention,
Based on the evaluation method described above, a laminate is produced based on the production method of the laminate using the substrate-0 as a substrate and the material consisting of the R-1 as a thermoplastic resin layer (2). The laminate strength was measured. The results are shown in Table 1.

As a comparative example for comparing the performance of the laminate of the present invention,
Based on the manufacturing method of the laminate, using the base material-0 as the base material, the AC (1) as the anchor coat layer (1), and the material consisting of the R-1 as the thermoplastic resin layer (2). A laminate was prepared and the laminate strength was measured based on the above evaluation method. The results are shown in Table 1.

  From Table 1, the laminates of the present invention obtained in Examples 1 to 5 are compared with the laminates obtained in Examples 6 to 10 as comparative examples for comparing the performance with the laminate of the present invention. And from the point of lamination strength, it is excellent in electrolyte solution tolerance. This is because the aluminum foil is provided with an epoxy-based or amino-based silane coupling agent as a primer layer, and the anchor coat layer (1) has a “polyethyleneimine polymer complex” The anchor coat (2) is made of “polymeric ion-crosslinked product containing polyacrylic acid as a main component and ionically crosslinked with a zirconium compound”, and further has a reactive functional group such as maleic anhydride as the thermoplastic resin (2). Since the modified polyolefin resin is used, the effect of combining the functional groups contained in each layer of the primer layer, the anchor coat layer (1), the anchor coat layer (2), and the thermoplastic resin (2) is obtained. A laminate having excellent liquid resistance can be obtained. Therefore, the laminate of the present invention can provide the electrolyte resistance required as a packaging material for lithium batteries, and is safer for the environment and the human body than conventional chromate treatment, Since the treatment process is simple as compared with the hydrothermal transformation treatment, it can be applied not only to a lithium battery exterior material but also to various packaging bodies.

It is a cross-sectional schematic diagram which shows an example of the laminated body of this invention.

Explanation of symbols

a: Thermoplastic resin layer (1)
b: Aluminum foil c: Primer layer d: Anchor coat layer (1)
e: Anchor coat layer (2)
f: Thermoplastic resin layer (2)
g: Adhesive layer

Claims (9)

At least in the laminate composed of the thermoplastic resin layer (1) / adhesive layer / aluminum foil layer / primer layer / thermoplastic resin layer (2) from the outside,
In the chemical formula represented by the following general formula, at least one of R ₁ , R ₂ , R ₃ , R ₄ is a reactive functional group (A), and the other substituents are hydrogen, halogen, alkyl. A layer formed from a compound comprising a substituent selected from a group, an alkoxyl group, a (meth) acryloxyl group, an allyl group, a vinyl group, or a derivative thereof, and the thermoplastic resin layer (2) is made of polyethylene , A layer formed from an acid modified product, an epoxy modified product, a silane modified product, or a mixture of two or more of these, such as an ethylene-α-olefin copolymer, polypropylene, and a propylene-α-olefin copolymer. A laminate comprising:

  Between the primer layer and the thermoplastic resin layer (2), a polymer complex comprising a polyethyleneimine and a polysaccharide having a carboxyl group, or a polymer comprising a copolymer of polyethyleneimine and ethylene and a monomer having a carboxyl group. The laminate according to claim 1, further comprising an anchor coat layer (1) comprising a layer formed of any one of the complexes or a mixture thereof.   The anchor coat layer (2) comprising a layer formed from a polymer ion crosslinked body containing a zirconium compound is provided between the primer layer and the anchor coat layer (1). Laminated body.   The reactive functional group (A) in the primer layer is reactive with at least one of the anchor coat layer (1), the anchor coat layer (2), and the thermoplastic resin layer (2). The laminate according to 2 or 3.   The laminate according to any one of claims 2 to 4, wherein the anchor coat layer (1) is reactive with the thermoplastic resin layer (2).   The laminate according to any one of claims 1 to 5, wherein the reactive functional group (A) is an epoxy group or an amino group.   The laminate according to any one of claims 3 to 6, wherein the anchor coat layer (2) is a polymer ion crosslinked body mainly composed of polyacrylic acid and ion-crosslinked with a zirconium compound. body.   A package comprising the laminate according to any one of claims 1 to 7.   A package comprising the laminate according to any one of claims 1 to 7 as an exterior material for a lithium battery.

Images