JP6826370B2 - Manufacturing method of resin-coated metal laminate and manufacturing method of battery exterior - Google Patents

Description

The present invention, various exterior body of a method for manufacturing applications useful resin-coated metal laminate package like, and, in the manufacturing method of the battery case body obtained by the production method of the resin-coated metal laminate Related.

In the field of exteriors and packaging used for industrial products such as electronic devices and batteries, and daily necessities such as foods, beverages, cosmetics, and pharmaceuticals, from resin layers located on the outer layer side and metal foils. A resin-coated metal laminate having a barrier layer and a sealant layer made of a resin having a heat-sealing property is used.

For example, as the exterior body used for a battery such as a secondary battery, the resin-coated metal laminate (battery exterior body) as described above is used for the purpose of miniaturization and weight reduction. Such a battery exterior laminate is formed by drawing or the like so as to form a tray having recesses to form an exterior container body. Further, in the same manner as the outer body container main body, the battery outer laminate is molded to obtain the outer body lid portion. After storing the battery body in the recess of the exterior container body, the exterior body lid is overlapped so as to cover the stored battery body, and the side edges of the container body and the exterior lid are fused. A battery in which the battery body is housed in the outer body can be obtained.

The exterior and packaging as described above are required to have functionality such as gas barrier properties and durability (heat resistance, water resistance, chemical resistance), as well as high designability regarding the appearance of the exterior and packaging. Is also required. As one of the methods for enhancing the design, a resin-coated metal laminate having a colored layer separately provided has been proposed.
For example, in Patent Document 1, in this order from the outer layer side, a heat-resistant resin stretched film layer (resin layer), an easy-adhesive layer, a colored ink layer, a first adhesive layer, a metal foil layer (barrier layer), and a second adhesive. A packaging material in which a layer and a thermoplastic resin layer (sealant layer) are laminated and which can be used for a battery exterior is described. In Patent Document 1, a film having a hot water shrinkage rate of 2 to 20% is used as the heat-resistant resin stretched film layer, and biaxially stretched nylon film, biaxially stretched polyethylene terephthalate film or biaxially stretched polyethylene naphthalate film is used. It is given as a preferable example and is used in Examples.

JP-A-2015-44626

In recent years, in portable electronic devices such as mobile phones, tablet terminals, and cameras, there is a demand for miniaturization, weight reduction, and thickness reduction of the external dimensions of the housing. In addition, these portable electronic devices tend to consume more electric power than conventional portable electronic devices, and not only miniaturization and thinning of batteries but also large capacity of batteries are required. ing. Therefore, the battery exterior that can be used in such electronic devices is also required to be further thinned.

In the laminate as described in Patent Document 1, the design is improved by providing the colored ink layer, but there is a problem that the thickness of the entire laminate is increased by further increasing the number of colored ink layers.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a resin-coated metal laminate having high designability and capable of thinning.

As a result of repeated studies to achieve the above object, the present inventors have found that by using a layer made of polyimide containing a colored pigment as a resin layer, both high designability and thinning can be achieved. Completed the invention.

That is, the present invention has adopted the following configuration.
The resin-coated metal laminate according to the first aspect of the present invention is a resin-coated metal laminate including at least a resin layer, a barrier layer, and a sealant layer in this order, and the resin layer contains a colored pigment. The resin layer is made of polyimide and has a thickness of 1 to 15 μm.
The colored pigment is preferably carbon black.
The resin layer preferably has a tensile elongation of 50% or more according to the method of JIS-K-7127 of the single layer of the resin layer.
It is preferable that the resin-coated metal laminate further includes an anchor layer between the resin layer and the barrier layer.
The barrier layer is preferably a stainless steel foil having a thickness of 30 μm or less.
The stainless steel foil is preferably a surface-treated metal leaf.
The resin-coated metal laminate is preferably used for the battery exterior.
The method for producing the resin-coated metal laminate according to the second aspect of the present invention is the method for producing the resin-coated metal laminate according to the first aspect, which is a polyamic acid on the barrier layer without an adhesive layer. Is applied and heated to form a resin layer containing a polyimide resin.
The battery exterior body of the third aspect of the present invention is a battery exterior body including the resin-coated metal laminate of the first aspect, has an internal space for accommodating the battery, and is a sealant of the resin-coated metal laminate. It is characterized in that the side of the layer is the side of the internal space.
The battery exterior is preferably a draw-molded body of the resin-coated metal laminate of the first aspect.
The battery of the fourth aspect of the present invention is characterized by including the battery exterior body of the third aspect.

According to the present invention, it is possible to provide a resin-coated metal laminate having high designability and capable of thinning.

It is a schematic sectional drawing which shows one Embodiment of the resin-coated metal laminate which concerns on this invention. It is a perspective view which shows an example of the secondary battery manufactured using the resin-coated metal laminate which concerns on this invention. It is a perspective view which shows the process of manufacturing a secondary battery using the resin-coated metal laminate which concerns on this invention.

Hereinafter, the present invention will be described based on preferred embodiments.

[Resin-coated metal laminate]
The resin-coated metal laminate according to the first aspect of the present invention (hereinafter, may be simply referred to as “laminate”) is a resin-coated metal laminate including at least a resin layer, a barrier layer, and a sealant layer in this order. In the body, the resin layer is made of polyimide containing a colored pigment, and the thickness of the resin layer is 1 to 15 μm.

FIG. 1 is a cross-sectional view showing a schematic configuration of a resin-coated metal laminate 10 (hereinafter, may be referred to as “laminate 10”) according to an embodiment of the present invention. In addition, in order to clarify the feature portion, the scale does not always match the actual aspect in all the drawings, and the laminated body 10 is not limited to the scale of the drawings.
The laminate 10 according to the present embodiment has a six-layer structure including a resin layer 11, a first corrosion prevention layer 12, a barrier layer 13, a second corrosion prevention layer 14, an adhesive layer 15, and a sealant layer 16 in this order. is there.
Hereinafter, each layer will be described in detail.

<Resin layer 11>
The resin layer 11 is made of polyimide containing a colored pigment.
Since the layer made of polyimide resin has higher mechanical strength than the layer made of other resins, it has excellent mechanical strength even when it is set to 1 to 15 μm in response to the thinning requirement for the laminate 10. Can be realized. Further, since the layer made of the polyimide resin has not only mechanical strength but also excellent high temperature resistance and excellent insulating property, the laminate 10 having the layer made of the polyimide resin on the outer layer side is under severe conditions. Good characteristics can be obtained even when used in.

The resin layer 11 contains a colored pigment. In the present invention, the "colored pigment" refers to a pigment that exhibits a chromatic color or an achromatic color under visible light. Since the resin layer 11 contains a colored pigment, it is possible to impart a high degree of design to the laminate 10 without providing a colored layer or the like separately from the resin layer 11, and the design and thinning of the laminate 10 can be achieved. It can be compatible.

The colored pigment contained in the resin layer 11 is not particularly limited, and can be appropriately selected from known inorganic pigments and organic pigments according to the requirements for the appearance of the laminate 10. For example, when there is a demand for the laminate 10 to be black, for example, a black organic pigment can be used. Carbon black is preferable as the black organic pigment.
As the colored pigment contained in the resin layer 11, only one type may be used alone, or two or more types may be used in combination.
The content of the colored pigment can be appropriately determined according to the desired appearance and the characteristics of the pigment used. For example, the colored pigment can be contained in the polyimide in an amount of 0.5 to 60% by mass, and 1 to 50. The mass% is more preferable, and 3 to 20% by mass is further preferable.

The tensile elongation of the single layer of the resin layer 11 according to the method of JIS-K-7127 is preferably 50% or more, more preferably 80% or more, further preferably 100% or more, and particularly preferably 110% or more. By using the resin layer 11 having such a relatively high tensile elongation, the followability of the resin layer 11 to the barrier layer 13, the sealant layer 16 and the like is improved, and a problem occurs even during deep drawing. A laminated body 10 that does not occur can be obtained.
The tensile elongation of the resin layer 11 can be measured as a tensile strain of plastic in accordance with JIS-K-7127.

The method for forming the resin layer 11 made of polyimide is not particularly limited.
For example, the resin layer 11 may be formed by applying the raw material of the resin layer made of polyimide on the barrier layer 13 on which the first corrosion prevention layer 12 is laminated by using a known coating device.

Polyimide includes a thermosetting polyimide generated by a dehydration condensation reaction by heating a polyamic acid and a solvent-soluble polyimide which is a non-dehydration condensation type solvent-soluble.
In thermosetting polyimide, first, a polyamic acid which is an imide precursor is synthesized by reacting a diamine with a carboxylic acid dianhydride in a polar solvent. This polyamic acid is dehydrated and cyclized by heating at about 200 to 300 ° C. or by reacting with a catalyst to form a polyimide layer.
On the other hand, the solvent-soluble polyimide is one in which the imidization of the polyimide is completed and is soluble in a solvent. Therefore, the polyimide layer can be formed by applying the solvent-soluble polyimide coating solution dissolved in the solvent and then volatilizing the solvent at a relatively low temperature of less than 200 ° C.

As described above, the thermosetting polyimide requires high temperature heating for layer formation. Therefore, there is a problem that it cannot be used when a material having low heat resistance is used for the lower layer or the like. On the other hand, in the solvent-soluble polyimide, the polyimide that has been imidized must be soluble in the solvent. Therefore, there is a problem that the structure of the polyimide is very limited and the degree of freedom for obtaining the polyimide having various characteristics is low.
In the present embodiment, the resin layer 11 made of polyimide is formed on the barrier layer 13 made of metal foil via the first corrosion prevention layer 12. Here, it is easy for the barrier layer 13 and the first corrosion prevention layer 12 to be a layer having high heat resistance or to have a structure having high heat resistance. Therefore, when the resin layer 11 is formed by coating in the present embodiment, it is preferable to form a thermosetting polyimide layer having a high degree of freedom in structure via a polyamic acid.

When the resin layer 11 made of polyimide is formed by the above coating, when the polyamic acid or the solvent-soluble polyimide coating liquid is applied on the lower layer (for example, the first corrosion prevention layer 12 described later), By dispersing the colored pigment in them, the resin layer 11 containing the colored pigment can be formed.
By forming the resin layer 11 containing a colored pigment inside, it is not necessary to provide a colored layer or the like as a separate layer, and the laminated body 10 can be made thinner.

Further, a polyimide film containing a colored pigment produced in advance may be laminated as a resin layer 11 on the barrier layer 13 on which the first corrosion prevention layer 12 is laminated. In the latter case, it is preferable that the first corrosion prevention layer 12 and the resin layer 11 are adhered to each other via an arbitrary adhesive layer. Details of this adhesive layer will be described later as an arbitrary "anchor layer".

In the present invention, the film thickness of the laminated body 10 is preferably thin. Therefore, from the viewpoint of omitting the adhesive layer (anchor layer), the resin layer 11 is preferably formed by coating, and is formed by applying a polyamic acid in which a colored pigment is dispersed on the lower layer and then heating the resin layer 11. Is preferable.

The thickness of the resin layer 11 is 1 to 15 μm, preferably 1 to 10 μm, and even more preferably 5 to 10 μm.

<Anchor layer>
The laminate 10 may include an arbitrary anchor layer (not shown) between the resin layer 11 and the first corrosion prevention layer 12. The anchor layer is a layer for adhering the resin layer 11 and the first corrosion prevention layer 12 or for improving the adhesiveness of these layers.

For example, when a film formed in advance is attached as the resin layer 11, an adhesive layer can be provided as an anchor layer. The adhesive layer may have the same structure as the adhesive layer 15 described later, or may be a layer made of an adhesive such as a general urethane-based adhesive or an epoxy-based adhesive. When the adhesive layer is provided as the anchor layer, the thickness thereof can be, for example, 0.05 to 10 μm, preferably 0.1 to 5 μm. By setting the thickness within this range, the resin layer 11 and the first corrosion prevention layer 12 can be adhered with a high adhesive force, and delamination can be prevented.

Further, when the resin layer 11 is formed by coating, it is preferable not to provide an anchor layer as an adhesive layer. On the other hand, if it is an undercoat layer that can improve the surface texture of the first corrosion prevention layer 12, it is also preferable to provide it as an anchor layer. By providing the undercoat layer, the adhesion between the resin layer 11 and the first corrosion prevention layer 12 can be improved. The undercoat layer is, for example, a layer made of a resin having a functional group having a high affinity with the polyimide resin used for the resin layer 11; reacts with the polyimide resin used for the resin layer 11 to form a structure such as cross-linking. Examples thereof include a layer made of the resin to be obtained.

<1st corrosion prevention layer 12 / 2nd corrosion prevention layer 14>
The first corrosion prevention layer 12 and the second corrosion prevention layer 14 both have an arbitrary structure in the present invention, and the barrier layer 13 (details will be described later), which is preferably a layer made of metal, is corroded by rust or the like. It is a surface treatment layer for preventing rust.
The first and second corrosion prevention layers 12 and 14 are all optional, but when the laminate 10 of the present invention is used in an application capable of coming into contact with a component capable of promoting metal corrosion, the first and second corrosion prevention layers 12 and 14 are used. 2 It is preferable to provide the corrosion prevention layers 12 and 14 on the surface of the barrier layer 13. For example, when the laminate 10 of the present invention is used for the exterior of a battery, there is a risk that a chemical solution such as an electrolytic solution may leak from the contained battery. Since such a leaked chemical solution can corrode the metal of the barrier layer 13, it is preferable to apply a corrosion prevention treatment (surface treatment) to the surface of the barrier layer 13. Further, in the case of battery exterior use, the side that is likely to come into contact with the electrolytic solution is the side of the contained battery, that is, the side of the sealant layer 16 of the barrier layer 13, so that at least the second corrosion prevention layer 14 is provided. It is preferable to provide it.

The first and second corrosion prevention layers 12 and 14 preferably contain a metal halide compound, and the surface of the barrier layer 13 may be directly plated with a metal halide compound as described later. By providing such first and second corrosion prevention layers 12 and 14, it is possible to impart a good rust prevention effect to the barrier layer 13.
Further, the first and second corrosion prevention layers 12 and 14 preferably further contain a water-soluble resin and a chelating agent or a crosslinkable compound in addition to the metal halide compound. Therefore, the first and second corrosion prevention layers 12 and 14 preferably contain a metal halide compound, a water-soluble resin, and a chelating agent or a crosslinkable compound; the first and second corrosion prevention layers 12 , 14 may be formed by applying an aqueous solution containing a halogen compound, a water-soluble resin, and a chelating agent or a crosslinkable compound onto an underlying layer, and then drying and curing the compound. preferable. Hereinafter, the material forming the first and second corrosion prevention layers 12 and 14 may be referred to as a "corrosion prevention treatment agent".

(Metal halide compound)
The metal halide compound has an action of improving chemical resistance such as electrolytic solution resistance. That is, the surface of the barrier layer 13 can be passivated and the corrosion resistance to the electrolytic solution can be enhanced. When the first and second corrosion prevention layers 12 and 14 contain a water-soluble resin described later, the metal halide also has an action of cross-linking the water-soluble resin.
The metal halide compound is preferably water-soluble in view of its miscibility with a water-soluble resin described later and the case where it is dispersed and applied to a water-soluble medium.
Examples of the metal halide compound include chromium halide, iron halide, zirconium halide, titanium halide, hafnium halide, hydrohydrogenate titanium halide, and salts thereof. Examples of the halogen atom include chlorine, bromine and fluorine, and chlorine or fluorine is preferable. Further, fluorine is particularly preferable. Since the metal halide compound contains fluorine, it becomes possible to generate hydrofluoric acid (HF) from the corrosion prevention treatment agent depending on the conditions.
Further, the metal halide compound may have an atom other than a halogen atom or a metal.
Among them, as the metal halide compound, chlorides or fluorides of iron, chromium, manganese or zirconium are preferable.

(Water-soluble resin)
As the water-soluble resin, it is preferable to use at least one selected from the group consisting of polyvinyl alcohol resins or derivatives thereof and polyvinyl ether-based resins.

The polyvinyl alcohol resin or its derivative is preferably a polyvinyl alcohol resin or a modified polyvinyl alcohol resin.
The polyvinyl alcohol resin can be produced, for example, by saponifying a polymer of a vinyl ester-based monomer or a copolymer thereof. The polyvinyl alcohol resin may be modified.
As the polymer of the vinyl ester-based monomer or its copolymer, a homopolymer of a fatty acid vinyl ester such as vinyl formate, vinyl acetate, vinyl butyrate, or a homopolymer of a vinyl ester-based monomer such as an aromatic vinyl ester such as vinyl benzoate, or Examples thereof include a copolymer and a copolymer of another monomer copolymerizable therewith. Other copolymerizable monomers are not particularly limited. In addition, polymerization and copolymerization can be carried out by a conventional method.

Examples of the polyvinyl ether-based resin include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, norbornyl vinyl ether, allyl vinyl ether, norbornenyl vinyl ether and 2-hydroxy. Examples thereof include homopolymers or copolymers of aliphatic vinyl ethers such as ethyl vinyl ether and diethylene glycol monovinyl ether, and copolymers of other monomers copolymerizable therewith. Examples of the other monomer copolymerizable with the vinyl ether-based monomer include those similar to the other monomers copolymerizable with the vinyl ester-based monomer described above.
In particular, polyvinyl ether-based resins containing an aliphatic vinyl ether having a hydroxyl group as a monomer, such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, and monovinyl ethers of various glycols and polyhydric alcohols, are water-soluble. It can be suitably used in the present invention because it has a cross-linking reaction with respect to a hydroxyl group.

As the water-soluble resin, only one of the polyvinyl alcohol resin or a derivative thereof and the polyvinyl ether-based resin may be used, or both may be used in combination.

(Chelating agent)
A chelating agent is a material that can coordinate-bond to a metal ion to form a metal ion complex.
The chelating agent binds a metal compound derived from a metal halide (such as chromium oxide) and the water-soluble resin to increase the compressive strength of the first and second corrosion prevention layers 12 and 14. Therefore, even if the thicknesses of the first and second corrosion prevention layers 12 and 14 exceed 0.2 μm and are 1.0 μm or less, the first and second corrosion prevention layers 12 and 14 become brittle and crack. No peeling occurs. Therefore, the adhesive strength and adhesiveness between the barrier layer 13 and the resin layer 11 and the adhesive layer 15 can be increased.
Further, the chelating agent has an action of making the water-soluble resin water-resistant by chemically reacting with the water-soluble resin or the metal halide compound.

As the chelating agent, for example, an aminocarboxylic acid-based chelating agent, a phosphonic acid-based chelating agent, an oxycarboxylic acid-based chelating agent, and a (poly) phosphoric acid-based chelating agent can be used.
Among them, as the chelating agent, a phosphoric acid-based chelating agent (phosphoric acid compound) such as a phosphonic acid-based chelating agent and a (poly) phosphoric acid-based chelating agent is preferable, and a phosphonic acid-based chelating agent is more preferable.

(Crosslinkable compound)
The crosslinkable compound refers to a compound that can react with the water-soluble resin to form a crosslinked structure. By using such a crosslinkable compound, the above-mentioned water-soluble resin and the crosslinkable compound form a dense crosslinked structure in the first and second corrosion prevention layers 12 and 14, and the passivation of the surface of the barrier layer 13 is formed. The properties and corrosion resistance can be further improved.
The crosslinkable compound is not particularly limited as long as it can react with a hydrophilic group (for example, a carboxy group, a carboxylic acid group, etc.) in the water-soluble resin to form a crosslinked structure. Examples thereof include a compound having an epoxy group and a compound having an oxazoline group.

In the corrosion prevention treatment agent, only one of the chelating agent and the crosslinkable compound may be used, or both may be used in combination.

The corrosion prevention treatment agent can be produced by dissolving a water-soluble resin, a metal halide compound, a chelating agent and / or a crosslinkable compound in a solvent containing water.

The thickness of the first and second corrosion prevention layers 12 and 14 is preferably 0.05 μm or more, more preferably more than 0.08 μm. Further, 1.0 μm or less is preferable, and 0.5 μm or less is more preferable.

<Barrier layer 13>
The barrier layer 13 plays an important role in the laminated body 10 in order to reduce leakage of the contents sealed by the laminated body (for example, liquid leakage of a battery). Further, by using a metal having high mechanical strength, it is possible to reduce the occurrence of pinholes when the laminate 10 is used and the recess for storing the battery is formed by drawing molding, and as a result, the laminate is sealed. It is possible to reduce the leakage of the contents (for example, the leakage of the battery).
The barrier layer 13 is not particularly limited as long as it is a thinly spread metal or alloy, and is a metal foil such as aluminum, copper, lead, zinc, iron, nickel, titanium, chromium; stainless steel or the like. Alloy foil can be mentioned. The stainless steel foil is not particularly limited as long as it is made of stainless steel such as austenite, ferrite, and martensitic. Examples of the austenitic system include SUS304, 316, 301 and the like, examples of the ferrite system include SUS430 and the like, and examples of the martensitic system include SUS410 and the like.
Of these, aluminum foil or stainless steel foil is preferable from the viewpoints of workability, availability, price, strength (piercing strength, tensile strength, etc.), corrosion resistance, and the like.

A metal foil or an alloy foil is used as the barrier layer 13, and such a barrier layer 13 has high mechanical strength. However, since the metal foil or the alloy foil has a higher mechanical strength than the resin thin film, the moldability is often low. Therefore, for example, in the case of drawing molding a laminate having a metal foil or an alloy foil as a barrier layer for a battery exterior, a part of the laminate is broken during drawing molding, and the corners of the molded body after drawing are formed. Problems such as some troubles may occur.
In the present invention, by using polyimide for the resin layer 11, good moldability can be obtained in draw molding and the like even when a metal foil or an alloy foil is used as the barrier layer 13. Although the reason why such an effect can be obtained is not clear, the barrier layer 13 made of a metal foil or an alloy foil having a high mechanical strength is coated with a resin layer 11 containing a polyimide having a high mechanical strength. It is considered that it is possible to prevent peeling between layers due to the difference in mechanical strength between the layers and tearing of the layer due to strain.

The above-mentioned effect on moldability can be obtained well even when a stainless steel foil is used as the barrier layer 13.
The stainless steel foil has particularly high mechanical strength as compared with aluminum foil and the like which have been widely used as a barrier layer material for a laminated body for a packaging body and a laminated body for an exterior body. Therefore, by using the stainless steel foil, good strength can be maintained even when the barrier layer 13 is made into a thin film, and thinning of the entire laminate 10 can be achieved. On the other hand, since the mechanical strength is particularly high, the moldability may be particularly inferior.
In the present invention, it has been found that the problem of moldability can be solved by using such a stainless steel foil in combination with polyimide. Then, by using the stainless steel foil and the polyimide in combination, it is possible to further reduce the film thickness of the entire laminate 10.

The thickness of the barrier layer 13 is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. More specifically, 5 to 30 μm is preferable, 10 to 30 μm is more preferable, and 10 to 20 μm is particularly preferable. By setting the value to the above lower limit value or more, sufficient mechanical strength can be given to the laminated body 10, and the durability of the battery can be enhanced when used in a battery such as a secondary battery. Further, by setting the thickness of the barrier layer 13 to be equal to or less than the above upper limit value, the laminated body 10 can be made sufficiently thin and sufficient drawability can be provided.

<Adhesive layer 15>
The adhesive layer 15 is an arbitrary layer in the present invention, and is a layer provided for adhering the sealant layer 16 and the barrier layer 13 on which the second corrosion prevention layer 14 is formed on the surface.
The material of the adhesive forming the adhesive layer 15 is not particularly limited as long as it can adhere the above layers well, but for example, it can satisfy adhesiveness and storage elasticity. Therefore, it is preferable to contain the acid-modified polyolefin resin (A). Further, it is more preferable that the layer is made of an adhesive containing an acid-modified polyolefin resin (A) and a compound (B) containing a plurality of epoxy groups.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “component (A)”, and the compound (B) containing a plurality of epoxy groups may be referred to as “component (B)”.

(Acid-modified polyolefin resin (A))
The acid-modified polyolefin resin (A) (component (A)) is a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof, and an acid such as a carboxy group or an anhydrous carboxylic acid group is contained in the polyolefin-based resin. It has a functional group.
The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, copolymerizing an acid functional group-containing monomer with olefins, or the like. Among them, the component (A) is preferably obtained by acid-modifying a polyolefin resin.

Examples of the polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a copolymer of propylene and ethylene, and a copolymer of propylene and an olefin monomer.
Examples of the olefin-based monomer in the case of copolymerization include 1-butene, isobutylene, 1-hexene and the like.

Among them, as the component (A), maleic anhydride-modified polypropylene is preferable from the viewpoint of adhesiveness, durability and the like.

(Compound (B) containing a plurality of epoxy groups)
The component (B) is a compound containing a plurality of epoxy groups. The component (B) is an additive added to the component (A) and is an arbitrary component. The component (B) may be a low molecular weight compound or a high molecular weight compound. From the viewpoint of improving miscibility and compatibility with the component (A), the component (B) is preferably a polymer compound (resin). On the other hand, when the adhesive is a solvent-type adhesive for dry laminating, it is also preferable that the component (B) is a low molecular weight compound from the viewpoint of improving the solubility in an organic solvent.

The structure of the component (B) is not particularly limited as long as it has a plurality of epoxy groups, and examples thereof include a phenoxy resin synthesized from bisphenols and epichlorohydrin; a phenol novolac type epoxy resin; and a bisphenol type epoxy resin. Among them, it is preferable to use a phenol novolac type epoxy resin because the epoxy content per molecule is high and a particularly dense crosslinked structure can be formed together with the component (A).

By using the component (B) as described above, both the acid functional group of the component (A) and the epoxy group of the component (B) are contained in the adherend (particularly, the second corrosion prevention layer 14). Adhesive to functional groups such as carboxy groups) By functioning as a functional group, it is possible to exhibit excellent adhesiveness to the sealant layer 16 and the barrier layer 13 having the second corrosion prevention layer 14 on the surface. It is thought that
Further, a part of the acid functional group of the component (A) and a part of the epoxy group of the component (B) react with each other, and the crosslinked structure of the component (A) and the component (B) forms a second corrosion prevention layer. As a result of being formed in 14, it is considered that the strength of the adhesive layer 15 is reinforced by this crosslinked structure, and good durability as well as excellent adhesiveness can be obtained.

The adhesive layer 15 preferably contains 1 to 30 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and (B) with respect to 100 parts by mass of the component (A). ) Is more preferably 3 to 20 parts by mass, and 5 to 10 parts by mass of the component (B) is particularly preferable with respect to 100 parts by mass of the component (A).

(Optional ingredient)
The adhesive used in the present invention may or may not further contain an organic solvent.
By containing an organic solvent and making it a liquid adhesive, it can be made into a solvent-type dry laminating adhesive. The adhesive layer 15 can be formed by applying and drying such a liquid adhesive on a lower layer (for example, a surface of the barrier layer 13 provided with the second corrosion prevention layer 14). .. By selecting coating instead of extrusion molding, the adhesive layer can be formed with a thinner layer, the adhesive layer can be made thinner, and the entire laminate using the adhesive layer can be made thinner.
On the other hand, when the organic solvent is not contained, the component (A) and the component (B) are melt-kneaded, or the component (A) is melted and then extruded to form an adhesive layer suitable for thermal lamination or the like. Can be formed.

When an organic solvent is contained, the above-mentioned component (A), component (B), and other optional components (details will be described later) are preferably dissolved as the organic solvent to be used to obtain a uniform solution. The solvent is not particularly limited as long as it can be used, and any known solvent can be used as the solvent for the solution type adhesive.

One type of organic solvent may be used alone, or two or more types may be used in combination as a mixed solvent. When a plurality of types of organic solvents are mixed and used, the ratio of each organic solvent is not particularly limited. For example, when toluene and methyl ethyl ketone are used in combination, the mixing ratio of these is toluene: methyl ethyl ketone = 60 to 60 to. 95: 5 to 40 (mass ratio) is preferable, and toluene: methyl ethyl ketone = 70 to 90: 10 to 30 (mass ratio) is more preferable.

The adhesive used in the present invention may contain the component (B) in addition to the above component (A), and may further contain other components in addition to the organic solvent. Examples of other components include miscible additives and additional resins, and more specifically, catalysts, cross-linking agents, plasticizers, stabilizers, colorants and the like can be used.

In the solid content of the adhesive used in the present invention, the component (A) is contained in an amount of more than 50 parts by mass and 99.5 parts by mass or less, and the component (B) is contained in an amount of 0.5 parts by mass or more and less than 50 parts by mass. It is preferable to be done. That is, more than half of the solid content of the adhesive is the component (A) in terms of mass ratio, and the adhesive used in the present invention contains the component (A) as the main component. More preferably, it is 0.5 to 30 parts by mass of the component (B) with respect to 70 to 99.5 parts by mass of the component (A); more preferably, it is (more preferably) with respect to 80 to 98 parts by mass of the component (A). B) 2 to 20 parts by mass of the component; 5 to 10 parts by mass of the (B) component is particularly preferable with respect to 90 to 95 parts by mass of the (A) component.

Further, even when the adhesive used in the present invention contains a solid component other than the component (A) and the component (B) as an optional component, the component (A) is always the main component. Therefore, even when an arbitrary component is contained, the component (A) in the total solid content of the adhesive is more than 50 parts by mass. For example, 70 to 99.5 parts by mass of the component (A), 0.5 to 29.5 parts by mass of the component (B), and 0.5 to 29.5 parts by mass of the other components in the total solid content. An adhesive containing and can be mentioned.

When the adhesive used in the present invention contains an organic solvent, the amount of the organic solvent used is particularly limited as long as it can satisfactorily dissolve each component such as the component (A), the component (B), and the optional component. However, in general, the solid content concentration is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 10 to 20% by mass.

The thickness of the adhesive layer 15 can be, for example, 0.1 to 50 μm, preferably 0.5 to 10 μm. By setting the thickness within this range, the sealant layer 16 and the barrier layer 13 provided with the second corrosion prevention layer 14 can be adhered with a high adhesive force, and delamination can be prevented.

<Sealant layer 16>
The sealant layer 16 is a layer capable of stacking the resin-coated metal laminates 10 of the present invention and adhering them to each other by heat sealing.
The sealant layer 16 is not particularly limited as long as it can function as the sealant layer as described above, but a layer made of polyolefin is preferable from the viewpoint of easy availability, heat sealability, and the like. .. Examples of the layer made of polyolefin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or α-olefin, and a block copolymer of propylene and ethylene or α-olefin. ..
Among them, since the adhesiveness with the adhesive layer 15 is improved, homopolypropylene (propylene homopolymer; hereinafter, sometimes referred to as “homoPP”) and propylene-ethylene block copolymer (hereinafter, “HomoPP”) Polypropylene-based resins such as "block PP") and a random copolymer of propylene-ethylene (hereinafter, may be referred to as "random PP") are preferable. Of these, homo-PP or block PP is more preferable, and block PP is particularly preferable because it has excellent mechanical strength.
The sealant layer 16 may have a single-layer structure or a multi-layer structure.

The melting point of the polyolefin layer used for the sealant layer 16 is not particularly limited as long as it has the heat resistance required for the laminate 10.
The thickness of the sealant layer 16 can be, for example, 1 to 50 μm, preferably 5 to 30 μm.

In the laminate 10 shown in FIG. 1, the resin layer 11 is the outermost layer, but a coating layer or a matte layer can also be formed on the outer surface side of the resin layer 11.
The coating layer (surface protective layer) includes urethane resin, acrylic resin, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer resin, maleic anhydride-modified polypropylene resin, polyester resin, epoxy resin, phenol resin, phenoxy resin, and fluorine resin. At least selected from the resin group consisting of cellulose ester resin, cellulose ether resin, polyamide resin, polyvinylidene ether resin (PPE), polyvinylidene sulfide resin (PPS), polyaryl ether resin (PAE), and polyether ether ketone resin (PEEK). It is made of one type of resin. The coating layer is preferably made of a material having excellent heat resistance. These resins may be used alone or in combination of two or more.

The coating layer is preferably a thin film cured layer formed by applying and drying a solvent-based paint prepared by dissolving the resin in a general organic solvent.
By forming the coating layer, effects such as improvement of insulating property, prevention of surface scratches, and improvement of surface printing characteristics can be obtained. Further, even if the laminated body 10 comes into contact with the electrolytic solution, it is possible to prevent a change in appearance (discoloration or the like).
Further, the coating layer can be colored or printed so as to display characters, figures, images, patterns, etc. to further enhance the design.
The thickness of the coating layer can be, for example, 0.001 to 10 μm, preferably 0.01 to 10 μm.

The mat layer is a layer for imparting a mat property to the laminated body 10. Not only can the matte layer provide a matte appearance, but it can also have the effect that scratches and the like on the surface of the laminate 10 are less visible than when the glossiness is high.
The mat layer preferably has fine particles in order to easily obtain a good mat effect. When the fine particles are contained in the mat layer, fine irregularities are formed on the surface of the mat layer, and the unevenness scatters light, resulting in a decrease in glossiness and a matte effect.
Specifically, the mat layer is preferably a layer composed of a composition in which fine particles are dispersed in a resin as a main agent, and a mat layer forming agent in which the resin and fine particles are dispersed in a solvent is thinly applied onto the resin layer 11. It is more preferable that the particles are formed.

Specific examples of the resin contained in the mat layer include acrylic resin, urethane resin, acrylic urethane resin, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer resin, maleic anhydride-modified polypropylene resin, polyester resin, epoxy resin, and phenol resin. , Phenoxy resin, fluororesin, cellulose ester resin, cellulose ether resin, polyamide resin, polyvinylidene ether resin (PPE), polyvinylidene sulfide resin (PPS), polyaryl ether resin (PAE), polyether ether ketone resin (PEEK), etc. Can be mentioned. One of these resins may be used alone, or two or more of these resins may be used in combination.
Among them, acrylic urethane resin is preferable as the resin of the mat layer.

The fine particles contained in the mat layer may be organic fine particles or inorganic fine particles. The fine particles include organic fine particles such as polystyrene, polycarbonate, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, epoxy resin, acrylic resin, methacrylic resin, silicone resin, and urethane resin; silica, alumina, zirconia, zinc oxide, titanium oxide, and glass. Examples thereof include inorganic fine particles such as beads. One of these fine particles may be used alone, or two or more of these fine particles may be used in combination.
The shape and size of the fine particles are not particularly limited and may be fixed or irregular, but a substantially spherical shape is preferable, and the size is preferably 1 to 10 μm in average particle diameter, and particularly preferably 2 to 5 μm.
Among them, as the fine particles of the mat layer, one or more selected from the group consisting of acrylic particles (acrylic beads) and silica particles is preferable, and the combined use of these is more preferable.

The mat layer forming agent for forming the mat layer preferably contains 70 to 98% by mass of the above resin and 2 to 30% by mass of the fine particles in the total solid content; 80 to 95% by mass of the resin. It is more preferable to contain 5 to 20% by mass of the fine particles; it is further preferable to contain 85 to 95% by mass of the resin and 5 to 15% by mass of the fine particles.

The mat layer is preferably formed thinly on the resin layer 11 in order to reflect fine irregularities that can be formed by the fine particles on the surface of the mat layer, and the mat layer forming agent as described above is applied onto the resin layer 11. It is preferable that it is formed by The coating method is not particularly limited, and for example, a known bar coater or the like can be used.
The amount of the mat layer forming agent applied to form the mat layer is not particularly limited, and the glossiness required for the laminate 10, the particle size, amount, shape, etc. of the fine particles used for the mat layer, etc. It is preferable that the determination is made as appropriate. As an example, when acrylic urethane resin, silica particles, and acrylic beads are used as a mat layer forming agent, a solution containing the component in a solid content of 10 to 50% by mass is prepared, and a bar coater or a gravure printing machine is used. It is preferable to apply the solution at ² to 15 g / m ² on the base material layer 13 using the above.
The film thickness of the mat layer formed in this manner can be, for example, 0.1 μm to 1 mm, preferably 0.5 μm to 100 μm.

The thickness of the resin-coated metal laminate 10 is preferably 10 to 200 μm, more preferably 20 to 100 μm, and even more preferably 30 to 85 μm.

The resin-coated metal laminate 10 of the present invention is particularly suitable for battery exterior use. Examples of the battery include those using an organic electrolyte as an electrolytic solution, such as a secondary battery such as a lithium ion battery which is a secondary battery, and a capacitor such as an electric double layer capacitor. The organic electrolyte is generally one in which carbonic acid esters such as propylene carbonate (PC), diethyl carbonate (DEC), and ethylene carbonate are used as a medium, but the organic electrolyte is not particularly limited thereto.

(Manufacturing method of resin-coated metal laminate 10)
The method for producing the resin-coated metal laminate 10 of the present embodiment is not particularly limited, and for example, it can be produced as follows.

First, a metal foil or the like to be the barrier layer 13 is prepared, and the first corrosion prevention layer 12 and the second corrosion prevention layer 14 are formed on both surfaces thereof.
Specifically, the above-mentioned anticorrosion treatment agent is applied to the surface of the barrier layer 13, and then heat-dried. At this time, only the second corrosion prevention layer 14 may be formed by applying the corrosion prevention treatment agent to only one side of the barrier layer 13, and by applying the corrosion prevention treatment agent to both sides of the barrier layer 13, the corrosion prevention treatment agent may be formed. The first corrosion prevention layer 12 may be formed at the same time. When providing corrosion prevention layers on both sides of the barrier layer 13, a method is adopted in which the barrier layer 13 is immersed in the corrosion prevention treatment agent, the corrosion prevention treatment agent is adhered to both sides of the barrier layer 13, and then heat drying is performed. However, it is also preferable to form the first and second corrosion prevention layers 12 and 14 at the same time.

Next, the resin layer 11 is formed on the first corrosion prevention layer 12 formed on the barrier layer 13.
When the resin layer 11 is formed by coating, the resin layer 11 is formed by applying a polyamic acid containing a colored pigment or a solvent-soluble polyimide coating liquid on the first corrosion prevention layer 12 and heating or drying the resin layer 11. It is formed. At this time, the anchor layer (undercoat layer) as described above may be formed on the first corrosion prevention layer 12, but it is preferable that the adhesive layer is not formed.
Further, when a resin layer 11 having a film formed in advance is used, the above-mentioned anchor layer (adhesive layer) is formed on the barrier layer 13 or the first corrosion prevention layer 12 by coating or the like. Dry if necessary.
After that, the polyimide film to be the resin layer 11 is laminated on the anchor layer, and if necessary, the resin layer 11 is formed.

After that, the adhesive layer 15 is formed on the second corrosion prevention layer 14 of the barrier layer 13 on which the resin layer 11 and the like are formed. Specifically, a layer made of the adhesive as described above is formed on the surface of the barrier layer 13 provided with the second corrosion prevention layer 14, and if necessary, it is heated and dried.

When the adhesive is a thermal laminating adhesive that does not contain an organic solvent, the components (A) and (B) are melt-kneaded to react both components, and then coated on the second corrosion prevention layer 14. By working, the adhesive layer 15 is formed.
For melt-kneading, a known device such as a uniaxial extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heating roll kneader or the like can be used. In order to suppress the decomposition of epoxy groups during melt-kneading, volatile components that can react with epoxy groups such as water should be removed from the device in advance, and if volatile components are generated during the reaction, degassing. It is desirable to discharge it to the outside of the device at any time. When the acid-modified polyolefin resin has an acid anhydride group as an acid functional group, it is preferable because the reactivity with the epoxy group is high and the reaction can be carried out under more mild conditions. The heating temperature at the time of melt-kneading is preferably selected from the range of 240 to 300 ° C. in that both components are sufficiently melted and do not thermally decompose. The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the adhesive in a molten state immediately after being extruded from the melt-kneading apparatus.

When the adhesive is a dry laminating adhesive containing an organic solvent, the component (A) or the component (A) and the component (B) are dissolved in the organic solvent, and then this solution is second-corroded. The adhesive layer 15 is formed by applying it on the prevention layer 14 and drying it. Further, the formation of the adhesive layer 15 may be performed as a series of steps using a known dry laminator or the like together with the laminating step with the sealant layer 20 described later.

After that, the sealant layer 16 and the formed adhesive layer 15 are arranged so as to be in contact with each other, and the laminated body is laminated. The laminate may be a dry laminate or a thermal laminate, but a dry laminate at 70 to 150 ° C. is preferable. The pressure at the time of dry lamination is preferably 0.1 to 0.5 MPa.
Specifically, a film constituting the sealant layer 20 is prepared in advance, the film is arranged on the adhesive layer 15, and then laminating is performed. The temperature of the laminate is not particularly limited as long as the sealant layer 16 is satisfactorily adhered to the second corrosion prevention layer 14 and the barrier layer 13 via the adhesive layer 15, and the adhesive layer 15 is not particularly limited. It can be determined in consideration of the material and melting point of the adhesive constituting the above. In the case of dry laminating, the temperature is generally 70 to 150 ° C, preferably 80 to 120 ° C.

The step of forming the adhesive layer 15 and the step of arranging the sealant layer 16 and performing (dry) laminating may be performed by using a (dry) laminating apparatus known as a series of steps.

The method for producing the resin-coated metal laminate 10 of the present embodiment is not limited to the above method, but when the resin layer 11 is formed by applying a polyamic acid, it is on the barrier layer 13 as described above. It is preferable to form the resin layer 11 via the first corrosion prevention layer 12 and then form the sealant layer 16 on the barrier layer 13 via the second corrosion prevention layer 14 and the adhesive layer 15. By doing so, the influence of heat when forming the resin layer 11 which is a polyimide layer using polyamic acid is not exerted on the resin of the sealant layer 16, and the material of the sealant layer 16 is selected. Wider width.

In this way, the resin-coated metal laminate 10 can be manufactured. The obtained laminate can be cut to a specified width and used.

Although one embodiment of the present invention has been described above based on the resin-coated metal laminate 10 shown in FIG. 1, the technical scope of the present invention is not limited to the above-described embodiment and deviates from the gist of the present invention. It is possible to make various changes to the extent that it does not.

[Battery exterior]
The battery exterior body of the second aspect of the present invention is a battery exterior body including the resin-coated metal laminate of the first aspect, has an internal space for accommodating the battery, and is the resin-coated metal laminate. The battery exterior is such that the side of the sealant layer is the side of the internal space. Specifically, it is obtained by molding the resin-coated metal laminate of the first aspect into a desired shape so that the sealant layer faces the internal space, and sealing the ends as necessary. ..
The shape, size, etc. of the battery outer body are not particularly limited, and can be appropriately determined according to the type of battery used.
The battery exterior may be composed of one member, or may be formed by combining two or more members (for example, a container body and a lid) as described later with reference to FIG. Good.

[battery]
The battery of the third aspect of the present invention includes the battery exterior of the second aspect.
Examples of the battery include a secondary battery such as a lithium ion battery which is a secondary battery, a capacitor such as an electric double layer capacitor, and the like using an organic electrolyte as an electrolytic solution. Since the resin-coated metal laminate of the present invention can have good chemical resistance (electrolyte resistance), it is possible to obtain a battery that can operate suitably even when an electrolytic solution containing LiPF ₆ or the like is used. It will be possible.
As an example, a perspective view of the secondary battery 50 is shown in FIG. The secondary battery 50 is a battery outer container 30 containing a lithium ion battery 37.
In the battery exterior container 30, the container body 40 made of the resin-coated metal laminate 10 of the first aspect of the present invention and the lid portion 43 made of the resin-coated metal laminate 10 are overlapped, and the peripheral edge portion 39 is heat-sealed. It is formed by. Reference numeral 38 is an electrode lead connected to the positive electrode and the negative electrode of the lithium ion battery 37.

The battery shown in FIG. 2 can be manufactured as follows.
First, as shown in FIG. 3A, the resin-coated metal laminate 10 is molded by drawing or the like so as to form a tray having recesses 41 to obtain a container body 40. The depth of the recess 41 can be, for example, 2 mm or more.
A lithium ion battery (lithium ion battery 37 in FIG. 2) is housed in the recess 41 of the container body 40.
Next, as shown in FIG. 3B, the lid portion 43 made of the resin-coated metal laminate 10 is superposed on the container body 40, and the flange portion 42 of the container body 40 and the peripheral edge portion 44 of the lid portion 43 are heat-sealed. By doing so, the secondary battery 50 shown in FIG. 2 can be obtained. That is, in the battery shown in FIG. 3, the upper surface of the container body 40 is covered with the lid portion 43, so that the recess 41 and the lid portion 43 form an internal space for accommodating the battery.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

[Examples 1 to 9, Comparative Example 1]
<Examples 1 to 7>
First, a stainless steel foil with a thickness of 15 μm is prepared as a barrier layer, anticorrosion treatment agents are applied to both sides of the stainless steel foil, and the mixture is heated and dried in an oven at 200 ° C. to prevent first corrosion with a thickness of 0.1 μm. A layer and a second corrosion prevention layer were formed on both sides, respectively. As the corrosion prevention treatment agent, a mixture of chromium fluoride, phosphoric acid and polyvinyl alcohol was used.
Next, a polyamic acid containing carbon black was applied onto the formed first corrosion prevention layer at the ratio shown in Table 1, and heated at 200 ° C. for 5 minutes to cause a dehydration condensation reaction, which is shown in Table 1. A thick resin layer was formed.

Further, an adhesive was applied on the second corrosion prevention layer formed above to form an adhesive layer having a thickness of 2 μm. As the adhesive, 5% by mass of epoxy resin was kneaded with maleic acid-modified polypropylene.
The adhesive layer in the laminate containing the metal foil and the sealant layer made of a polypropylene resin (block PP) film having a thickness of 15 μm were laminated by dry lamination.
Then, the resin-coated metal laminate was obtained by aging treatment at 60 ° C. for 2 days, then at 80 ° C. for 3 days, and then at 40 ° C. for 1 day.

<Example 8>
A resin-coated metal laminate was obtained in the same manner as in Examples 1 to 7 except that the first and second corrosion prevention layers were not provided on the stainless steel foil.

<Example 9, Comparative Example 1>
The first and second corrosion prevention layers were formed on both sides of the stainless steel foil in the same manner as in Examples 1 to 7.
Next, an adhesive was applied onto the formed first corrosion prevention layer to form an anchor layer (adhesive layer) having a thickness of 3 μm. A urethane-based adhesive was used as the adhesive.
Further, a polyimide film containing 10% by mass of carbon black and having the thickness shown in Table 1 was laminated on the formed anchor layer, and laminated by dry lamination by thermocompression bonding at 80 ° C.
Then, in the same manner as in Examples 1 to 7, a sealant layer was laminated on the second corrosion prevention layer via an adhesive, and a resin-coated metal laminate was obtained through aging.

(Measurement of tensile elongation)
With respect to the resin layer used in each of the above examples, the tensile elongation of the single layer of the resin layer was measured according to JIS-K-7127 "Plastic-Special Tensile Test Method-Test Conditions for Films and Sheets".
Specifically, the resin layers of each of the above examples were formed, and the tensile elongation was measured using an Instron type tensile tester (manufactured by Shimadzu Corporation).
The results are shown in Table 1 as "single layer tensile elongation".

(Thin film characteristics)
The total film thickness of the laminates obtained in each of the above examples was evaluated according to the following criteria. The results are shown in Table 1 as "thin film characteristics".
A: 40 μm or less B: Over 40 μm, 50 μm or less C: Over 50 μm

(Appearance of laminated body)
The laminates obtained in each of the above examples were visually observed and evaluated under the following evaluation conditions. The results are shown in Table 1 as "laminate appearance".
In the following evaluation criteria, B-1 and B-2 had the same degree of preference as a laminated body, and similarly, C-1 and C-2 had the same degree of preference.
A: No obvious defects such as peeling were observed, and the flatness was high.
B: No obvious defects such as peeling were observed, and the surface had sufficient flatness.
C-1: A portion with low flatness was observed.
C-2: There was some peeling between layers.
D: Peeling between layers occurred, and the flatness was very low.

(Battery exterior appearance)
A battery exterior was manufactured by deep drawing using the laminates obtained in each of the above examples. The obtained battery exterior was visually observed and evaluated under the following evaluation conditions. The results are shown in Table 1 as "Battery exterior appearance".
In the following evaluation criteria, B-1 and B-2 had the same degree of preference as the battery exterior, and C-1 and C-2 had the same degree of preference. ..
A: Both the corner portion and the flat portion of the battery exterior body formed by deep drawing have a uniform black color.
B-1: Black looks pale as a whole.
B-2: The shape of the corner portion by deep drawing was partially insufficient.
C-1: The black color at the corners appears light.
C-2: The black color of the corners is as uniform as that of the flat surface, but the corners are wrinkled.

From the results shown in Table 1, Examples 1 to 9 using the resin-coated metal laminate provided with the resin layer according to the present invention have excellent thin film characteristics, reduced surface defects, and batteries as compared with Comparative Example 1. It was confirmed that it has excellent characteristics when used as an exterior body.

10 Resin-coated metal laminate, 11 Resin layer, 12 1st corrosion prevention layer, 13 Barrier layer, 14 2nd corrosion prevention layer, 15 Adhesive layer, 16 Sealant layer, 30 Battery exterior container, 37 Lithium ion battery, 38 Electrode lead, 39 peripheral part, 40 container body, 41 concave part, 42 flange part, 43 lid part, 44 peripheral part, 50 secondary battery

Claims (8)

A method for producing a resin-coated metal laminate including at least a resin layer, a barrier layer, and a sealant layer in this order.
The resin layer is made of a polyimide resin containing a colored pigment.
The thickness of the resin layer is Ri 1~15μm der,
The barrier layer is a stainless steel foil having a thickness of 30 μm or less.
A method for producing a resin-coated metal laminate , which comprises applying a polyamic acid on the barrier layer without an adhesive layer and heating the barrier layer to form the resin layer . A method for producing a resin-coated metal laminate including at least a resin layer, a barrier layer, and a sealant layer in this order.
The resin layer is made of a polyimide resin containing a colored pigment.
The thickness of the resin layer is Ri 1~10μm der,
The barrier layer is a stainless steel foil having a thickness of 30 μm or less.
A method for producing a resin-coated metal laminate , which comprises applying a polyamic acid on the barrier layer without an adhesive layer and heating the barrier layer to form the resin layer . The method for producing a resin-coated metal laminate according to claim 1 or 2, wherein the colored pigment is carbon black. The method for producing a resin-coated metal laminate according to any one of claims 1 to 3, wherein the resin layer has a tensile elongation of 50% or more according to the method of JIS-K-7127 of the resin layer single layer. .. The method for producing a resin-coated metal laminate according to any one of claims 1 to 4, further comprising an anchor layer between the resin layer and the barrier layer. The method for producing a resin-coated metal laminate according to any one of claims 1 to 5, wherein the stainless steel foil is a surface-treated metal foil. The method for producing a resin-coated metal laminate according to any one of claims 1 to 6 , wherein the resin-coated metal laminate is for a battery exterior. A method for manufacturing a battery exterior body, which comprises a resin-coated metal laminate, has an internal space for accommodating a battery, and has a sealant layer side of the resin-coated metal laminate on the side of the internal space.
The resin-coated metal laminate is produced by the method for producing a resin-coated metal laminate according to any one of claims 1 to 7, and the resin-coated metal laminate is provided so that the sealant layer faces the internal space. A method for manufacturing a battery exterior body, which comprises molding.

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