JP2018015986A - Resin-coated metal laminate, battery outer package, and battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-coated metal laminate having excellent visibility and good physical properties such as strength, a battery exterior body provided with the resin-coated metal laminate, and a battery provided with the battery exterior body. A resin-coated metal laminate including at least a base material layer and a barrier layer in this order, wherein the base material layer contains a resin component and a colorant component, and the colorant component is 1 mass part or more is contained with respect to 100 mass parts of resin components, and the particle diameter of the said colorant component is 10 nm or more and 100 nm or less, The resin coating metal laminated body characterized by the above-mentioned. [Selection diagram] None

Description

  The present invention relates to a resin-coated metal laminate, a battery outer package, and a battery.

  In the field of exterior products and packaging for industrial products such as electronic devices and batteries, and daily necessaries such as food, beverages, cosmetics, and pharmaceuticals, in the field of packaging, resin films such as polyethylene and polypropylene, aluminum foil, etc. A resin-coated metal laminate obtained by combining and laminating metal foils is used.

  For example, an exterior body used for a battery such as a secondary battery may be described as the above resin-coated metal laminate (hereinafter referred to as “battery exterior laminate”) for the purpose of miniaturization and weight reduction. Is used). Such a laminated body for battery exterior is formed by drawing or the like so as to be a tray having a concave portion to obtain an exterior container body. Further, in the same manner as in the outer package container main body, a battery outer laminate is formed to obtain an outer package lid. After storing the battery body in the recess of the exterior body container body, the exterior body cover part is overlapped so as to cover the stored battery body, and the side edges of the container body and the exterior body cover part are bonded, thereby A battery in which the battery body is housed in the body is obtained.

Since the exterior body and the packaging body as described above are required to have gas barrier properties and various durability (heat resistance, water resistance, chemical resistance), metal foil such as aluminum foil or alloy foil is used for the barrier layer. It has been.
For example, Patent Document 1 discloses a molding packaging in which a mat layer (mat coat layer), an outer base material layer made of a heat resistant resin, a metal foil as a barrier layer, and an inner sealant layer made of a thermoplastic resin are laminated in this order. The materials are listed.

JP 2013-226838 A

Recently, the exterior and package as described above are required to have design properties, and attempts have been made to provide a printed layer containing a colorant on the resin-coated metal laminate.
However, when a separate print layer is provided, the visibility may be poor, such as small print loss (also referred to as “color loss”) in the print layer, concealment, and the like. In addition, the resin-coated metal laminate used for the battery exterior body is required to have a reduced total thickness. In the case where the total thickness of the laminate is equal to or less than that, if a separate printing layer is provided, it is necessary to thin the resin film layer serving as the substrate. When the thickness of the base resin film is thin, wrinkles are liable to occur during printing, resulting in poor workability.
In order to solve these problems, it can be recalled that the resin component and the colorant component forming the base material layer are kneaded so that the base material layer and the printing layer are combined into one layer.
However, as a result of studies by the present inventors, it has been found that physical properties such as rubbing resistance and strength of the laminate are reduced simply by kneading the resin component and the colorant component.

  The present invention has been made in view of the above circumstances, a resin-coated metal laminate having excellent visibility and good physical properties such as strength, a battery exterior body including the resin-coated metal laminate, and the battery exterior It is an object to provide a battery including a body.

  As a result of repeated studies to achieve the above object, the present inventors kneaded a predetermined amount of a resin component forming a base material layer and a specific colorant component, and combining the base material layer and the printing layer into one. It has been found that the above-mentioned problems can be solved by using a layer.

That is, the present invention employs the following configuration.
[1] A resin-coated metal laminate comprising at least a base material layer and a barrier layer in this order, wherein the base material layer contains a resin component and a colorant component, and the colorant component is the resin. 1 resin part or more is contained with respect to 100 mass parts of components, The particle size of the said colorant component is 10 nm or more and 100 nm or less, The resin-coated metal laminated body characterized by the above-mentioned.
[2] A resin-coated metal laminate comprising at least a base material layer, a barrier layer, and a sealant layer in this order, wherein the side on the base material layer side of the resin-coated metal laminate is folded upward. The resin-coated metal laminate according to [1], wherein the formed test piece has a rubbing resistance of 50 reciprocations or more when a rubbing test is performed on a smooth stainless steel shaft having a diameter of 1.5 cm under the following conditions.
(conditions)
-Test piece size: 7cm x 12.5cm
-Test machine installation conditions: Grasping a portion 2.5 cm above the side formed on the test piece-Test conditions: Pressing against a stainless steel shaft at a load of 200 g under room temperature conditions, reciprocating in the extending direction with a reciprocating width of 10 cm.
[3] The resin-coated metal laminate according to [1] or [2], wherein the colorant component is one or both of carbon black and carbon nanotubes.
[4] The resin-coated metal laminate according to any one of [1] to [3], wherein the barrier layer is made of an alloy foil, and the alloy foil is a stainless steel foil having a thickness of 50 μm or less.
[5] The resin-coated metal laminate according to any one of [1] to [4], wherein the base material layer is polyethylene terephthalate, polyamide, or polyimide having a thickness of 6 μm or more.
[6] The resin-coated metal laminate according to any one of [1] to [5], which has a mat layer on the base material layer.
[7] The resin-coated metal laminate according to [6], wherein the mat layer includes silica particles having a particle size of 2 μm or more and 5 μm or less, an acrylic urethane resin, or acrylic beads.
[8] A battery outer package comprising the resin-coated metal laminate according to any one of [1] to [7].
[9] A battery comprising the battery outer package according to [8].

  According to the present invention, there are provided a resin-coated metal laminate having excellent visibility and good physical properties such as strength, a battery outer package provided with the resin-coated metal laminate, and a battery provided with the battery outer package. be able to.

It is a schematic sectional drawing which shows an example of the resin coating metal laminated body which concerns on this invention. It is a perspective view which shows an example of the secondary battery produced using the resin coating metal laminated body which concerns on this invention. It is a perspective view which shows the process of manufacturing a secondary battery using the resin coating metal laminated body which concerns on this invention. It is a perspective view which shows the process of manufacturing a secondary battery using the resin coating metal laminated body which concerns on this invention. It is a schematic diagram of the testing machine used for the rubbing test of the resin-coated metal laminate according to the present invention.

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

<Resin-coated metal laminate>
The present invention is a resin-coated metal laminate comprising at least a base material layer and a barrier layer in this order, wherein the base material layer contains a resin component and a colorant component, and the colorant component is 1 mass parts or more is contained with respect to 100 mass parts of resin components, The particle diameter of the said colorant component is 10 nm or more and 100 nm or less, It is a resin-coated metal laminated body characterized by the above-mentioned.

<< First Embodiment >>
FIG. 1 is a cross-sectional view showing a schematic configuration of a resin-coated metal laminate 10 (hereinafter sometimes referred to as “laminate 10”) according to the first embodiment of the present invention. In addition, in order to clarify a characteristic part, the scale does not necessarily correspond with the actual aspect in all drawings, and the laminated body 10 is not limited to the scale of drawing.
The laminate 10 according to this embodiment includes a surface protective layer 11, a mat layer 12, a base material layer 13, a first adhesive layer 14, a first corrosion prevention layer 15, a barrier layer 16, a second corrosion prevention layer 17, It is a 9-layer configuration comprising 2 adhesive layers 18 and a sealant layer 19 in this order.

In the laminate 10 according to the present embodiment, the base material layer 13 contains a resin component and a colorant component. That is, the base material layer 13 serves as a base material layer and also serves as a printing layer. The base material layer 13 is formed by mixing a specific amount of constituent resin components and colorant components. For this reason, since the base material layer 10 exhibits design properties and at the same time, the resin component and the colorant component are directly mixed, no small printing omission occurs. Moreover, in this embodiment, since the base material layer 13 also serves as a print layer, it is not necessary to provide a separate print layer. For this reason, the total thickness of the laminated body 10 can be made thin, ensuring the thickness of the base material layer 13 enough.
Moreover, since the laminated body 10 which concerns on this embodiment does not need to provide a separate printing layer, it can reduce the number of processes and can reduce cost. Further, by eliminating the printing process, it is possible to solve the problem of missing prints and wrinkles that have been a problem in the printing process.
Each layer which comprises the laminated body 10 of this embodiment is mentioned later.

<< Second Embodiment >>
The resin-coated metal laminate of the second embodiment is a resin-coated metal laminate comprising at least a base material layer, a barrier layer, and a sealant layer in this order among the resin-coated metal laminate of the first embodiment. Then, the surface of the resin-coated metal laminate is formed by folding the surface of the base material layer side face up to form a side, and the rubbing resistance when a rubbing test is performed on a smooth stainless steel shaft under the following conditions is 50 That's it.
(conditions)
-Test piece size: 7cm x 12.5cm
-Test machine installation conditions: Grasping a portion 2.5 cm above the side formed on the test piece-Test conditions: Pressing against a stainless steel shaft at a load of 200 g under room temperature conditions, reciprocating in the extending direction with a reciprocating width of 10 cm.
As in the first embodiment, the resin-coated metal laminate of this embodiment is a laminate 10 having a nine-layer structure as shown in FIG.

FIG. 5 shows a schematic diagram of a testing machine 70 used in the present embodiment.
An example in the case of performing a rubbing test using the test apparatus 70 shown in FIG. 5 will be described.
The resin-coated metal laminate of the present invention cut out to 7 cm × 25 cm is formed by folding the surface of the base material layer 13 face up to form the side 71a.
A test piece 71 is installed at the tip of the sliding jig 72 of the test apparatus 70 shown in FIG. At this time, it is installed so as to grip a portion 2.5 cm above the side 71a. A stainless shaft 73 is attached so as to intersect the side 71a of the test piece 71. The test piece 71 is pressed against a stainless steel shaft 73 having a diameter of 1.5 cm with a load of 200 g, and the stainless steel shaft 73 is reciprocated in the extending direction indicated by reference numeral 74 under room temperature conditions. At this time, the reciprocating width L is 10 cm.
The laminate of this embodiment does not break even when rubbed 50 times or more under the above conditions. Since the laminated body 10 of this embodiment can increase the thickness of the base material layer 13 to the extent that the printing layer can be omitted, the friction resistance can be improved.

  Hereinafter, each layer will be described in detail.

[Surface protective layer 11]
The surface protective layer 11 has an arbitrary configuration in the present invention, and is provided on a mat layer 12 to be described later to improve printing characteristics when printing a pattern or a character on the surface of the laminate 10, that is, the surface protective layer 11. It is something to be made.

As a material for forming the surface protective layer 11, a processing agent commercially available as a release agent, a surfactant, a release agent, or the like, or a surface protective agent for forming the surface protective layer 11 can be used.
Specific examples of the surface protective agent include non-silicone release agents (release agents) such as polymers of vinyl monomers containing long chain alkyl groups and polymers of fluorinated alkyl vinyl monomers; interfaces such as fluorosurfactants Active agents; and the like.
The thickness of the surface protective layer 11 is preferably 0.1 μm or less, more preferably 0.0001 μm to 0.01 μm, and still more preferably 0.0005 μm to 0.005 μm.

[Matte layer 12]
In the present invention, it is preferable to have the mat layer 12. The mat layer is a layer for imparting mat properties to the laminate 10. The mat layer 12 provides not only a matte appearance but also an effect that it is difficult to see scratches on the surface of the laminate 10 as compared with a case where the glossiness is high.
Specifically, the mat layer 12 is preferably a layer made of a composition in which fine particles are dispersed in a main resin. A mat layer forming agent in which a resin and fine particles are dispersed in a solvent is thinly formed on the base material layer 13. More preferably, it is formed by coating. The fine particles contained in the mat layer 12 are preferably substantially spherical, and the size is preferably 1 to 10 μm, particularly preferably 2 to 5 μm in terms of the average particle size.
Among them, the fine particles of the mat layer 12 are preferably silica particles having a particle size of 2 μm or more and 5 μm or less, an acrylic urethane resin, or acrylic beads, and a combination thereof is more preferable. The thickness of the mat layer 12 can be, for example, 0.1 μm to 1 mm, and preferably 0.5 μm to 100 μm.

[Base Material Layer 13]
The base material layer 13 contains a resin component and a colorant component. When the base material layer 13 contains a resin component and a colorant component, the base material layer 13 can also serve as a printing layer. For this reason, it is not necessary to provide a separate printing layer, the number of processes can be reduced, and cost can be reduced. Further, by eliminating the printing process, it is possible to solve the problem of missing prints and wrinkles that have been a problem in the printing process.

Resin component The resin component is not particularly limited as long as it has sufficient mechanical strength. For example, polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); nylon A layer (film) made of polyamide resin such as (Ny); polyolefin resin such as expanded polypropylene (OPP); polyether ether ketone (PEEK), polyphenylene sulfide (PPS), or the like can be used. In particular, when the resin-coated metal laminate is used for a battery exterior body, there is no risk of dissolution in the electrolyte solution, and since the line running property is good, a layer made of PET, polyamide resin, and polyimide resin is used. More preferred.

Colorant component The colorant component is a pigment component having a particle size of 10 nm to 100 nm. When the particle size is equal to or greater than the above lower limit, sufficient concealment can be imparted to the base material layer 13 and color loss can be prevented. Moreover, sufficient intensity | strength can be provided to the base material layer 13 because a particle size is below the said upper limit.

The colorant component is preferably one or both of carbon black and carbon nanotubes.
When either one or both of carbon black and carbon nanotube is employed as the colorant component, the tensile strength and elongation of the base material layer 13 can be improved.
As will be described later, a stainless steel foil is suitably used for the barrier layer 16. However, stainless steel foil is hard and difficult to stretch, and is sensitive to the pressing pressure setting and drawing depth during drawing, and depending on the processing conditions, tearing due to stress concentration occurs.
Therefore, when the base layer 13 having high tensile strength and elongation, which employs one or both of carbon black and carbon nanotubes as the colorant component, is used, the base layer 13 complements the poor workability of the stainless steel foil. In addition, the workability such as drawability can be improved. Moreover, when the tensile strength / elongation of the base material layer 13 is high, the occurrence of cracks in the base material layer 13 can be suppressed.

  In the present invention, the colorant component is contained in an amount of 1 part by mass or more, preferably 1.5 parts by mass or more, and more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin component. When two or more kinds of colorant components are contained, the total amount of the colorant components may be set to the above-described blending amount. When the content of the colorant component is not less than the above lower limit value, a base material layer free from color loss can be obtained.

The thickness of the base material layer 13 can be 1-50 micrometers, for example, 1-30 micrometers is preferable and 3-15 micrometers is more preferable.
In the present invention, the base material layer 13 is preferably polyethylene terephthalate, polyamide, or polyimide having a thickness of 6 μm or more.

  The base material layer 13 may have a single layer structure or a multilayer structure. Examples of the base material layer 13 having a multilayer structure include a two-layer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy). The base material layer 13 may have a multilayer structure in which three or more films are laminated.

[First adhesive layer 14]
The first adhesive layer 14 may have any configuration in the present invention, and may have the same configuration as the second adhesive layer 18 described later, and an adhesive such as a general urethane adhesive or epoxy adhesive. The layer which consists of may be sufficient. The thickness of the 1st adhesive bond layer 14 can be 0.5-10 micrometers, for example. By setting the thickness within this range, the base material layer 13 and the barrier layer 17 can be bonded with high adhesive force, and delamination can be prevented.

[First corrosion prevention layer 15 and second corrosion prevention layer 17]
The first corrosion prevention layer 15 and the second corrosion prevention layer 17 are both arbitrarily structured in the present invention, and the corrosion of the barrier layer 16 (details will be described later), preferably a metal layer, is caused by rust or the like. It is a layer to prevent.
The first and second corrosion prevention layers 15 and 17 are both optional, but when the laminate 10 of the present invention is used in an application that can come into contact with a component capable of enhancing metal corrosion, the first and second corrosion prevention layers 15 and 17 may be used. 2 It is preferable to provide the corrosion prevention layers 15 and 17 on the surface of the barrier layer 16. For example, when the laminated body 10 of the present invention is used for battery exterior use, there is a risk that a chemical solution such as an electrolyte may leak from the contained battery, and the leaked chemical solution may corrode the metal of the barrier layer 16. Therefore, it is preferable to subject the surface of the barrier layer 16 to a corrosion prevention treatment. In the case of battery exterior use, the side that is highly likely to come into contact with the electrolyte is the side of the battery to be encapsulated, that is, the side of the sealant layer 19 of the barrier layer 16, and therefore at least the second corrosion prevention layer 17 is provided. It is preferable to provide it.

The first and second corrosion prevention layers 15 and 17 preferably contain a metal halide compound, and a metal halide compound as described later may be directly plated on the surface of the barrier layer 16. By providing the first and second corrosion preventing layers 15 and 17 as described above, it becomes possible to give the barrier layer 16 a good rust preventing effect.
The first and second corrosion prevention layers 15 and 17 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 15 and 17 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 15. 17 is preferably formed by applying an aqueous solution containing a halogen compound, a water-soluble resin, and a chelating agent or a crosslinkable compound on the lower layer, followed by drying and curing. Hereinafter, the material forming the first and second corrosion prevention layers 15 and 17 may be referred to as a “corrosion prevention treatment agent”.

(Metal halide compounds)
The metal halide compound has an action of improving chemical resistance such as resistance to electrolytic solution. That is, it is possible to passivate the surface of the barrier layer 16 and enhance the corrosion resistance against the electrolytic solution.
When the first and second corrosion prevention layers 15 and 17 contain a water-soluble resin described later, the metal halide compound also has a function of crosslinking the water-soluble resin.
The metal halide compound is preferably water-soluble in consideration of miscibility with a water-soluble resin described later and the case where it is dispersed and applied in a water-soluble medium.
Examples of the metal halide compound include chromium halide, iron halide, zirconium halide, titanium halide, hafnium halide, titanium hydrohalic acid, and salts thereof. Examples of the halogen atom include chlorine, bromine and fluorine, with chlorine or fluorine being preferred. Particularly preferred is fluorine. When the halogenated metal compound contains fluorine, depending on conditions, it becomes possible to generate hydrofluoric acid (HF) from the corrosion inhibitor.
Further, the metal halide compound may have a halogen atom or an atom other than a metal.
Especially, as a metal halide compound, the chloride or fluoride of iron, chromium, manganese, or zirconium is 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 resins.

The polyvinyl alcohol resin or derivative thereof 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 monomer or a copolymer thereof. The polyvinyl alcohol resin may be modified.
As a polymer of a vinyl ester monomer or a copolymer thereof, a homopolymer of a vinyl ester monomer such as a fatty acid vinyl ester such as vinyl formate, vinyl acetate, vinyl butyrate, an aromatic vinyl ester such as vinyl benzoate, or the like Examples thereof include copolymers and copolymers of other monomers copolymerizable therewith. Other monomers that can be copolymerized are not particularly limited.
Moreover, polymerization and copolymerization can be performed by a conventional method.

Polyvinyl ether resins 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, 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 monomer include those similar to the other monomers copolymerizable with the vinyl ester monomer described above.
In particular, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, and other polyvinyl ether resins containing a hydroxyl group-containing aliphatic vinyl ether as a monomer, such as monovinyl ethers of various glycols and polyhydric alcohols, are water-soluble. And a crosslinking reaction with respect to a hydroxyl group is possible, so that it can be suitably used in the present invention.

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

(Chelating agent)
A chelating agent is a material that can coordinate to a metal ion to form a metal ion complex.
The chelating agent binds a metal compound (such as chromium oxide) derived from a metal halide compound and the water-soluble resin to increase the compressive strength of the first and second corrosion prevention layers 15 and 17. Even if the thickness of the second corrosion prevention layers 15 and 17 is, for example, more than 0.2 μm and 1.0 μm or less, the first and second corrosion prevention layers 15 and 17 become brittle and cause cracks and peeling. There is no. For this reason, the adhesive strength and adhesiveness between the barrier layer 16 and the 1st, 2nd adhesive bond layers 14 and 18 can be improved.
In addition, 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, aminocarboxylic acid chelating agents, phosphonic acid chelating agents, oxycarboxylic acid chelating agents, (poly) phosphoric acid chelating agents, and inorganic phosphoric acid can be used.
Among these chelating agents, phosphoric acid chelating agents (phosphoric acid compounds) such as phosphonic acid chelating agents and (poly) phosphoric acid chelating agents are preferred, and phosphonic acid chelating agents are more preferred.

(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 aforementioned water-soluble resin and the crosslinkable compound form a dense crosslink structure in the first and second corrosion preventing layers 15 and 17, and the surface of the barrier layer 16 is passive. And corrosion resistance can be further improved.
The crosslinkable compound is not particularly limited as long as it can form a crosslinked structure by reacting with a hydrophilic group (for example, carboxy group, carboxylic acid group, etc.) in the water-soluble resin. Examples thereof include compounds having an epoxy group and compounds having an oxazoline group.

  In the corrosion prevention treatment agent, either 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 15 and 17 is preferably 0.05 μm or more, and more preferably more than 0.1 μm. Moreover, 1.0 micrometer or less is preferable and 0.5 micrometer or less is more preferable.

[Barrier layer 16]
In this embodiment, the barrier layer 16 consists of a metal foil strip or an alloy foil strip.
The barrier layer 16 plays an important role in the laminate 10 in order to reduce leakage of contents sealed by the laminate (for example, battery leakage). In addition, by using a metal having high mechanical strength, it is possible to reduce the occurrence of pinholes when forming the concave portion for battery storage by drawing using the laminate 10, and as a result, the laminate is hermetically sealed. It is possible to reduce leakage of the content that has been made (for example, battery leakage).

The barrier layer 16 is not particularly limited as long as it is a metal foil strip or alloy foil strip obtained by thinly spreading a metal or alloy, and a metal such as aluminum, copper, lead, zinc, iron, nickel, titanium, or chromium. Foil; alloy foil such as stainless steel can be used. The stainless steel foil is not particularly limited as long as it is made of stainless steel such as austenite, ferrite, and martensite. Examples of the austenite type include SUS304, 316, 301, etc., examples of the ferrite type include SUS430, and examples of the martensite type include SUS410.
Among these, as the metal foil strip or the alloy foil strip, aluminum foil or stainless steel foil is preferable from the viewpoint of workability, availability, price, strength (puncture strength, tensile strength, etc.), corrosion resistance, and the like. Stainless steel foil is particularly preferred.

  The thickness of the barrier layer 16 is preferably 100 μm or less, preferably 5 to 40 μm, more preferably 10 to 30 μm, and particularly preferably 10 to 20 μm. By setting it to the above lower limit value or more, sufficient mechanical strength is given to the laminate 10, and the durability of the battery can be enhanced when used for a battery such as a secondary battery. Further, by setting the thickness of the barrier layer 16 to be equal to or less than the above upper limit value, the laminate 10 can be made sufficiently thin, and sufficient drawability can be given.

[Second adhesive layer 18]
The second adhesive layer 18 is an arbitrary layer in the present invention, and is a layer provided for bonding the sealant layer 19 and the barrier layer 16 having the second corrosion prevention layer 17 formed on the surface thereof. .
The material for forming the second adhesive layer 18 is not particularly limited as long as it can adhere the above layer satisfactorily. For example, it satisfies the adhesiveness and the storage elastic modulus. From the viewpoint of obtaining, a layer made of an adhesive containing an acid-modified polyolefin resin (A) and a compound (B) containing a plurality of epoxy groups is preferable.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “(A) component”, and the compound (B) containing a plurality of epoxy groups may be referred to as “(B) component”.

(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 a carboxylic anhydride group is contained in the polyolefin-based resin. It has a functional group.
The component (A) can be obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an acid functional group-containing monomer with an olefin. Especially, as (A) component, what was obtained by acid-modifying polyolefin resin is preferable.

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

  Among these, as the component (A), maleic anhydride-modified polypropylene is preferable from the viewpoints 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) may be a low molecular compound or a high molecular 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 dry laminating adhesive, the component (B) is preferably a low molecular 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 phenoxy resins synthesized from bisphenols and epichlorohydrin; phenol novolac type epoxy resins; bisphenol type epoxy resins. Among these, it is preferable to use a phenol novolac type epoxy resin because it has a high epoxy content per molecule and can form a particularly dense cross-linked structure 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 adhered to the adherend (especially the first corrosion prevention layer 15). By functioning as an adhesive functional group with respect to a functional group such as a carboxy group, it is possible to exhibit excellent adhesion to the sealant layer 19 and the barrier layer 16 having the second corrosion prevention layer 17 on the surface. It is thought that it becomes.
In addition, a part of the acid functional group of the component (A) reacts with a part of the epoxy group of the component (B), and the crosslinked structure of the component (A) and the component (B) has a second adhesive layer. As a result, the strength of the second adhesive layer 18 is reinforced by this cross-linked structure, and it is considered that good durability is obtained along with excellent adhesiveness.

  In the 2nd adhesive bond layer 18, it is preferable that 1-20 mass parts of (B) component are contained with respect to 100 mass parts of (A) component, and with respect to 100 mass parts of (A) component, 5-10 mass parts of (B) component are more preferable, and 5-7 mass parts of (B) component are especially preferable with respect to 100 mass parts of (A) component.

(Optional component)
The adhesive used in the present invention may or may not contain an organic solvent.
By using an organic solvent as a liquid adhesive, a solvent-type dry laminate adhesive can be obtained. The second adhesive layer 18 is formed by applying and drying such a liquid adhesive on the lower layer (for example, the surface of the barrier layer 16 provided with the second corrosion prevention layer 17). Can do. By selecting application instead of extrusion, the adhesive layer can be formed with a thinner layer, and the adhesive layer can be made thinner and the entire laminate using the adhesive layer can be made thinner.
On the other hand, when it does not contain an organic solvent, an adhesive layer suitable for heat lamination or the like can be formed by melt-kneading the component (A) and the component (B) and then extrusion-molding.

  In the case of containing an organic solvent, the organic solvent to be used preferably dissolves the above component (A), the component (B), and other optional components used as necessary (details will be described later) to make a uniform solution. The solvent is not particularly limited as long as it can be used, and any solvent can be used from among known solvents for solution-type adhesives.

  An organic solvent may be used individually by 1 type, and may be used as a mixed solvent combining 2 or more types. When a mixture of a plurality of types of organic solvents is used, the ratio of each organic solvent is not particularly limited. For example, when a combination of toluene and methyl ethyl ketone is used, the mixing ratio is toluene: methyl ethyl ketone = 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 further contain other components in addition to the component (A), the component (B) and the organic solvent. Examples of other components include miscible additives and additional resins. More specifically, a catalyst, a crosslinking agent, a plasticizer, a stabilizer, a colorant, 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 to less than 50 parts by mass. It is preferred that That is, in the solid content of the adhesive, more than half of the mass ratio is the component (A), and the adhesive used in the present invention has the component (A) as a main component. More preferably, it is 0.5-30 mass parts of (B) component with respect to 70-99.5 mass parts of (A) component; More preferably, with respect to 80-98 mass parts of (A) component ( B) 2 to 20 parts by mass of component; (A) 5 to 10 parts by mass of component (B) are particularly preferable with respect to 90 to 95 parts by mass of component.

  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, also when it contains an arbitrary component, (A) component will be more than 50 mass parts in the total solid of an adhesive agent. For example, in the total solid content, 70 to 99.5 parts by mass of component (A), 0.5 to 29.5 parts by mass of component (B), and 0.5 to 29.5 parts by mass of other components And an adhesive containing

  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 each component such as the component (A), the component (B), and the optional component can be dissolved satisfactorily. In general, however, the solid content concentration is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass.

  The thickness of the 2nd adhesive bond layer 18 can be 0.1-5 micrometers, for example, and 0.5-2 micrometers is preferable. By setting the thickness within this range, the sealant layer 19 and the barrier layer 16 provided with the second corrosion prevention layer 17 can be bonded with high adhesive force, and delamination can be prevented.

[Sealant layer 19]
The sealant layer 19 is a layer that allows the laminates 10 of the present invention to be stacked and bonded together by heat sealing.
The sealant layer 19 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 viewpoints of 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. .
Especially, since adhesiveness with the 2nd adhesive bond layer 18 improves, a homopolypropylene (propylene homopolymer; hereafter may be called "homo PP"), a block copolymer of propylene-ethylene (henceforth). Polypropylene resins such as a random copolymer of propylene-ethylene (hereinafter sometimes referred to as “random PP”) are preferred. Among these, homo PP or block PP is more preferable, and since the mechanical strength is excellent, it is particularly preferable to include block PP.
The sealant layer 19 may have a single layer structure or a multilayer structure.

The melting point of the layer made of polyolefin used for the sealant layer 19 is not particularly limited as long as it has heat resistance necessary for the laminate 10.
The thickness of the sealant layer 19 can be, for example, 1 to 50 μm, and preferably 5 to 30 μm.

  The thickness of the laminate 10 is preferably 10 to 100 μm, more preferably 20 to 80 μm, and still more preferably 30 to 60 μm. According to the present invention, since the base material layer also functions as a print layer and it is not necessary to provide a separate print layer, the thickness of the laminated body 10 can be set to the upper limit value or less. Moreover, since the thickness of the base material layer 13 can be ensured while making the thickness of the laminated body 10 below the said upper limit, it can be set as the laminated body which improved friction resistance.

(Manufacturing method of the laminated body 10)
Although the method of manufacturing the laminated body 10 of this invention is not specifically limited, For example, it can manufacture as follows.

First, the mat layer forming agent is applied to one surface of the base material layer 13, and the mat layer 12 is formed by drying using an oven or the like. The mat layer forming agent can be applied using a known coating apparatus such as a bar coater. The temperature at the time of drying is not particularly limited, and is appropriately formed according to the heat resistance of the material of the base material layer 13, but it is usually preferably performed at about 70 to 80 ° C. The formed mat layer 12 is preferably aged in advance before moving to the next step.
Aging can be performed at about 38 to 60 ° C. for 3 to 30 hours.
The base material layer 13 used here is the base material layer 13 described above, and is a base material layer containing a predetermined amount of a resin component and a specific colorant component.
Thereafter, a surface protective agent is applied on the formed mat layer 12 to form the surface protective layer 11. The surface protective layer 11 can be formed in the same manner as the mat layer 12. Aging may or may not be performed.
The original fabric of the three-layer laminate (surface protective layer 11, mat layer 12, and base material layer 13) can be obtained by the above procedure.

  On the other hand, a metal foil or the like to be the barrier layer 17 is prepared, and the first corrosion prevention layer 15 and the second corrosion prevention layer 17 are formed on both surfaces thereof.

  Specifically, after applying a corrosion inhibitor as described above to the surface of the barrier layer 16, it is dried by heating. At this time, only the second corrosion prevention layer 17 may be formed by applying the corrosion prevention treatment agent only to one side of the barrier layer 16, or by applying the corrosion prevention treatment agent to both sides of the barrier layer 16, The first corrosion prevention layer 14 may be formed at the same time. In addition, when providing a corrosion prevention layer on both surfaces of the barrier layer 16, a method is adopted in which the barrier layer 16 is immersed in the corrosion prevention treatment agent and the corrosion prevention treatment agent is adhered to both surfaces of the barrier layer 16 and then dried by heating. It is also preferable to form the first and second corrosion prevention layers 15 and 17 simultaneously.

  Next, a second adhesive layer 18 is formed on the second corrosion prevention layer 17 on the surface of the barrier layer 16. Specifically, a layer made of the adhesive as described above is formed on the surface of the barrier layer 16 on which the second corrosion prevention layer 17 is provided, and is heated and dried as necessary.

When the adhesive is an adhesive for thermal lamination that does not contain an organic solvent, the components (A) and (B) are melted and kneaded to react both components, and then applied onto the second corrosion prevention layer 17. Then, the second adhesive layer 18 is formed by drying.
For melt kneading, a known apparatus such as a single screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. In order to suppress decomposition of the epoxy group during melt-kneading, volatile components that can react with the epoxy group such as moisture are removed beforehand from the apparatus, and degassing occurs when volatile components are generated during the reaction. It is desirable to discharge from the device as needed. 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 performed under milder 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 not thermally decomposed. The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the molten adhesive immediately after being extruded from the melt-kneading apparatus.

  When the adhesive is an adhesive for dry laminate containing an organic solvent, the component (A) and the component (B) are dissolved in the organic solvent, and then this solution is applied onto the second corrosion prevention layer 17. Then, the second adhesive layer 18 is formed by drying. The formation of the second adhesive layer 18 may be performed as a series of steps using a known dry laminator or the like together with a laminating step with a sealant layer 19 described later.

Thereafter, the sealant layer 19 and the formed second adhesive layer 18 are arranged so as to contact each other, and the laminate is laminated. The laminate may be a dry laminate or a thermal laminate, but a dry laminate at 70 to 150 ° C. is preferred. The pressure during dry lamination is preferably 0.1 to 0.5 MPa.
Specifically, a film constituting the sealant layer 19 is prepared in advance, and the film is placed on the second adhesive layer 18 and then laminated. The temperature of the laminate is not particularly limited as long as it is a temperature at which the sealant layer 19, the second corrosion prevention layer 17, and the barrier layer 16 are favorably bonded via the first adhesive layer. It can be determined in consideration of the material and melting point of the adhesive constituting the agent layer 18. The temperature in the case of dry lamination is generally 70 to 150 ° C, and preferably 80 to 120 ° C.

Since the laminate 10 of the present invention has a structure in which the sealant layer 19, the second corrosion prevention layer 17 and the barrier layer 16 are bonded via the second adhesive layer 18, the dry laminate as described above is applied at the time of bonding. It can also be adopted. By adopting dry lamination as required, the temperature during lamination can be greatly reduced.
In general, when high heat is applied to a metal foil that has low thermal conductivity and is difficult to expand, distortion (curl) is likely to occur in the width direction of the metal foil. When performing thermal lamination using such a metal foil, heat does not propagate sufficiently in the plane, and there is a part that is not in contact with the thermocompression roller in the width direction, that it is not in contact with the roll, The distortion itself may cause creases and wrinkles during thermocompression bonding. In addition, when heating to a high temperature at which the metal foil is not distorted, the production efficiency may be reduced due to a reduction in processing speed or an increase in the amount of heat required. In addition, by lowering the temperature at the time of laminating, it becomes possible to prevent whitening due to heat of the sealant layer 20, etc., preventing deterioration of the sealant layer 19, and widening the selection range of the sealant layer 19.
And when employ | adopting a dry laminate in manufacture of the laminated body 10 of this invention, generation | occurrence | production of a crease | fold, wrinkles, resin whitening etc. can be suppressed, and the suitable laminated body 10 can be manufactured with high production efficiency.

  In addition, you may perform the process of forming the 2nd adhesive bond layer 18, and the process of arrange | positioning the sealant layer 19 (dry) lamination using a well-known (dry) laminating apparatus as a series of processes.

  In this way, an original fabric of the five-layer laminate (first corrosion prevention layer 16, barrier layer 17, second corrosion prevention layer 18, second adhesive layer 19, and sealant layer 20) can be obtained.

  Finally, an adhesive is applied onto the first corrosion prevention layer 15 of the obtained five-layer laminate to form the first adhesive layer 14, and the first adhesive layer 14 and the base material of the three-layer laminate Dry lamination or the like is performed with the layer 13 facing the layer 13. Then, the laminated body 10 which consists of all 10 layers can be manufactured by performing an aging process as needed.

  As described above, one embodiment of the present invention has been described based on the laminate 10 shown in FIG. 1, but the technical scope of the present invention is not limited to the above-described embodiment, and does not depart from the spirit of the present invention. Various changes can be made.

In the laminate 10 shown in FIG. 1, the first corrosion prevention layer 15 and the second corrosion prevention layer 17 are formed on both surfaces of the barrier layer 16, but these are not essential components, and only one of them is formed. It does not have to be formed together. When only one of them is formed, it is preferable to provide only the second corrosion prevention layer 17 on the inner layer side.
In the laminate 10 shown in FIG. 1, the first adhesive layer 14 is formed between the base material layer 13 and the barrier layer 16, and the second adhesive layer is interposed between the barrier layer 16 and the sealant layer 19. 18 is formed. However, these are not essential components, and only one of them may be formed or not formed together.

  For example, the surface protective layer 11 may not be provided and an eight-layer configuration may be used. The first and second corrosion prevention layers 15 and 17 may be omitted, and a seven-layer configuration may be used. Further, the first and second adhesive layers 15 and 18 and the first and second corrosion prevention layers 16 and 17 are not provided, and the surface protective layer 11, the mat layer 12, the base material layer 13, the barrier layer 16 and the sealant layer 19 are provided. It is good also as a 5 layer structure. Furthermore, it is good also as an 11-layer structure by adding arbitrary layers.

<Battery exterior>
The second aspect of the present invention is a battery outer package including the resin-coated metal laminate according to the first aspect of the present invention.
The battery outer package is a battery outer package including the resin-coated metal laminate of the first aspect, and has an internal space for storing a battery, and the sealant layer side of the resin-coated metal laminate is the internal space. It is the battery exterior body used as the side. 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, and the like of the battery outer package are not particularly limited, and can be determined as appropriate according to the type of battery used.
The battery exterior body 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 will be described later with reference to FIG. Good.

<Battery>
The battery according to the third aspect of the present invention includes the battery outer package according to the second aspect.
Examples of the battery include a secondary battery such as a lithium ion battery that is a secondary battery, and a capacitor that uses an organic electrolyte as an electrolyte, such as a capacitor such as an electric double layer capacitor. Since the laminated body for battery exterior according to the present invention has high electrolytic solution 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.
As an example, a perspective view of the secondary battery 40 is shown in FIG. The secondary battery 40 is one in which a lithium ion battery 27 is included in a battery exterior container 21.
The battery exterior container 21 is formed by stacking the container main body 30 made of the resin-coated metal laminate 10 and the lid portion 33 made of the resin-coated metal laminate 10 according to the first aspect of the present invention, and heat-sealing the peripheral portion 29. It is formed by. Reference numeral 28 denotes an electrode lead connected to the positive electrode and the negative electrode of the lithium ion battery 27.

The battery shown in FIG. 2 can be manufactured as follows.
First, as shown in FIG. 3 (a), the resin-coated metal laminate 10 is pressed from the sealant layer side of the resin-coated metal laminate 10 by drawing or the like so as to form a tray having a recess 31. Thus, the container body 30 is obtained. The depth of the recessed part 31 can be 2 mm or more, for example.
A lithium ion battery (lithium ion battery 27 in FIG. 2) is accommodated in the recess 31 of the container body 30.
Next, as shown in FIG. 3B, the lid portion 33 made of the resin-coated metal laminate 10 is overlaid on the container body 30, and the flange portion 32 of the container body 30 and the peripheral portion 34 of the lid portion 33 are heat sealed. By doing so, the secondary battery 40 shown in FIG. 2 is obtained. That is, in the battery shown in FIG. 3, the upper surface of the container body 30 is covered with the lid portion 33, whereby an internal space for accommodating the battery is formed by the concave portion 31 and the lid portion 33.

The battery according to the present invention can also be manufactured as follows.
First, as shown in FIG. 4A, a part of one end side in the longitudinal direction of the rectangular resin-coated metal laminate 50 is pressed and molded from the sealant layer side of the resin-coated metal laminate 50 by drawing or the like. Then, a molded body 55 having the recess 51 is obtained. The depth of the recessed part 51 can be 2 mm or more, for example.
Next, although not shown, the lithium ion battery (lithium ion battery 27 in FIG. 2) is accommodated in the recess 51 of the molded body 55.

    Next, the molded body 55 is bent toward the sealant layer so as to form a fold line L extending in the short direction of the molded body 55 at a part on the other end side where the concave portion 51 is not formed. Here, in the molded body 55, the region on the recess 51 side with respect to the fold line L is referred to as a “first region 551”, and the region on the opposite side of the fold line L from the recess 51 is referred to as a “second region 552”.

    Next, the sealant layer around the recess 51 in the first region 551 is overlaid with the sealant layer (peripheral portion 54) overlapping the periphery 52 in the second region 552. As a result, the second region 552 overlaps the concave portion 51 of the first region 551.

    Next, as shown in FIG. 4B, the secondary battery 60 having the battery outer package made of one member is obtained by heat-sealing the sealant layer around the recess 51 and the sealant layer in the second region 552. can get. That is, in the battery shown in FIG. 4B, the upper surface of the recess 51 is covered with the second region 552, so that the recess 51 and the second region 552 form an internal space that accommodates the battery.

    EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Examples 1 to 12, Comparative Examples 1 to 4, Reference Example 1>
First, a single-sided corona-treated substrate film having a thickness of 6 μm was prepared. The base film is a base film described as “base layer” in Table 1 below. Specifically, it is a base film having a specific amount of each resin component and each colorant component shown in Table 1 and a thickness shown in Table 1.
A mat layer forming agent (90 parts by mass of acrylic urethane resin, 10 parts by mass of silica particles having a particle size of 2 μm, and 1 part of acrylic beads (particle size of 5 μm) was used on the corona-treated surface of the base film. A mat layer forming agent in which 30 parts by mass of solid content was dispersed in methyl ethyl ketone so as to have a solid content of 30% by mass, and a solid content of 30% by mass) was applied at 6.0 g / m ² .
Then, it heated for 30 second in 70 degreeC-80 degreeC oven, and formed the mat layer.
Then, it left still for 8 hours on 40 degreeC conditions, and performed aging. The average thickness of the mat layer was 5 μm.
Then, after applying a surface protective agent (long-chain alkyl pendant release agent, solid content 0.003% by mass) on the mat layer at 3 g / m ² using a bar coater, in an oven at 80 ° C. The surface protective layer was formed by heating and drying for 30 seconds. The thickness of the surface protective layer was 0.001 μm. Thereafter, it was slit to a specified width.

Moreover, the metal foil or alloy foil shown in Table 1 is prepared as a barrier layer, a corrosion inhibitor (coating amount 4 g / m ² ) is applied to both surfaces of the metal foil or alloy foil, and is heated and dried in an oven at 200 ° C. Then, a first corrosion prevention layer and a second corrosion prevention layer having a thickness of 0.2 μm were formed on both sides. As the corrosion inhibitor, a mixture of chromium fluoride, phosphoric acid and polyvinyl alcohol was used.
Next, a second adhesive was applied on the formed second corrosion prevention layer to form a second adhesive layer having a thickness of 3 μm. The 2nd adhesive agent used what knead | mixed 5 weight part of epoxy resins with the maleic acid modified polypropylene.
The second adhesive layer in the laminate including the metal foil and the sealant layer made of a polypropylene resin (block PP) film having a thickness of 20 μm were laminated by dry lamination.
Then, after applying the first adhesive at 4.0 g / m ² on the first corrosion prevention layer using a gravure coater, heating in an oven at 80 ° C. for 30 seconds to form the first adhesive layer did. A urethane-based adhesive was used as the first adhesive.
This 1st adhesive bond layer and the base material layer in the laminated body obtained above were made to oppose, and it laminated | stacked by 80 degreeC dry lamination.
Thereafter, after aging treatment at 60 ° C. for 3 days, surface protective layer / matte layer / base material layer / first adhesive layer / first corrosion prevention layer / barrier layer / second corrosion prevention layer / second adhesive layer / A resin-coated metal laminate having a laminate structure of sealant layers was obtained.

<Comparative Example 5>
First, a single-sided corona-treated PET film having a thickness of 6 μm was prepared. A mat layer forming agent (90 parts by mass of acrylic urethane resin, 10 parts by mass of silica particles having a particle size of 2 μm, and 1 mass of acrylic beads (particle size of 5 μm) was applied to the corona-treated surface of this PET film using a bar coater. Part, and a mat layer forming agent dispersed in methyl ethyl ketone so as to have a solid content of 30% by mass, solid content of 30% by mass) was applied at 6.0 g / m ² .
Then, it heated for 30 seconds in 70 degreeC-80 degreeC oven, and formed the mat | matte layer.
Then, it left still for 8 hours on 40 degreeC conditions, and performed aging. The average thickness of the mat layer was 5 μm.
Next, a black ink having a solid content of 25% by mass was applied to the surface opposite to the surface on which the mat layer of the PET film was formed, using a bar coater at 5.0 to 5.5 g / m ² . Then, it heated in 70 degreeC-80 degreeC oven, and formed the colored layer.
Then, after applying a surface protective agent (long-chain alkyl pendant release agent, solid content 0.003% by mass) on the mat layer at 3 g / m ² using a bar coater, in an oven at 80 ° C. The surface protective layer was formed by heating and drying for 30 seconds. The thickness of the surface protective layer was 0.001 μm. Thereafter, it was slit to a specified width.

Moreover, the metal foil or alloy foil shown in Table 1 is prepared as a barrier layer, a corrosion prevention treatment agent (application amount: 12 g / m ² ) is applied to both surfaces of the metal foil or alloy foil, and is heated and dried in an oven at 200 ° C. Then, a first corrosion prevention layer and a second corrosion prevention layer having a thickness of 0.2 μm were formed on both sides. As the corrosion inhibitor, a mixture of chromium fluoride, phosphoric acid and polyvinyl alcohol was used.
Next, a second adhesive was applied on the formed second corrosion prevention layer to form a second adhesive layer having a thickness of 3 μm. The 2nd adhesive agent used what knead | mixed 5 weight part of epoxy resins with the maleic acid modified polypropylene.
The second adhesive layer in the laminate including the metal foil and the sealant layer made of a polypropylene resin (block PP) film having a thickness of 20 μm were laminated by dry lamination.
Then, after applying the first adhesive at 4.0 g / m ² on the first corrosion prevention layer using a gravure coater, heating in an oven at 80 ° C. for 30 seconds to form the first adhesive layer did. A urethane-based adhesive was used as the first adhesive.
This 1st adhesive bond layer and the colored layer in the laminated body obtained above were made to oppose, and it laminated | stacked by 80 degreeC dry lamination.
Then, after aging treatment at 60 ° C. for 3 days, surface protective layer / matte layer / base material layer (PET resin layer) / colored layer (black printing layer) / first adhesive layer / first corrosion prevention layer / barrier layer A resin-coated metal laminate having a laminated structure of / second corrosion prevention layer / second adhesive layer / sealant layer was obtained.

<Reference Examples 2-3>
A resin-coated metal laminate was obtained in the same manner as in Example 1 except that no colorant component was added to the base film.

In the said Table 1, the addition amount of a coloring agent component is the addition amount (mass part) with respect to 100 mass parts of resin components of a base material layer. In Table 1, each symbol indicates the following material.
・ CB: Carbon black ・ CNT: Carbon nanotube ・ SUS: Stainless steel foil ・ Al: Aluminum steel foil

[Evaluation]
The following evaluation was performed about the resin coating metal laminated body of Examples 1-12, Comparative Examples 1-5, and Reference Examples 1-3.

(Visibility)
・ Hiding property A paper with a black magic pattern on a white background was laid on the sealant layer side of the resin-coated metal laminates of Examples 1 to 12, Comparative Examples 1 to 5, and Reference Examples 1 to 3, and from the surface protective layer side. It was confirmed by visual observation whether the drawn pattern was seen through. Table 2 shows “◯” when the pattern was not seen through and “x” when the pattern was seen.
Coloring missing For the resin-coated metal laminates of Examples 1 to 12, Comparative Examples 1 to 5, and Reference Examples 1 to 3, “x” is printed when there are one or more missing prints in 2000 m, and printing in 2000 m The case where there are no missing pieces is shown in Table 2 as “◯”.

(Physical properties)
Rubbing test A rubbing test was performed using a test apparatus (rubbing tester, manufactured by Taihei Rika Kogyo Co., Ltd.) shown in FIG. The sides 71a are formed by folding the resin-coated metal laminates of Examples 1 to 12, Comparative Examples 1 to 5, and Reference Examples 1 to 3 cut to 7 cm × 12.5 cm with the base layer 13 side facing up. This was used as a test piece. A test piece 71 was placed at the tip of the sliding jig 72 of the test apparatus 70 shown in FIG. At this time, a portion 2.5 cm above the side 71a was gripped. A stainless shaft 73 was attached so as to intersect the side 71 a of the test piece 71. The test piece 71 was pressed against the stainless shaft 73 with a load of 200 g, and the stainless shaft 73 was reciprocated in the extending direction indicated by reference numeral 74. At this time, the reciprocating width L was 10 cm.
As a result, “◎” indicates that the object was not torn even after reciprocating 100 times or more, “◯” indicates that it was not torn even if it was reciprocated 70 times to less than 100 times, and it was not torn even if it was reciprocated 50 times to less than 70 times. Table 2 shows the results as “Δ” and those that were broken less than 50 times as “x”.

・ Puncture strength Measurement of puncture strength: Examples 1 to 12 and Comparative Examples 1 to 5, according to the measurement method defined in JIS Z 1707 “General Rules for Plastic Films for Food Packaging 7.4 Puncture Strength Test” The resin-coated metal laminates of Examples 1 to 3 were evaluated according to the following evaluation items. The results are listed in Table 2.
○: 30N or more ×: Less than 30N

(Appropriate thickness)
About the resin coating metal laminated body of Examples 1-12, Comparative Examples 1-5, and Reference Examples 1-3, thickness appropriateness was evaluated according to the following evaluation item. The results are listed in Table 2.
○: 70 μm or less △: 80 μm or less ×: Thicker than 80 μm

As shown in the above results, Examples 1 to 12 to which the present invention was applied all had good visibility, physical properties, and appropriate thickness. On the other hand, in Comparative Example 1 in which the present invention was not applied, the particle size of the colorant component was too small, so that the concealability was poor. In Comparative Example 2 to which the present invention was not applied, the particle size of the colorant component was too large, so that the strength decreased and the result of the rubbing test was poor. In Comparative Example 3 to which the present invention was not applied, the amount of the colorant component added was too small, so that the hiding property was poor. In Comparative Example 4 to which the present invention was not applied, a dye was used as a colorant, the hiding property was not good, and the result of the rubbing test was also poor. In Comparative Example 5 to which the present invention was not applied, the base material layer and the colorant layer were independent layers, and thus color loss was observed. In Comparative Example 5, wrinkles occurred in the printing process for forming the printing layer.
As in the results of Reference Example 1, when aluminum steel foil was used for the barrier layer, the piercing strength was poor, but the results of visibility and rubbing test were good. In Reference Example 2, the resin layer used as the base material layer was as thick as 12 μm, and the rubbing test result was good. In Reference Example 3, although the thickness of the base resin layer was 6 μm, the result of the rubbing test was poor because it did not contain a colorant component.

DESCRIPTION OF SYMBOLS 10 ... Laminated body (or resin-coated metal laminated body), 11 ... Surface protective layer, 12 ... Matt layer, 13 ... Base material layer, 14 ... 1st adhesive layer, 15 ... 1st corrosion prevention layer, 16 ... Barrier layer 17 ... second corrosion prevention layer, 18 ... second adhesive layer, 19 ... sealant layer, 21 ... battery outer casing, 27 ... lithium ion battery, 28 ... electrode lead, 29 ... peripheral part, 30 ... container body, 31 , 51 ... Recessed part, 32 ... Flange part, 33 ... Lid part, 34 ... Peripheral part, 40, 60 ... Secondary battery

Claims (9)

At least a resin-coated metal laminate comprising a base material layer and a barrier layer in this order,
The base material layer contains a resin component and a colorant component,
The colorant component is contained in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin component,
The resin-coated metal laminate, wherein the colorant component has a particle size of 10 nm or more and 100 nm or less. At least a resin-coated metal laminate comprising a base material layer, a barrier layer and a sealant layer in this order,
The surface of the resin-coated metal laminate is formed by folding the surface of the base material layer face-up and forming a side, and the rubbing resistance when a rubbing test is performed on a smooth stainless steel shaft under the following conditions is 50 reciprocations or more. The resin-coated metal laminate according to claim 1.
(conditions)
-Test piece size: 7cm x 12.5cm
・ Testing machine installation conditions: Grasping the part 2.5 cm above the side formed on the test piece ・ Testing conditions: Pressing against a stainless steel shaft at a load of 200 g under room temperature, reciprocating in the extending direction with a reciprocating width of 10 cm   The resin-coated metal laminate according to claim 1 or 2, wherein the colorant component is one or both of carbon black and carbon nanotubes.   The resin-coated metal laminate according to claim 1, wherein the barrier layer is made of an alloy foil, and the alloy foil is a stainless steel foil having a thickness of 50 μm or less.   The resin-coated metal laminate according to any one of claims 1 to 4, wherein the base material layer is polyethylene terephthalate, polyamide, or polyimide having a thickness of 6 µm or more.   The resin-coated metal laminate according to claim 1, further comprising a mat layer on the base material layer.   The resin-coated metal laminate according to claim 6, wherein the mat layer includes silica particles having a particle diameter of 2 μm or more and 5 μm or less, an acrylic urethane resin, or acrylic beads.   A battery outer package comprising the resin-coated metal laminate according to any one of claims 1 to 7.   A battery comprising the battery outer package according to claim 8.

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