JP7240825B2 - Molded packaging materials and molded cases - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is suitably used, for example, as a case for laptop computers, mobile phones, vehicles, and stationary secondary batteries (lithium-ion secondary batteries), and is also suitable as a packaging material for food and a packaging material for pharmaceuticals. It relates to a molding packaging material and a molding case used for.

In recent years, along with the thinning and weight reduction of mobile electric devices such as smartphones and tablet terminals, the demand for power storage devices such as lithium-ion secondary batteries, lithium-polymer secondary batteries, lithium-ion capacitors, and electric double layer capacitors mounted on these devices has increased. The exterior material consists of a heat-resistant resin layer (base material layer) / outer adhesive layer / metal foil layer / inner adhesive layer / heat-fusible resin layer (inner sealant layer) instead of the conventional metal can. A laminate is used (see Patent Document 1). In addition, power sources for electric vehicles, large power sources for power storage, capacitors, and the like are also increasingly being sheathed with the above-described laminated body (exterior material). By subjecting the exterior material to stretch molding or deep drawing, the exterior material is molded into a three-dimensional shape such as a substantially rectangular parallelepiped shape. By molding into such a three-dimensional shape, it is possible to secure a housing space for housing the electricity storage device main body.

In order to protect the exterior material and improve moldability, an exterior material is known in which a matte coat layer is provided on the outer side of the base material layer (see Patent Document 2). The mat coat layer is made of a resin composition containing 0.1% by mass to 1% by mass of inorganic fine particles having an average particle size of 1 μm to 10 μm in a heat-resistant resin. By providing such a matte coat layer, good lubricity is imparted to the surface, and moldability can be improved.

JP 2003-288865 A JP 2013-224014 A

By the way, on the surface of the matte coat layer (protective layer), which is the outer surface of the exterior material, the surface of the exterior material is coated so as to prevent appearance defects such as scratches on the surface of the exterior material during the manufacturing process of the battery. A protective tape is attached to the surface (the surface of the matte coat layer). However, in some cases, the matte coat layer was peeled off when the protective tape was peeled off after manufacturing the battery.

In addition, on the surface of the matte coat layer, which is the outer surface of the exterior material, printing such as the manufacturer's name, model number, capacity, lot number, bar code, CR code, etc. is printed, but this printing may be corrected. At this time, the print is wiped off with a cloth impregnated with ethanol or MEK (methyl ethyl ketone). At that time, there is also a problem that the mat coat layer (protective layer) is easily peeled off from the substrate layer (outer layer).

The present invention has been made in view of this technical background, and can prevent the protective layer from peeling from the heat-resistant resin stretched film layer, including when the protective tape is peeled off. It is an object of the present invention to provide a molding packaging material and a molding case which are excellent in both.

In order to achieve the above object, the present invention provides the following means.

[1] A molding packaging material comprising a heat-resistant resin stretched film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer disposed between these layers,
A packaging material for molding, wherein a protective layer is laminated and integrated on the outer surface of the outer layer via an easy-adhesion layer.

[2] The easy-adhesion layer contains one or more resins selected from the group consisting of epoxy resins, urethane resins, acrylic acid ester resins, methacrylic acid ester resins, and polyethyleneimine resins. The molding packaging material described in .

[3] The packaging material for molding according to the above item 1, wherein the easy-adhesion layer contains a urethane resin and an epoxy resin.

[4] The molding packaging material according to [3] above, wherein the urethane resin/epoxy resin content ratio in the easily adhesive layer is in the range of 98/2 to 40/60.

[5] The molding according to the preceding item 1, wherein the easy adhesion layer contains one or more acrylic resins selected from the group consisting of acrylic acid ester resins and methacrylic acid ester resins, and an epoxy resin. packaging material.

[6] The molding packaging material according to [5] above, wherein the acrylic resin/epoxy resin content ratio in the easily adhesive layer is in the range of 98/2 to 40/60.

[7] The molding packaging material according to any one of the preceding items 1 to 6, wherein the easy adhesion layer is an adhesion layer formed by applying a resin-water emulsion to the heat-resistant resin stretched film layer.

[8] The molding packaging material according to any one of the preceding items 1 to 7, wherein the protective layer is a layer made of a resin composition in which inorganic fine particles and/or organic fine particles are dispersed in a heat-resistant resin.

[9] A molded case comprising a deep-drawn molded product or stretch-molded product of the packaging material for molding according to any one of 1 to 8 above.

In the invention [1], since the protective layer is laminated and integrated on the outer surface of the heat-resistant resin stretched film layer via the easy-adhesion layer, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is improved, and the protective layer is protected. It is possible to sufficiently prevent the peeling of the protective layer from the heat-resistant resin stretched film layer, including when the tape is peeled off, and to improve the organic solvent resistance.

In the invention [2], the easy-adhesion layer contains one or more resins selected from the group consisting of epoxy resins, urethane resins, acrylic acid ester resins, methacrylic acid ester resins, and polyethyleneimine resins. With this structure, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is improved, and the peeling of the protective layer from the heat-resistant resin stretched film layer can be sufficiently prevented, including when the protective tape is peeled off. , the organic solvent resistance can be improved.

In the invention [3], since the easy-adhesion layer contains a urethane resin and an epoxy resin, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, and the heat-resistant resin stretched film layer It is possible to more sufficiently prevent the protective layer from being peeled off, and to further improve the organic solvent resistance.

In the invention [4], since the content mass ratio of the urethane resin/epoxy resin is in the range of 98/2 to 40/60, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, and the heat-resistant resin It is possible to more sufficiently prevent the protective layer from being peeled off from the stretched film layer, and to further improve the organic solvent resistance.

In the invention [5], since the easy-adhesion layer contains a specific acrylic resin and an epoxy resin, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, and the heat-resistant resin stretched While being able to prevent peeling of a protective layer from a film layer more fully, an organic-solvent resistance can be improved more.

In the invention [6], since the content mass ratio of the acrylic resin/epoxy resin is in the range of 98/2 to 40/60, the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is further improved, and the heat-resistant resin It is possible to more sufficiently prevent the protective layer from being peeled off from the stretched film layer, and to further improve the organic solvent resistance.

In the invention [7], the easy-adhesion layer is an adhesive layer formed by applying a resin-water-based emulsion to the heat-resistant resin stretched film layer in advance, so that the adhesive strength between the heat-resistant resin stretched film layer and the protective layer is can be sufficiently prevented from peeling of the protective layer from the heat-resistant resin stretched film layer, and the organic solvent resistance can be improved.

In the invention [8], the protective layer is composed of a resin composition in which inorganic fine particles and/or organic fine particles are dispersed in a heat-resistant resin. We can improve further.

In the invention [9], the protective layer does not peel off from the stretched heat-resistant resin film layer, including when the protective tape is peeled off, and a molded case excellent in organic solvent resistance can be provided.

1 is a cross-sectional view showing an embodiment of a moldable packaging material according to the present invention; FIG. 1 is a cross-sectional view showing an embodiment of an electricity storage device according to the present invention; FIG. FIG. 3 is a perspective view showing an exterior material (planar one), an electricity storage device body, and a molded case (three-dimensional molded body) constituting the electricity storage device of FIG. 2 in a separated state before being heat-sealed.

An embodiment of a moldable packaging material 1 according to the present invention is shown in FIG. This molding packaging material 1 is used as a packaging material for a lithium ion secondary battery case. That is, the molding packaging material 1 is subjected to molding such as deep drawing and used as a secondary battery case.

In the molding packaging material 1, a heat-resistant resin stretched film layer (outer layer) 2 is laminated and integrated on one side of a metal foil layer 4 via a first adhesive layer 5, and the metal foil layer 4 The thermoplastic resin layer (inner layer) 3 is laminated and integrated on the other surface of the second adhesive layer 6 via the second adhesive layer 6 . Furthermore, a protective layer 20 is laminated and integrated on the outer surface of the stretched heat-resistant resin film layer 2 (the surface opposite to the metal foil layer) via a first easy-adhesion layer 11 (see FIG. 1). .

In this embodiment, the first easy-adhesion layer 11 is laminated on the outer surface of the heat-resistant resin stretched film layer 2 by a gravure coating method.

Further, in the present embodiment, the second easy-adhesion layer 12 is laminated on the lower surface of the heat-resistant resin stretched film layer 2 (the surface on the metal foil layer side), and the lower surface of the second easy-adhesion layer 12 (the metal foil layer side surface). A colored ink layer 13 is laminated on the foil layer side surface), and the colored ink layer 13 and the metal foil layer 4 are bonded and integrated via a first adhesive layer 5 (see FIG. 1). That is, a colored ink layer 13 is arranged between the metal foil layer 4 and the heat-resistant resin stretched film layer 2 . In this embodiment, the second easy-adhesion layer 12 is laminated on the lower surface of the heat-resistant resin stretched film layer 2 by a gravure coating method, and the colored ink layer 13 is laminated on the lower surface of the second easy-adhesion layer 12 by printing. ing.

In the present invention, the protective layer (mat coat layer) 20 is a layer made of a resin composition in which inorganic fine particles and/or organic fine particles are dispersed in a heat-resistant resin. The heat-resistant resin is preferably a two-component curing type heat-resistant resin. The content of at least one fine particle selected from the group consisting of inorganic fine particles and organic fine particles in the resin composition is preferably 0.1% by mass to 60% by mass. Also, the average particle size of the inorganic fine particles and the organic fine particles is preferably 0.5 μm to 10 μm. Examples of the heat-resistant resin that constitutes the protective layer 20 include acrylic resins, epoxy resins, urethane resins, polyolefin resins, fluorine resins, phenoxy resins, etc. Among them, urethane resins are preferable. be. By providing such a protective layer 20, good lubricity is imparted to the surface, and the moldable packaging material 1 with excellent moldability can be obtained. The thickness of the protective layer 20 is preferably set to 0.1 μm to 10 μm.

Examples of the inorganic fine particles include, but are not limited to, silica, alumina, calcium oxide, calcium carbonate, calcium sulfate, calcium silicate, etc. Among them, silica is preferred. Examples of the organic fine particles include, but are not limited to, acrylic resin beads, styrene resin beads, urethane resin beads, etc. Among them, acrylic resin beads and urethane resin beads are preferably used. Also, a lubricant may be added to the protective layer 20 . Examples of the lubricant include, but are not limited to, fatty acid amides (erucic acid amide, behenic acid amide, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide, etc.), waxes (polyethylene wax, poly tetrafluoroethylene (PTFE) wax, etc.).

The method for forming the protective layer 20 is not particularly limited. method, reverse roll coating method, lip roll coating method, and the like.

The heat-resistant resin stretched film layer (outer layer) 2 is a member that mainly plays the role of ensuring good moldability as a packaging material, that is, plays the role of preventing breakage due to necking of the metal foil during molding. is. As the heat-resistant resin constituting the stretched heat-resistant resin film layer 2, a heat-resistant resin that does not melt at the heat-sealing temperature at which the molding packaging material 1 is heat-sealed is used. As the heat-resistant resin, it is preferable to use a heat-resistant resin having a melting point higher than the melting point of the resin constituting the thermoplastic resin layer 3 by 10°C or more, and 20°C or more than the melting point of the resin constituting the thermoplastic resin layer 3. It is particularly preferred to use heat-resistant resins with high melting points.

In the present invention, the heat-resistant resin stretched film layer 2 is preferably composed of a heat-resistant resin stretched film having a hot water shrinkage of 2% to 20%. When the hot water shrinkage rate is 2% or more, it is possible to sufficiently prevent the protective layer from peeling off from the heat-resistant resin stretched film layer, and when the hot water shrinkage rate is 20% or less, deep drawing molding or It is possible to sufficiently prevent the peeling of the protective layer from the heat-resistant resin stretched film layer when molding such as stretch molding is performed. Among them, it is preferable to use a heat-resistant resin stretched film having a hot water shrinkage of 2.5 to 10% as the heat-resistant resin stretched film. Furthermore, it is more preferable to use a heat-resistant resin stretched film having a hot water shrinkage of 3.0% to 6.0%, and more preferably a heat-resistant resin stretched film having a hot water shrinkage of 3.5% to 5.0%. It is particularly preferred to use films.

The above-mentioned "hot water shrinkage ratio" refers to the dimension in the stretching direction of the test piece before and after immersion in hot water at 95°C for 30 minutes when the test piece (10 cm x 10 cm) of the heat-resistant resin stretched film 2 is immersed. It is the rate of change and is obtained by the following formula.

Hot water shrinkage (%) = {(XY)/X} x 100
X: Dimension in the stretching direction before immersion treatment Y: Dimension in the stretching direction after immersion treatment.

The hot water shrinkage rate in the case of adopting a biaxially stretched film is the average value of the dimensional change rates in the two stretching directions.

The hot water shrinkage of the heat-resistant resin stretched film can be controlled, for example, by adjusting the heat setting temperature during stretching.

The heat-resistant resin stretched film layer (outer layer) 2 is not particularly limited, but examples thereof include stretched polyamide films such as stretched nylon films, stretched polyester films, and the like. Among them, as the heat-resistant resin stretched film layer 2, a biaxially stretched polyamide film such as a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film, or a biaxially stretched It is particularly preferred to use polyethylene naphthalate (PEN) films. As the heat-resistant resin stretched film layer 2, it is preferable to use a heat-resistant resin biaxially stretched film stretched by a simultaneous biaxial stretching method. In addition, a heat-resistant resin biaxially stretched film having a ratio (MD/TD) of "hot water shrinkage in the M direction" to "hot water shrinkage in the T direction" in the range of 0.9 to 1.1 is used. is preferred. When the ratio (MD/TD) is in the range of 0.9 to 1.1, a moldable packaging material having particularly good moldability can be obtained. The "M direction" means the "machine flow direction", and the "T direction" means the "direction perpendicular to the M direction". Examples of the nylon include, but are not particularly limited to, 6 nylon, 6,6 nylon, MXD nylon, and the like. The heat-resistant resin stretched film layer 2 may be formed of a single layer (single stretched film), or may be a multilayer (stretched PET film/stretched film) made of, for example, a stretched polyester film/stretched polyamide film. It may be formed of a multilayered film made of a nylon film, etc.).

Among them, as the heat-resistant resin stretched film layer 2, a biaxially stretched polyamide film with a shrinkage rate of 2 to 20%, a biaxially stretched polyethylene naphthalate (PEN) film with a shrinkage rate of 2 to 20%, or a shrinkage rate of 2 to A 20% biaxially oriented polyethylene terephthalate (PET) film is preferably used. In this case, the effect of preventing peeling of the protective layer 20 from the heat-resistant resin stretched film layer 2, including when peeling the protective tape from the protective layer 20, can be further enhanced.

The thickness of the heat-resistant resin stretched film layer 2 is preferably 6 μm to 50 μm. When using a polyester film, the thickness is preferably between 9 μm and 50 μm, and when using a nylon film, the thickness is preferably between 12 μm and 50 μm. Sufficient strength as a packaging material can be ensured by setting it to the preferred lower limit value or more, and by setting it to the preferred upper limit value or less, the stress during stretch molding and draw forming can be reduced to improve formability. can be done.

In the present invention, it is necessary to laminate the first easy-adhesion layer 11 on the outer surface of the stretched heat-resistant resin film layer 2 (the surface opposite to the metal foil layer). That is, the protective layer 20 is laminated integrally with the first easy-adhesion layer 11 on the outer surface of the stretched heat-resistant resin film layer 2 (see FIG. 1). The surface of the heat-resistant resin stretched film layer 2, which originally has poor adhesiveness, is coated with a polar resin or the like having excellent adhesiveness and adhesiveness, and the first easy-adhesion layer 11 is laminated to improve adhesion with the protective layer 20, Adhesion can be improved. The outer surface of the heat-resistant resin stretched film layer 2 (the surface on which the first easy-adhesion layer 11 is laminated) is previously subjected to a corona treatment or the like to increase the wettability before the first easy-adhesion layer 11 is laminated. It is preferable to leave

In addition, in the present invention, the inner surface (surface on the metal foil layer side) of the heat-resistant resin stretched film layer 2 is subjected to corona treatment, or the inner surface (surface on the metal foil layer side) is provided with an easy adhesion layer (second easy adhesion layer). Adhesive layer) 12 is preferably laminated. When laminating the easy-adhesion layer (second easy-adhesion layer) 12, the surface of the heat-resistant resin stretched film layer 2, which originally has poor adhesiveness, is coated with a polar resin or the like having excellent adhesiveness and adhesiveness to form a second layer. By laminating the easy-adhesion layer 12, it is possible to improve adhesion and adhesiveness with the colored ink layer 13. FIG. The inner surface of the heat-resistant resin stretched film layer 2 (the surface on which the second easy-adhesion layer 12 is laminated) is previously subjected to a corona treatment or the like to increase the wettability before the second easy-adhesion layer 12 is laminated. It is preferable to leave

The method for forming the first easy-adhesion layer 11 and the second easy-adhesion layer 12 is not particularly limited. The easy adhesion layers 11 and 12 can be formed by applying and drying an aqueous emulsion (aqueous emulsion) of one or more resins selected from the group consisting of acid ester resins and polyethyleneimine resins. Examples of the coating method include, but are not limited to, a spray coating method, a gravure roll coating method, a reverse roll coating method, a lip coating method, and the like.

Thus, the first easy-adhesion layer 11 and the second easy-adhesion layer 12 are each selected from the group consisting of epoxy resin, urethane resin, acrylic acid ester resin, methacrylic acid ester resin, and polyethyleneimine resin. Alternatively, it is preferable to have a configuration containing two or more kinds of resins. When the preferred configuration is adopted in the first easy-adhesion layer 11 , peeling of the protective layer 20 from the stretched heat-resistant resin film layer 2 can be prevented more sufficiently. In addition, when the preferred configuration is adopted in the second easy-adhesion layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved.

Among them, the first easy-adhesion layer 11 and the second easy-adhesion layer 12 are configured to contain a urethane resin and an epoxy resin, or contain a (meth)acrylic acid ester resin and an epoxy resin, respectively. A configuration is particularly preferred. When the particularly preferable configuration is adopted for the first easy-adhesion layer 11 , it is possible to more sufficiently prevent the protective layer 20 from peeling off from the heat-resistant resin stretched film layer 2 . Further, when the particularly preferable configuration is adopted in the second easy-adhesion layer 12, the adhesion between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved.

In the case of adopting the former configuration, the mass ratio of urethane resin/epoxy resin content in the first and second easy adhesion layers 11 and 12 is preferably in the range of 98/2 to 40/60. When such a content mass ratio (range) is adopted in the first easy adhesion layer 11, it is possible to further sufficiently prevent the protective layer 20 from peeling from the heat-resistant resin stretched film layer 2, and When such a content mass ratio (range) is adopted in the adhesive layer 12, the adhesive strength between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved. If the urethane resin content ratio is higher than the urethane resin/epoxy resin content mass ratio (98/2), the degree of cross-linking will be insufficient, making it difficult to obtain sufficient solvent resistance and adhesive strength, which is not preferred. . On the other hand, when the content ratio of the urethane resin is smaller than the content ratio of the urethane resin/epoxy resin (40/60), it takes too long to complete the cross-linking, which is not preferable. Above all, it is more preferable that the content mass ratio of urethane resin/epoxy resin in the first and second easy adhesion layers 11 and 12 is in the range of 90/10 to 50/50.

In the case of adopting the latter configuration, the content mass ratio of (meth)acrylic acid ester resin/epoxy resin in the first and second easy adhesion layers 11 and 12 is in the range of 98/2 to 40/60. is preferred. When such a content mass ratio (range) is adopted in the first easy adhesion layer 11, it is possible to further sufficiently prevent the protective layer 20 from peeling from the heat-resistant resin stretched film layer 2, and When such a content mass ratio (range) is adopted in the adhesive layer 12, the adhesive strength between the heat-resistant resin stretched film layer 2 and the colored ink layer 13 can be further improved. When the content ratio of the (meth)acrylic acid ester resin is larger than the content ratio (98/2) of the (meth)acrylic acid ester resin/epoxy resin by mass, the degree of cross-linking becomes insufficient, and the solvent resistance and adhesive strength deteriorate. Since it becomes difficult to obtain enough, it is not preferable. On the other hand, when the content ratio of the (meth)acrylic acid ester resin is smaller than the content ratio (40/60) of the (meth)acrylic acid ester resin/epoxy resin, it takes too much time to complete the cross-linking. I don't like it. Above all, it is more preferable that the mass ratio of (meth)acrylic acid ester resin/epoxy resin content in the first and second easy adhesion layers 11 and 12 is in the range of 90/10 to 50/50.

Surfactants such as glycols and ethylene oxide adducts of glycols are added to the aqueous resin emulsion (resin-water emulsion) for forming the first easy adhesion layer 11 and the second easy adhesion layer 12. In this case, a sufficient defoaming effect can be obtained in the aqueous resin emulsion, so that the first easy-adhesion layer 11 and the second easy-adhesion layer 12 having excellent surface smoothness can be formed. The surfactant is preferably contained in the aqueous resin emulsion in an amount of 0.01% by mass to 2.0% by mass.

In addition, the resin-based emulsion (resin-water-based emulsion) for forming the first easy-adhesion layer 11 and the second easy-adhesion layer 12 preferably contains inorganic fine particles such as silica and colloidal silica. In some cases, an anti-blocking effect can be obtained. The inorganic fine particles are preferably added in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the resin.

It is preferable that the amount of formation of the first easy-adhesion layer 11 and the second easy-adhesion layer 12 (solid content after drying) is in the range of 0.01 g/m ² to 0.5 g/m ² . When it is 0.01 g/m ² or more, the heat-resistant resin stretched film layer 2 and the protective layer 20 can be sufficiently bonded to each other for the first easy-adhesion layer 11, and the heat-resistant resin for the second easy-adhesion layer 12. The stretched film layer 2 and the colored ink layer 13 can be sufficiently adhered. In addition, since it is 0.5 g/m ² or less, the cost can be reduced and it is economical.

The resin content (content after drying) in the first easy-adhesion layer 11 and the second easy-adhesion layer 12 is preferably 88% by mass to 99.9% by mass.

The thermoplastic resin layer (inner layer) 3 provides excellent chemical resistance to highly corrosive electrolytes used in lithium ion secondary batteries and the like, and provides heat sealability to packaging materials. It has a role to play.

Although the thermoplastic resin layer 3 is not particularly limited, it is preferably an unstretched thermoplastic resin film layer. The thermoplastic resin unstretched film layer 3 is not particularly limited, but at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, olefinic copolymers, acid-modified products thereof, and ionomers. It is preferably composed of an unstretched film made of resin. Among them, a three-layer laminate structure in which coating layers containing random polypropylene are laminated on both sides of an intermediate layer containing block polypropylene is more preferable. The thermoplastic resin layer 3 may be a single layer or multiple layers.

The thickness of the thermoplastic resin layer 3 is preferably set to 20 μm to 80 μm. By setting the thickness to 20 μm or more, it is possible to sufficiently prevent the occurrence of pinholes, and by setting the thickness to 80 μm or less, it is possible to reduce the amount of resin used, thereby reducing costs. Above all, it is particularly preferable to set the thickness of the thermoplastic resin layer 3 to 30 μm to 50 μm.

The metal foil layer 4 plays a role of imparting a gas barrier property to the molding packaging material 1 to prevent permeation of oxygen and moisture. Examples of the metal foil layer 4 include, but are not limited to, aluminum foil, copper foil, nickel foil, stainless steel foil, etc. Aluminum foil is generally used. As the aluminum foil, A8079 and A8021 defined in JIS H4160 are preferable. The thickness of the metal foil layer 4 is preferably 20 μm to 100 μm. When the thickness is 20 μm or more, it is possible to prevent the occurrence of pinholes during rolling when manufacturing the metal foil, and when it is 100 μm or less, the stress during stretch forming or draw forming can be reduced, and formability can be improved. can.

Preferably, at least the inner surface 4a (surface on the inner layer 3 side) of the metal foil layer 4 is subjected to a chemical conversion treatment. Such chemical conversion treatment can sufficiently prevent corrosion of the metal foil surface due to contents (eg, battery electrolyte, food, pharmaceuticals, etc.). For example, the metal foil is chemically treated by the following treatment. That is, for example, on the surface of a metal foil that has been degreased,
1) Aqueous solution consisting of a mixture of metal salts of phosphoric acid, chromic acid and fluoride 2) Aqueous solution consisting of a mixture of phosphoric acid, chromic acid, fluoride metal salts and non-metal salts 3) Acrylic resin and/or phenolic resin or an aqueous solution consisting of a mixture of phosphoric acid, chromic acid and fluoride metal salt is applied and then dried to perform chemical conversion treatment.

In the present invention, a colored ink layer 13 may be provided between the heat-resistant resin stretched film layer (outer layer) 2 and the metal foil layer 4 (see FIG. 1). By providing such a colored ink layer 13, a color (including an achromatic color) can be imparted to the outer surface side (protective layer 20 side) of the molding packaging material 1.

The colored ink layer 13 is not particularly limited, but includes, for example, a black ink layer, a white ink layer, a gray ink layer, a red ink layer, a blue ink layer, a green ink layer, a yellow ink layer, and the like. .

The black ink layer 13 will be described. The black ink layer 10 is usually made of a composition containing carbon black.

Above all, the black ink layer 13 preferably has a structure containing carbon black, diamine, polyol and a curing agent, but is not particularly limited to such a structure.

In the black ink layer (ink layer after drying) 13, the carbon black content is 15% by mass to 60% by mass, and the total content of the diamine, polyol and curing agent is 40% by mass to 85% by mass. is preferred. Among them, it is particularly preferable that the content of carbon black is 20% by mass to 50% by mass.

If the content of carbon black is less than 15% by mass, the metallic luster of the metal foil layer 4 remains, impairing the solid feeling, and partial color unevenness occurs during molding, which is not preferable. On the other hand, when the content of carbon black exceeds 60% by mass, the black ink layer 13 becomes hard and brittle, so that the adhesive force to the metal foil layer 4 is reduced, and the metal foil layer 4 and the black ink layer 13 are separated from each other during molding. It is not preferable because peeling tends to occur between

The black ink layer 13 preferably contains 2 to 20 parts by mass of the curing agent per 100 parts by mass of the total amount of the carbon black, the diamine and the polyol. If the curing agent is less than 2 parts by mass, the metal foil layer 4 and the black ink layer 13 are likely to separate during molding. Blocking occurs when unwinding (unwinding), and problems such as transfer and adhesion to the outer surfaces of the protective layer 20 and the thermoplastic resin layer 3 occur, which is not preferable.

It is preferable to use carbon black having an average particle diameter of 0.2 μm to 5 μm.

Examples of the diamine include, but are not limited to, ethylenediamine, dimerdiamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, dicyclohexylmethanediamine, 2-hydroxyethylpropylenediamine, and the like. Among them, it is preferable to use one or more diamines selected from the group consisting of ethylenediamine, dimerdiamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine and dicyclohexylmethanediamine as the diamine.

The diamine has a faster reaction rate with a curing agent (isocyanate, etc.) than a polyol, and can be cured in a short time. That is, the diamine reacts with the curing agent together with the polyol to accelerate cross-linking curing of the ink composition.

Although the polyol is not particularly limited, it is preferable to use one or more polyols selected from the group consisting of polyurethane-based polyols, polyester-based polyols and polyether-based polyols.

The number average molecular weight of the polyol is preferably in the range of 1000-8000. When it is 1000 or more, the adhesive strength after curing can be increased, and when it is 8000 or less, the reaction rate with the curing agent can be increased.

Examples of the curing agent include, but are not limited to, isocyanate compounds. As the isocyanate compound, for example, various aromatic, aliphatic, and alicyclic isocyanate compounds can be used. Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate, xylylene diisocyanate, and polymers of these exemplified isocyanates (adduct with polyhydric alcohol, isocyanurate, burette body, etc.).

The colored ink layer (excluding the black ink layer) will be described. The colored ink layer (excluding the black ink layer) 13 contains a two-component curable polyester urethane resin binder composed of a polyester resin as a main agent and a polyfunctional isocyanate compound as a curing agent, and a coloring pigment containing an inorganic pigment. It is preferably composed of a cured film of a colored ink composition.

As the color pigment, a configuration containing at least an inorganic pigment is adopted. Examples of the coloring pigment include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, etc., in addition to the inorganic pigments. Examples of the inorganic pigment include, but are not limited to, carbon black, calcium carbonate, titanium oxide, zinc oxide, iron oxide, and aluminum powder. As the inorganic pigment, those having an average particle size of 0.1 μm to 5 μm are preferably used, and those having an average particle size of 0.5 μm to 2.5 μm are particularly preferably used. When dispersing the color pigment, it is preferable to disperse the color pigment using a pigment disperser. When dispersing the color pigment, a pigment dispersant such as a surfactant may be used.

It is preferable that 50 mass % or more of the color pigment is composed of the inorganic pigment. In this case, the colored ink layer 13 having a specific color tone can be formed, which can sufficiently provide the hiding power to hide the metal foil layer 4 and sufficiently impart a feeling of dignity and luxury. Among them, it is more preferable that 60% by mass or more of the coloring pigment is composed of the inorganic pigment.

The thickness (after drying) of the colored ink layer 13 is preferably 1 μm to 4 μm. When the thickness is 1 μm or more, the color tone of the colored ink layer 10 does not remain transparent, and the color and luster of the metal foil layer 4 can be sufficiently hidden. Further, when the thickness is 4 μm or less, it is possible to sufficiently prevent the colored ink layer 10 from being partially cracked during molding.

Although the colored ink layer 13 is not particularly limited, for example,
1) an ink composition containing carbon black, a diamine, a polyol, a curing agent and an organic solvent; A colored ink composition containing a colored pigment containing a pigment is printed (applied) on the surface of the second easy adhesion layer 12 on the lower surface of the heat-resistant resin stretched film layer 2 by a gravure printing method or the like. be able to. Examples of the organic solvent include, but are not limited to, toluene, methyl ethyl ketone, ethyl acetate, and normal propyl acetate.

A method for forming the colored ink layer 13 is not particularly limited, but examples thereof include a gravure printing method, a reverse roll coating method, a lip roll coating method, and the like.

Examples of the first adhesive layer 5 include, but are not limited to, an adhesive layer formed of a two-liquid reactive adhesive. As the two-liquid reactive adhesive, for example, a first liquid consisting of one or more polyols selected from the group consisting of polyurethane-based polyols, polyester-based polyols and polyether-based polyols, and a second liquid consisting of isocyanate A two-liquid reactive adhesive composed of a liquid (curing agent) and the like can be used. In the first adhesive layer 5, for example, an adhesive such as the two-liquid reactive adhesive is applied to the "upper surface of the metal foil layer 4" and/or "the lower surface of the heat-resistant resin layer 2." It is formed by coating the lower surface of the colored ink layer 13 laminated via the 2 easy adhesion layer 12 by a method such as a gravure coating method.

Examples of the second adhesive layer 6 include, but are not limited to, polyurethane adhesives, acrylic adhesives, epoxy adhesives, polyolefin adhesives, elastomer adhesives, and fluorine adhesives. and the like. Among them, it is preferable to use an acrylic adhesive or a polyolefin adhesive. In this case, the electrolytic solution resistance and the water vapor barrier property of the molding packaging material 1 can be improved.

A molded case (battery case, etc.) 10 can be obtained by molding (deep drawing, stretch molding, etc.) the molding packaging material 1 of the present invention described above (see FIG. 3). The exterior material 1 of the present invention can be used as it is without being subjected to molding (see FIG. 3).

FIG. 2 shows an embodiment of an electricity storage device 30 constructed using the molding packaging material 1 of the present invention. This power storage device 30 is a lithium ion secondary battery. In the present embodiment, as shown in FIGS. 2 and 3, an exterior member 15 is composed of a molded case 10 obtained by molding the molding packaging material 1 and the planar packaging material 1 . Thus, a substantially rectangular parallelepiped electricity storage device main body (electrochemical element or the like) 31 is accommodated in the accommodation recess of the molded case 10 obtained by molding the molding packaging material 1 of the present invention. The packaging material 1 of the present invention is placed on the portion 31 without being molded, with the heat-fusible resin layer 3 side facing inward (lower side). The peripheral portion of the resin layer 3 and the heat-fusible resin layer 3 of the flange portion (sealing peripheral portion) 29 of the molding case 10 are heat-sealed and sealed, thereby forming the structure of the present invention. A power storage device 30 is configured (see FIGS. 2 and 3). The inner surface of the housing recess of the molded case 10 is the heat-sealable resin layer 3, and the outer surface of the housing recess is the protective layer 20 (see FIG. 3).

In FIG. 2, reference numeral 39 denotes a heat-sealed portion where the peripheral portion of the packaging material 1 and the flange portion (sealing peripheral portion) 29 of the molded case 10 are joined (welded). In addition, in the electricity storage device 30, the tip of the tab lead connected to the electricity storage device main body 31 is led out to the outside of the exterior member 15, but the illustration is omitted.

The electricity storage device main body 31 is not particularly limited, but examples thereof include a battery main body, a capacitor main body, and a capacitor main body.

In the above-described embodiment, the exterior member 15 is composed of the molded case 10 obtained by molding the molding packaging material 1 and the planar packaging material 1 (see FIGS. 2 and 3). ), it is not particularly limited to such a combination.

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Adhesive for forming first and second easy-adhesion layers>
(Adhesive composition W)
70 parts by mass of "Takelac W-6010" manufactured by Mitsui Chemicals, Inc. as a water-based urethane resin, 30 parts by mass of "Denacol EX-521" manufactured by Nagase Chemtech Co., Ltd. as a water-based epoxy resin, and Nissan Chemical Industries, Ltd. as an anti-blocking agent 5 parts by mass of colloidal silica "Snowtex ST-C" (average particle size 10 nm to 20 nm) is mixed, and ion-exchanged water is added to dilute to obtain an adhesive composition W having a nonvolatile content of 2% by mass. Obtained.
(Adhesive composition V)
Chuo Rika Kogyo Co., Ltd. "Licabond SA-513" 70 parts by weight as a water-based acrylic acid ester resin, Nagase Chemtech Co., Ltd. "Denacol EX-521" 30 parts by weight as a water-based epoxy resin, Nissan Chemical Industry Co., Ltd. as an antiblocking agent Adhesive composition with a non-volatile content of 2% by mass by mixing 5 parts by mass of colloidal silica "Snowtex ST-C" (average particle size 10 nm to 20 nm) manufactured by the company and further adding ion-exchanged water to dilute. I got the thing V.
(Adhesive composition Z)
100 parts by mass of “Denacol EX-521” manufactured by Nagase Chemtech Co., Ltd. as a water-based epoxy resin, and 5 masses of colloidal silica “Snowtex ST-C” manufactured by Nissan Chemical Industries, Ltd. (average particle size 10 nm to 20 nm) as an antiblocking agent. The parts were mixed and further diluted with ion-exchanged water to obtain an adhesive composition Z having a non-volatile content of 2% by mass.

<Example 1>
50 parts by mass of carbon black having an average particle size of 0.8 μm, 5 parts by mass of ethylenediamine, and 45 parts by mass of polyester polyol (number average molecular weight: 2500) were blended to obtain a main component. An ink composition was obtained by blending 3 parts by mass of tolylene diisocyanate (TDI) as a curing agent with 100 parts by mass of the main agent, and further blending 50 parts by mass of toluene, followed by thorough stirring.

Biaxially stretched nylon (6 nylon) film with a thickness of 15 μm and a hot water shrinkage of 4.0% (heat-resistant resin stretched film layer, MD / TD = 0.95) obtained by stretching by simultaneous biaxial stretching ) on one surface (inner surface) of 2, the adhesive composition W is applied by a gravure roll coating method, dried, and then allowed to stand in an environment of 40° C. for one day to allow the curing reaction to proceed, forming A second easy adhesion layer 12 was formed in an amount of 0.1 g/m ² .

Next, after printing (applying) the ink composition on the surface of the second easy adhesion layer 12 of the biaxially oriented nylon film 2 by gravure printing, the ink composition is allowed to stand in an environment of 40° C. for one day. A cross-linking reaction progressed along with drying to form a black ink layer (colored ink layer) 13 having a thickness of 3 μm.

On the other hand, both sides of an aluminum foil 4 having a thickness of 35 μm were coated with a chemical conversion treatment liquid consisting of polyacrylic acid, a trivalent chromium compound, water, and alcohol, and dried at 180° C. to obtain a chromium adhesion amount of 10 mg/m ² . was made to be

Next, the biaxially stretched nylon film 2 is attached to one surface of the chemically treated aluminum foil 4 via a polyester-based polyurethane adhesive 5 on the black ink layer (colored ink layer) 13 side, and then aluminum An unstretched polypropylene film (thermoplastic resin layer) 3 having a thickness of 30 μm is attached to the other surface of the foil 4 via a polyacrylic adhesive 6, and then left in an environment of 40° C. for 5 days to laminate. got a body

Further, the adhesive composition W was applied to the outer surface (non-laminated surface; corona-treated) of the biaxially oriented nylon film 2 of the laminate by a gravure roll coating method, dried, and then placed in an environment of 40°C. The curing reaction was allowed to proceed by leaving for one day, and the first easy adhesion layer 11 was formed in a formation amount of 0.1 g/m ² .

Next, on the surface (outer surface) of the first easy adhesion layer 11, 20 parts by mass of urethane resin, 3 parts by mass of powdered silica having an average particle size of 2 μm, 5 parts by mass of acrylic resin beads having an average particle size of 3 μm, By applying a resin composition consisting of 5 parts by mass of powdery barium sulfate with an average particle size of 1 μm, 1 part by mass of polytetrafluoroethylene (PTFE) wax with an average particle size of 3 μm, and 66 parts by mass of toluene by gravure coating. , a protective layer 20 having a thickness of 2 μm was formed to obtain a molding packaging material 1 shown in FIG.

<Example 2>
Instead of a biaxially stretched 6 nylon film (MD/TD = 0.95) with a thickness of 15 µm and a hot water shrinkage of 4.0%, a 15 µm thick, heat A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1 except that a biaxially oriented 6 nylon film (MD/TD=0.9) having a water shrinkage of 2.5% was used.

<Example 3>
Instead of a biaxially stretched 6 nylon film (MD/TD = 0.95) with a thickness of 15 µm and a hot water shrinkage of 4.0%, a 15 µm thick, heat A biaxially oriented 6 nylon film (MD/TD=1.0) with a water shrinkage of 3.5% is used, and the resin composition forming the protective layer 20 is 20 parts by mass of a polyester resin and a powder having an average particle size of 2 μm. 3 parts by mass of silica, 5 parts by mass of acrylic resin beads with an average particle size of 3 μm, 5 parts by mass of powdered barium sulfate with an average particle size of 1 μm, and 1 part by mass of polytetrafluoroethylene (PTFE) wax with an average particle size of 3 μm. , using a resin composition consisting of 66 parts by mass of toluene, the second easy adhesion layer 12 was not provided (that is, a black ink layer (coloring ink layer ) 13 was laminated) in the same manner as in Example 1 to obtain a molding packaging material 1 shown in FIG.

<Example 4>
Instead of a biaxially stretched 6 nylon film (MD/TD = 0.95) with a thickness of 15 µm and a hot water shrinkage of 4.0%, a 15 µm thick, heat A biaxially oriented 6 nylon film (MD/TD=1.1) with a water shrinkage rate of 5.0% is used. 3 parts by mass of powdered alumina, 5 parts by mass of acrylic resin beads with an average particle size of 3 μm, 5 parts by mass of powdered barium sulfate with an average particle size of 1 μm, and 1 mass of polytetrafluoroethylene (PTFE) wax with an average particle size of 3 μm A molding packaging material 1 shown in FIG.

<Example 5>
Instead of a biaxially stretched 6 nylon film (MD/TD = 0.95) with a thickness of 15 µm and a hot water shrinkage of 4.0%, a 15 µm thick, heat A biaxially stretched polyethylene terephthalate (PET) film (MD/TD=1.1) with a water shrinkage of 2.0% is used, and the resin composition forming the protective layer 20 is 20 parts by mass of a urethane resin and an average particle diameter of 3 parts by mass of powdery calcium carbonate with an average particle size of 2 µm, 5 parts by mass of acrylic resin beads with an average particle size of 3 µm, 5 parts by mass of powdered barium sulfate with an average particle size of 1 µm, and polytetrafluoroethylene with an average particle size of 3 µm ( A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1, except that a resin composition comprising 1 part by mass of PTFE wax and 66 parts by mass of toluene was used.

<Example 6>
Molding shown in FIG. A packaging material 1 was obtained.

<Example 7>
Molding shown in FIG. A packaging material 1 was obtained.

<Example 8>
Instead of a biaxially stretched 6 nylon film (MD/TD = 0.95) with a thickness of 15 µm and a hot water shrinkage of 4.0%, a 15 µm thick, heat A biaxially stretched polyethylene terephthalate (PET) film (MD/TD=1.1) with a water shrinkage of 5.0% is used, and the resin composition forming the protective layer 20 is 20 parts by mass of an epoxy resin, an average particle diameter of 3 parts by mass of powdered silica with an average particle size of 3 µm, 5 parts by mass of acrylic resin beads with an average particle size of 3 µm, 5 parts by mass of powdered barium sulfate with an average particle size of 1 µm, and polytetrafluoroethylene (PTFE) with an average particle size of 3 µm. A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 7 except that a protective layer 20 having a thickness of 3 μm was formed using a resin composition containing 1 part by mass of wax and 66 parts by mass of toluene. rice field.

<Example 9>
15 μm thick, 4.0% hot water shrinkage biaxially stretched nylon 6 film (MD/TD=1.0) instead of 15 μm thick, 3.5% hot water shrinkage biaxially stretched nylon 6 film A film (MD / TD = 0.95) is used, and the outer surface of the biaxially stretched 6 nylon film is not subjected to corona treatment. 3 parts by mass of powdery alumina with an average particle size of 1 µm, 5 parts by mass of acrylic resin beads with an average particle size of 3 µm, 5 parts by mass of powdered barium sulfate with an average particle size of 1 µm, and polytetrafluoroethylene with an average particle size of 3 µm The packaging material for molding shown in FIG. got 1.

<Comparative Example 1>
In the same manner as in Example 2, except that the first easy-adhesion layer 11 was not provided (that is, the protective layer 20 was laminated directly on the outer surface (corona-treated) of the biaxially oriented nylon film 2). Got the packaging.

<Comparative Example 2>
In the same manner as in Example 3, except that the first easy-adhesion layer 11 was not provided (that is, the protective layer 20 was laminated directly on the outer surface (corona-treated) of the biaxially oriented nylon film 2). Got the packaging.

Each packaging material for molding obtained as described above was evaluated based on the following evaluation methods. Table 1 shows the results.

<Solvent resistance evaluation method A (ethanol resistance)>
Using a Gakushin rubbing fastness tester (with an aluminum jig with a load of 200 g) manufactured by Tester Sangyo Co., Ltd., the aluminum jig is wrapped with absorbent cotton and impregnated with ethanol. (the surface of the protective layer 20) was reciprocated 20 times and then the presence or absence and extent of peeling of the protective layer was examined to evaluate the ethanol resistance based on the following criteria.
(criterion)
"◯": No peeling of the protective layer was observed "Δ": Slight peeling of the protective layer was observed but hardly noticeable "X": Clear peeling of the protective layer was observed.

<Solvent resistance evaluation method B (MEK resistance)>
Using a Gakushin rubbing fastness tester (with an aluminum jig with a load of 200 g) manufactured by Tester Sangyo Co., Ltd., an evaluation jig is formed by winding absorbent cotton around the aluminum jig and impregnating it with MEK (methyl ethyl ketone). After reciprocating 20 times on the surface of the packaging material (the surface of the protective layer 20), the peeling of the protective layer and the degree of peeling were examined, and the ethanol resistance was evaluated based on the following criteria.
(criterion)
"◯": No peeling of the protective layer was observed "Δ": Slight peeling of the protective layer was observed but hardly noticeable "X": Clear peeling of the protective layer was observed.

<Tape peeling resistance (resistance to tape peeling) evaluation method>
A piece measuring 10 cm long by 10 cm wide was cut out of the packaging material for molding to obtain a test piece. "Scotch tape #600" (protective tape) manufactured by 3M was attached to the surface of the test piece fixed on the substrate (surface of the protective layer 20) with a roller load of 2 kg, and immediately after that, the protective tape was applied. A "tape peeling test" was repeated 15 times to observe the state of the protective layer by vigorously peeling the protective layer, and the tape peeling resistance was evaluated based on the following criteria.
(criterion)
"◯": No peeling of the protective layer was observed even after repeating the tape peeling test 15 times. "△": No peeling of the protective layer was observed even after repeating the tape peeling test 10 times. , Peeling was observed in the protective layer in the 12th, 13th or 14th tape peeling test. "X": The protective layer was peeled off until the tape peeling test was repeated 10 times.

<Formability evaluation method>
Using a straight mold with no molding depth, the packaging material for molding is subjected to one-stage deep drawing molding under the following molding conditions, and each molding depth (6.0 mm, 5.5 mm, 5.0 mm, 4.5 mm, 4.0 mm, 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm), and the maximum molding depth ( mm), and the moldability was evaluated based on the following criteria. The presence or absence of pinholes was examined by visually observing the presence or absence of transmitted light passing through the pinholes.
(Molding condition)
Mold: Punch: 33.3 mm x 53.9 mm, Die: 80 mm x 120 mm, Corner R: 2 mm, Punch R: 1.3 mm, Die R: 1 mm
Wrinkle pressing pressure: Gauge pressure: 0.475 MPa, actual pressure (calculated value): 0.7 MPa
Material: SC (carbon steel) material, only punch R is chrome plated.
(criterion)
"◎" ... The maximum molding depth that does not cause pinholes and cracks is 5.5 mm or more (accepted)
"○" ... The maximum molding depth at which pinholes and cracks do not occur is 4.5 mm or more and less than 5.5 mm (accepted)
"△" ... The maximum molding depth at which pinholes and cracks do not occur is 3.0 mm or more and less than 4.5 mm (accepted)
"X": The maximum molding depth at which pinholes and cracks do not occur is less than 3.0 mm.

As is clear from Table 1, the molding packaging materials of Examples 1 to 9 of the present invention are excellent in moldability and sufficiently prevent the protective layer from peeling from the heat-resistant resin stretched film layer. At the same time, it was also excellent in organic solvent resistance.

On the other hand, Comparative Examples 1 and 2, in which the first easy-adhesion layer was not provided, were inferior in resistance to tape peeling, and Comparative Example 2 was also inferior in solvent resistance.

The molding packaging material according to the present invention is suitably used as a case for batteries such as laptop computers, mobile phones, vehicles, and stationary lithium ion polymer secondary batteries. Although it is suitable as a packaging material for pharmaceuticals, it is not particularly limited to these uses. Among others, it is particularly suitable for battery cases.

1... Packaging material for molding 2... Heat-resistant resin stretched film layer (outer layer)
3... Thermoplastic resin layer (inner layer)
4... Metal foil layer 10... Forming case 11... First easy adhesion layer 20... Protective layer

Claims (9)

A molding packaging material comprising a heat-resistant resin stretched film layer as an outer layer, a thermoplastic resin layer as an inner layer, and a metal foil layer disposed between these layers,
A protective layer is laminated and integrated on the outer surface of the outer layer via a first easy-adhesion layer,
A second easy-adhesion layer is laminated on the inner surface of the heat-resistant resin stretched film layer between the heat-resistant resin stretched film layer and the metal foil layer, and a colored ink layer is laminated on the inner surface of the second easy-adhesion layer. An adhesive layer is laminated on the inner surface of the ink layer ,
A molding packaging material , wherein the first easy-adhesion layer and the second easy-adhesion layer are made of the same adhesive composition . The first easy-adhesion layer and the second easy-adhesion layer contain one or more resins selected from the group consisting of epoxy resins, urethane resins, acrylate ester resins, methacrylate ester resins, and polyethyleneimine resins. The molding packaging material according to claim 1, comprising: 2. The molding packaging material according to claim 1, wherein said first easy-adhesion layer and said second easy-adhesion layer contain urethane resin and epoxy resin. 4. The molding packaging material according to claim 3, wherein the first easy-adhesion layer and the second easy-adhesion layer have a content mass ratio of the urethane resin/the epoxy resin in the range of 98/2 to 40/60. The first easy-adhesion layer and the second easy-adhesion layer contain one or more acrylic resins selected from the group consisting of acrylic acid ester resins and methacrylic acid ester resins, and an epoxy resin. The molding packaging material according to claim 1. 6. The molding packaging material according to claim 5, wherein the acrylic resin/epoxy resin content ratio in the first easy-adhesion layer and the second easy-adhesion layer is in the range of 98/2 to 40/60. The first easy-adhesion layer and the second easy-adhesion layer according to any one of claims 1 to 6, which are adhesion layers formed by applying a resin-water emulsion to the heat-resistant resin stretched film layer. molding packaging material. The molding packaging material according to any one of claims 1 to 7, wherein the protective layer is a layer made of a resin composition in which inorganic fine particles are dispersed in a heat-resistant resin. A molded case comprising a deep-drawn body or stretch-molded body of the molding packaging material according to any one of claims 1 to 8.

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